Artículos SCI destacados

Osmotic shock in a vesicle or cell is the stress build-up and subsequent rupture of the phospholipid membrane that occurs when a relatively high concentration of salt is unable to cross the membrane and instead an inflow of water alleviates the salt concentration gradient. This is a well-known failure mechanism for cells and vesicles (for example, hypotonic shock) and metal alloys (for example, hydrogen embrittlement). We propose the concept of collective osmotic shock, whereby a coordinated explosive fracture resulting from multiplexing the singular effects of osmotic shock at discrete sites within an ordered material results in regular bicontinuous structures. The concept is demonstrated here using self-assembled block copolymer micelles, yet it is applicable to organized heterogeneous materials where a minority component can be selectively degraded and solvated whilst ensconced in a matrix capable of plastic deformation. We discuss the application of these self-supported, perforated multilayer materials in photonics, nanofiltration and optoelectronics.

2012 | 35.75

Fischer-Tropsch Synthesis (FTS) allows the conversion of syngas to high-density liquid fuels, playing a key role in the petrochemical and global energy sectors over the last century. However, the current Global Challenges impose the need to recycle CO2 2 and foster green fuels, opening new opportunities to adapt traditional processes like FTS to become a key player in future bioenergy scenarios. This review discusses the implementation of CO2- 2- rich streams and in tandem catalysis to produce sustainable fuels via the next generation of FTS. Departing from a brief revision of the past, present, and future of FTS, we analyse a disruptive approach coupling FTS to upstream and downstream processes to illustrate the advantages of process intensification in the context of biofuel production via FTS. We showcase a smart tandem catalyst design strategy addressing the challenges to gather mechanistic insights in sequential transformations of reagents in complex reaction schemes, the precise control of structure-activity parameters, catalysts aging-deactivation, optimization of reaction parameters, as well as reaction engineering aspects such as catalytic bed arrangements and non-conventional reactor configurations to enhance the overall performance. Our review analysis includes technoeconomic elements on synthetic aviation fuels as a case of study for FTS applications in the biofuel context discussing the challenges in market penetration and potential profitability of synthetic biofuels. This comprehensive overview provides a fresh angle of FTS and its enormous potential when combined with CO2 2 upgrading and tandem catalysis to become a front-runner technology in the transition towards a low-carbon future.

2024 | 32.00

The aim of this review article on recent developments of mechanochemistry (nowadays established as a part of chemistry) is to provide a comprehensive overview of advances achieved in the field of atomistic processes, phase transformations, simple and multicomponent nanosystems and peculiarities of mechanochemical reactions. Industrial aspects with successful penetration into fields like materials engineering, heterogeneous catalysis and extractive metallurgy are also reviewed. The hallmarks of mechanochemistry include influencing reactivity of solids by the presence of solid-state defects, interphases and relaxation phenomena, enabling processes to take place under non-equilibrium conditions, creating a well-crystallized core of nanoparticles with disordered near-surface shell regions and performing simple dry time-convenient one-step syntheses. Underlying these hallmarks are technological consequences like preparing new nanomaterials with the desired properties or producing these materials in a reproducible way with high yield and under simple and easy operating conditions. The last but not least hallmark is enabling work under environmentally friendly and essentially waste-free conditions (822 references).

2013 | 30.43

Transition to low carbon societies requires advanced catalysis and reaction engineering to pursue green routes for fuels and chemicals production as well as CO2 conversion. This comprehensive review provides a fresh perspective on the dry reforming of methane reaction (DRM) which constitutes a straightforward approach for effective CO2 conversion to added value syngas. The bottleneck for the implementation of this process at industrial scale is the development of highly active and robust heterogeneous catalysts able to overcome the CO2 activation barrier and deliver sufficient amount of the upgrading products at the desired operation conditions. Also, its high energy demand due to the endothermic nature of the reaction imposes extra difficulties. This review critically discusses the recent progresses on catalysts design ranging from traditional metal-supported catalysts to advanced structured and nanostructured systems with promising performance. The main advantages and culprits of the different catalytic systems are introduced aiming to inspire the catalysis community to further refine these formulations towards the development of "supercatalysts" for DRM. Besides the design of increasingly complex catalyst morphologies as well as other promising alternatives aiming at reducing the energy consumption of the process or tackle deactivation through reactor design are introduced.

2022 | 29.50

The main handicap still hindering the eventual exploitation of organometal halide perovskite-based solar cells is their poor stability under prolonged illumination, ambient conditions, and increased temperatures. This article shows for the first time the vacuum processing of the most widely used solid-state hole conductor (SSHC), i.e., the Spiro-OMeTAD [2,2 ',7,7 '-tetrakis (N,N-di-p-methoxyphenyl-amine) 9,9 '-spirobifluorene], and how its dopant-free crystalline formation unprecedently improves perovskite solar cell (PSC) stability under continuous illumination by about two orders of magnitude with respect to the solution-processed reference and after annealing in air up to 200 degrees C. It is demonstrated that the control over the temperature of the samples during the vacuum deposition enhances the crystallinity of the SSHC, obtaining a preferential orientation along the pi-pi stacking direction. These results may represent a milestone toward the full vacuum processing of hybrid organic halide PSCs as well as light-emitting diodes, with promising impacts on the development of durable devices. The microstructure, purity, and crystallinity of the vacuum sublimated Spiro-OMeTAD layers are fully elucidated by applying an unparalleled set of complementary characterization techniques, including scanning electron microscopy, X-ray diffraction, grazing-incidence small-angle X-ray scattering and grazing-incidence wide-angle X-ray scattering, X-ray photoelectron spectroscopy, and Rutherford backscattering spectroscopy.

2020 | 29.37

Direct Laser Writing (DLW) has been increasingly selected as a microfabrication route for efficient, cost-effective, high-resolution material synthesis and conversion. Concurrently, lasers participate in the patterning and assembly of functional geometries in several fields of application, of which electronics stand out. In this review, recent advances and strategies based on DLW for electronics microfabrication are surveyed and outlined, based on laser material growth strategies. First, the main DLW parameters influencing material synthesis and transformation mechanisms are summarized, aimed at selective, tailored writing of conductive and semiconducting materials. Additive and transformative DLW processing mechanisms are discussed, to open space to explore several categories of materials directly synthesized or transformed for electronics microfabrication. These include metallic conductors, metal oxides, transition metal chalcogenides and carbides, laser-induced graphene, and their mixtures. By accessing a wide range of material types, DLW-based electronic applications are explored, including processing components, energy harvesting and storage, sensing, and bioelectronics. The expanded capability of lasers to participate in multiple fabrication steps at different implementation levels, from material engineering to device processing, indicates their future applicability to next-generation electronics, where more accessible, green microfabrication approaches integrate lasers as comprehensive tools. This review covers recent progress and breakthroughs in direct laser writing for multimaterial synthesis and conversion, toward processing and fabrication of electronics. Predominant laser-material processing mechanisms for the writing of conductive and semiconductive materials are discussed, alongside important considerations on laser operation and implementation for both rigid and flexible electronics, including microelectronics, energy harvesting and storage, sensors, and bioelectronics. image

2024 | 27.40

The rapid growth of global energy consumption and the increasing demand for sustainable and renewable energy sources have urged vast research into harnessing energy from various sources. Among them, the most promising approaches are nanogenerators (NGs) and solar cells (SCs), which independently offer innovative solutions for energy harvesting. This review paper presents a comprehensive analysis of the integration of NGs and SCs, exploring advanced hybrid structures and their diverse applications. First, an overview of the principles and working mechanisms of NGs and SCs is provided for seamless hybrid integrations. Then, various design strategies are discussed, such as piezoelectric and triboelectric NGs with different types of SCs. Finally, a wide range of applications are explored that benefit from the synergistic integration of NGs and SCs, including self-powered electronics, wearable devices, environmental monitoring, and wireless sensor networks. The potential for these hybrid systems is highlighted to address real-world energy needs and contribute to developing sustainable and self-sufficient technologies. In conclusion, this review provides valuable insights into the state-of-the-art developments in NGs and SCs integration, shedding light on advanced hybrid structures and their diverse applications.

2024 | 24.40

The proposed study tries to reply on one important question concerning glucose dehydration: What is the role of bare or tandem Lewis/Bronsted acid sites in the reaction and which are better? A series of mono and bifunctional catalyst are designed and screened for the glucose dehydration reaction. The results clearly reveal that catalyst activity is a function of catalyst composition. The presence of Lewis sites the reaction toward first step isomerization, while the Brunsted acid dehydrate directly glucose to HMF via levoglucosane intermediate. This study proposed also a kinetic modelling of the included reactions and their contrast with the empirical observations.

2021 | 24.32

The signal crosstalk and electromagnetic interference (EMI) problems direly need to be resolved in the rapid development of modern microwave communication technology for a better working frequency and transmission power of electronic systems. Where the new absorbing materials such as molybdenum disulfide (MoS2)/titania (TiO2)/Ti2CTx and MoS2/Ti2CTx composites could meet the requirement of "thin, strong, light weight, and wide band" for excellent absorbing performance. In this work, a lighter Ti2CTx material was selected as the matrix, and MoS2 was in-situ grown on Ti2CTx matrix by traditional hydrothermal method and microwave solvothermal method. The fabricated composite exhibited synergic effect of two-dimensional heterostructural interface and double dielectric elements, where a small amount of TiO2 and a certain proportion of MoS2 jointly improve the impedance matching of the composite material. In here, the extreme reflection loss (RLmin) can reach - 54.70 dB (with a frequency of 7.59 GHz, 3.39 mm thickness), and the maximum effective absorption bandwidth (EAB(max)) can reach 4 GHz. Polyethylene glycol 200 was used as the solvent instead of water to make Ti2CTx less oxidized during the composite process, where the microwave heating would attain fast speed, short time, high efficiency, and uniform product. Since, the MoS2/Ti2CTx composite without oxidizing possessed a wider effective absorption bandwidth (EAB) at a thinner thickness, thus resulting in the excellent microwave absorption performance and confirming the validity and rationality of new microwave absorption materials.

2023 | 23.20

In this study, the promoting effect of rhenium addition as a co-dopant on Mo/ZSM-5 catalysts system has been analysed. Hence, bimetallic (Re-Mo/ZSM-5) catalysts have been synthesized using a sequential impregnation methodology. The catalytic performance for direct aromatization of methane reaction has been determined and correlated with their physical and chemical state combining multiple characterization techniques. An important synergy between Mo and Re, affected by the sequential impregnation, has been observed. Thus, Re1-Mo4/ZSM-5 in which Re has been incorporated first shows notably higher aromatic yields and stability against deactivation. Characterization results suggest that catalytic enhancement is due to the important effect of Re presence in close interaction with Mo. Improved evolution of ethane through C-C coupling would be correlated to this catalytic performance. As we discuss, Mo nature and location in the bimetallic systems are strongly conditioned by Re and the impregnation sequence and favours such intermediate step.

2022 | 22.10

In order to enhance optical absorption, light trapping by multiple scattering is commonly achieved in dye sensitized solar cells by adding particles of a different sort. Herein we propose a theoretical method to find the structural parameters (particle number density and size) that optimize the conversion efficiency of electrodes of different thicknesses containing spherical inclusions of diverse composition. Our work provides a theoretical framework in which the response of solar cells containing diffuse scattering particles can be rationalized. Optical simulations are performed by combining a Monte Carlo approach with Mie theory, in which the angular distribution of scattered light is accounted for. Several types of scattering centers, such as anatase, gold and silver particles, as well as cavities, are considered and their effect compared. Estimates of photovoltaic performance, insight into the physical mechanisms responsible for the observed enhancements, and guidelines to improve the cell design are provided. We discuss the results in terms of light transport in weakly disordered optical media and find that the observed variations between the optimum scattering configurations attained for different electrode thicknesses can be understood as the result of the randomization of the light propagation direction at different depths within the active layer. A primary conclusion of our study is that photovoltaic performance is optimised when the scattering properties of the film are adjusted so that the distance over which incident photons are randomized is comparable to the thickness of the film. This simple relationship could also be used as a design rule to attain the optimum optical design in other photovoltaic materials.

2014 | 20.52

Hybrid organic-inorganic perovskite materials have risen up as leading components for light-harvesting applications. However, to date many questions are still open concerning the operation of perovskite solar cells (PSCs). A systematic analysis of the interplay among structural features, optoelectronic performance, and ionic movement behavior for FA(0.83)MA(0.17)Pb(I0.83Br0.17)(3) PSCs is presented, which yield high power conversion efficiencies up to 20.8%.

2016 | 19.79

In the current study, synthesis and detailed characterization of cellulose biochars as a waste biomass model component and vine shoot biochars as a real waste biomass catalyst was performed. Although initially biochars exhibit poor textural properties, a simple activation process can make them much more suitable as a catalyst supports. A combination of physical (CO2) and chemical activation (ZnCl2) was evaluated. The characterization results indicated that the surface area and pore volume of the biochars have increased significantly by chemical activation treatment with ZnCl2. A series of metal catalysts (Pd, Au and Ru) supported on biochars was prepared and characterized. The prepared materials represent a set of noble metal catalysts supported on biochars with different textural and surface properties, which can be used to evaluate the catalytic role of the active phase and carbon support nature in catalytic reactions of interest, such as hydrodeoxygenation, described in the part II.

2020 | 19.50

Novel composite photo-catalysts having (NH4)(4)[NiMo6O24H6]center dot 5H(2)O Polyoxometalate (POM) species deposited over g-C3N4 are synthesized. Materials were characterized through a multitechnique approach showing the stability of the carbon nitride component both through the synthesis process and under reaction. Contrarily, the POM component evolves under reaction conditions to maximize the interaction with the support. Such a behavior renders, as measured by the quantum efficiency, highly active photo-catalysts in the photo-oxidation of 2-propanol and styrene both under UV and sunlight illumination, setting up the basis for a green catalytic process. The material having a 4 wt. % POM showed improved activity with respect to both parent constituents but also higher selectivity to the partial oxidation of the alcohol and the aromatic hydrocarbon to generate added value chemical compounds. A multitechnique approach investigating charge carrier fate demonstrates the key role played by the interaction between components to promote activity and selectivity in selective oxidation reactions.

2020 | 19.50

Y3Al5O12 (YAG) is a widely used phosphor host. Its optical properties are controlled by chemical substitution at its YO8 or AlO6/AlO4 sublattices, with emission wavelengths defined by rare-earth and transition-metal dopants that have been explored extensively. Nonstoichiometric compositions Y3+xAl5-xO12 (x not equal 0) may offer a route to new emission wavelengths by distributing dopants over two or more sublattices simultaneously, producing new local coordination environments for the activator ions. However, YAG typically behaves as a line phase, and such compositions are therefore challenging to synthesize. Here, a series of highly nonstoichiometric Y3+xAl5-xO12 with 0 <= x <= 0.40 is reported, corresponding to <= 20% of the AlO6 sublattice substituted by Y3+, synthesized by advanced melt-quenching techniques. This impacts the up-conversion luminescence of Yb3+/Er3+-doped systems, whose yellow-green emission differs from the red-orange emission of their stoichiometric counterparts. In contrast, the YAG:Ce3+ system has a different structural response to nonstoichiometry and its down-conversion emission is only weakly affected. Analogous highly nonstoichiometric systems should be obtainable for a range of garnet materials, demonstrated here by the synthesis of Gd3.2Al4.8O12 and Gd3.2Ga4.8O12. This opens pathways to property tuning by control of host stoichiometry, and the prospect of improved performance or new applications for garnet-type materials.

2023 | 18.50

Herein a versatile and scalable method to prepare periodically corrugated nanophosphor surface patterns displaying strongly polarized and directional visible light emission is demonstrated. A combination of inkjet printing and soft lithography techniques is employed to obtain arbitrarily shaped light emitting motifs. Such predesigned luminescent drawings, in which the polarization and angular properties of the emitted light are determined and finely tuned through the surface relief, can be used as anti-counterfeiting labels, as these two specific optical features provide additional means to identify any unauthorized or forged copy of the protected item. The potential of this approach is exemplified by processing a self-standing photoluminescent quick response code whose emission is both polarized and directionally beamed. Physical insight of the mechanism behind the directional out-coupled photoluminescence observed is provided by finite-difference time-domain calculations.

2023 | 18.50

We introduce herein the advanced application of low-pressure plasma procedures for the development of piezo and triboelectric mode I hybrid nanogenerators. Thus, plasma assisted deposition and functionalization methods are presented as key enabling technologies for the nanoscale design of ZnO polycrystalline shells, the formation of conducting metallic cores in core@shell nanowires, and for the solventless surface modification of polymeric coatings and matrixes. We show how the perfluorinated chains grafting of polydimethylsiloxane (PDMS) provides a reliable approach to increase the hydrophobicity and surface charges at the same time that keeping the PDMS mechanical properties. In this way, we produce efficient Ag/ZnO convoluted piezoelectric nanogenerators supported on flexible substrates and embedded in PDMS compatible with a contact-separation triboelectric architecture. Factors like crystalline texture, ZnO thickness, nanowires aspect ratio, and surface chemical modification of the PDMS are explored to optimize the power output of the nanogenerators aimed for harvesting from low-frequency vibrations. Just by manual triggering, the hybrid device can charge a capacitor to switch on an array of color LEDs. Outstandingly, this simple three-layer architecture allows for harvesting vibration energy in a wide bandwidth, thus, we show the performance characteristics for frequencies between 1 Hz and 50 Hz and demonstrate the successful activation of the system up to ca. 800 Hz.

2022 | 17.60

Nanogenerators and self-powered nanosensors have shown the potential to power low-consumption electronics and human-machine interfaces, but their practical implementation requires reliable, environmentally friendly and scalable processes for manufacturing and processing. Furthermore, the emerging flexible and wearable electronics technology demands direct fabrication onto innovative substrates such as paper and plastics typically incompatible with high process temperatures. This article presents a plasma synthesis approach for the fabri-cation of piezoelectric nanogenerators (PENGs) and self-powered sensors on paper substrates. Polycrystalline ZnO nanocolumnar thin films are deposited by plasma-enhanced chemical vapour deposition on common paper supports using a microwave electron cyclotron resonance reactor working at room temperature yielding high growth rates and low structural and interfacial stresses. Applying Kinetic Monte Carlo simulation, we elucidate the basic shadowing mechanism behind the characteristic microstructure and porosity of the ZnO thin films, relating them to an enhanced piezoelectric response to periodic and random inputs. The piezoelectric devices are assembled by embedding the ZnO films in polymethylmethacrylate (PMMA) and using Au thin layers as elec-trodes in two different configurations, namely laterally and vertically contacted devices. We present the response of the laterally connected devices as a force sensor for low-frequency events with different answers to the applied force depending on the impedance circuit, i.e. load values range, a behaviour that is theoretically analyzed. The characterization of the vertical devices in cantilever-like mode reaches instantaneous power densities of 80 nW/ cm2 with a mean power output of 20 nW/cm2. Besides, we analyze their actual-scenario performance by acti-vation with a fan and handwriting. Overall, this work demonstrates the advantages of implementing plasma deposition for piezoelectric films to develop robust, flexible, stretchable, and enhanced-performance nano-generators and self-powered piezoelectric sensors compatible with inexpensive and recyclable supports.

2023 | 16.80

The Calcium Looping performance of limestone for thermochemical energy storage has been investigated under novel favorable conditions, which involve calcination at moderate temperatures under CO2 at low pressure (0.01 and 0.1 bar) and carbonation at high temperature under CO2 at atmospheric pressure. Calcining at low CO2 pressures allows to substantially reduce the temperature to achieve full calcination in short residence times. Moreover, it notably enhances CaO multicycle conversion. The highest values of conversion are obtained for limestone samples calcined under 0.01 bar CO2 at 765 degrees C. Under these conditions, the residual conversion is increased by a factor of 10 as compared to conditions involving calcination under CO2 at atmospheric pressure. The enhancement of CaO conversion is correlated to the microstructure of the CaO samples obtained after calcination. As seen from SEM, BET surface and XRD analysis, calcination under low CO2 pressure leads to a remarkable decrease of pore volume and CaO crystallite size. Consequently, CaO surface area available for carbonation in the fast reaction-controlled regime and therefore reactivity in short residence times is promoted.

2021 | 16.74

The effects of the metal oxide support on the activity, selectivity, resistance to carbon deposition and high temperature oxidative aging on the Rh-catalyzed dry reforming of methane (DRM) were investigated. Three Rh catalysts supported on oxides characterized by very different oxygen storage capacities and labilities (gamma-Al2O3, alumina-ceria-zirconia (ACZ) and ceria-zirconia (CZ)) were studied in the temperature interval 400-750 degrees C under both integral and differential reaction conditions. ACZ and CZ promoted CO2 conversion, yielding CO enriched synthesis gas. Detailed characterization of these materials, including state of the art XPS measurements obtained via sample transfer between reaction cell and spectrometer chamber, provided clear insight into the factors that determine catalytic performance. The principal Rh species detected by post reaction XPS was Rh, its relative content decreasing in the order Rh/CZ(100%) > Rh/ACZ(72%) > Fth/gamma Al2O3(55%). The catalytic activity followed the same order, demonstrating unambiguously that Rh is indeed the key active site. Moreover, the presence of CZ in the support served to maintain Rh in the metallic state and minimize carbon deposition under reaction conditions. Carbon deposition, low in all cases, increased in the order Rh/CZ < Rh/ACZ < Rh/gamma-Al2O3 consistent with a bi-functional reaction mechanism whereby backspillover of labile lattice O2- contributes to carbon oxidation, stabilization of Rh and modification of its surface chemistry; the resulting O vacancies in the support providing centers for dissociative adsorption of CO2. The lower apparent activation energy observed with CZ-containing samples suggests that CZ is a promising support component for use in low temperature DRM.

2019 | 16.68

The thin film configuration presents obvious practical advantages over the 1D implementation in energy harvesting systems such as easily manufacturing and processing, and long-lasting and stable devices. However, ZnO-based piezoelectric nanogenerators (PENGs) generally rely on the exploitation of single-crystalline nanowires because of their self-orientation in the c-axis direction and ability to accommodate long deformations resulting in high piezoelectric performance. Herein, we show an innovative approach to produce PENGs by combining polycrystalline ZnO layers fabricated at room temperature by plasma-assisted deposition with supported small-molecule organic nanowires (ONWs) acting as 1D scaffolds. Such hybrid nanostructures present convoluted core-shell morphology, formed by a single-crystalline organic nanowire conformally surrounded by a poly-crystalline ZnO shell and combine the organic core mechanical properties with the ZnO layer piezoelectric response. In a step forward towards the integration of multiple functions within a single wire, we have also developed ONW-Au-ZnO nanoarchitectures including a gold shell acting as inner electrode achieving output piezo-voltages up to 170 mV. The synergistic combination of functionalities in the ONW-Au-ZnO devices promotes an enhanced performance generating piezo-currents one order of magnitude larger than the ONW-ZnO nanowires and superior to the thin film nanogenerators for equivalent and higher thicknesses.

2019 | 16.60

The steel industry is the most relevant sector in emerging economies due to its application in numerous fields. However, steel manufacturing involves large energy investment and produces significant greenhouse gas emissions. The current world economic and environmental scenario therefore necessitates that improvements in the footprint of the steel industry be made without affecting its viability. Considering the present challenge, we report two possible processes for Carbon Capture and Utilization (CCU). The first process is the competitive capture of CO2-SO2, followed by CO2 valorisation to methane. However, the CO2 capture capacity and lifetime for the adsorbent after multiple cycles could be improved through preliminary desulphurization of the gas current. The improved system demonstrates net profitability in a typical stainless steel plant. Therefore, it can be implemented in an industrial setting without profitability loss to steelmaking operations, fulfilling bot the goal of reducing CO2 emissions while protecting the mainstay of the plant.

2023 | 16.30

Rational design of low-cost and efficient transition-metal catalysts for low-temperature CO2 activation is significant and poses great challenges. Herein, a strategy via regulating the local electron density of active sites is developed to boost CO2 methanation that normally requires >350 °C for commercial Ni catalysts. An optimal Ni/ZrO2 catalyst affords an excellent low-temperature performance hitherto, with a CO2 conversion of 84.0 %, CH4 selectivity of 98.6 % even at 230 °C and GHSV of 12,000 mL g−1 h−1 for 106 h, reflecting one of the best CO2 methanation performance to date on Ni-based catalysts. Combined a series of in situ spectroscopic characterization studies reveal that re-constructing monoclinic-ZrO2 supported Ni species with abundant oxygen vacancies can facilitate CO2 activation, owing to the enhanced local electron density of Ni induced by the strong metal-support interactions. These findings might be of great aid for construction of robust catalysts with an enhanced performance for CO2 emission abatement and beyond.

2024 | 16.10

Photon upconversion via triplet-triplet annihilation (TTA-UC) provides a pathway to overcoming the thermodynamic efficiency limits in single-junction solar cells by allowing the harvesting of sub-bandgap photons. Here, we use mixed halide perovskite nanocrystals (CsPbX3, X = Br/I) as triplet sensitizers, with excitation transfer to 9,10-diphenylanthracene (DPA) and/or 9,10-bis[(triisopropylsilyl)ethynyl]anthracene (TIPS-An) which act as the triplet annihilators. We observe that the upconversion efficiency is five times higher with the combination of both annihilators in a composite system compared to the sum of the individual single-acceptor systems. Our work illustrates the importance of using a composite system of annihilators to enhance TTA upconversion, demonstrated in a perovskite-sensitized system, with promise for a range of potential applications in light-harvesting, biomedical imaging, biosensing, therapeutics, and photocatalysis.

2024 | 15.80

Nanostructuration and 2D patterning of thin films are common strategies to fabricate biomimetic surfaces and components for microfluidic, microelectronic or photonic applications. This work presents the fundamentals of a surface nanotechnology procedure for laterally tailoring the nanostructure and crystalline structure of thin films that are plasma deposited onto acoustically excited piezoelectric substrates. Using magnetron sputtering as plasma technique and TiO2 as case example, it is demonstrated that the deposited films depict a sub-millimetre 2D pattern that, characterized by large lateral differences in nanostructure, density (up to 50%), thickness, and physical properties between porous and dense zones, reproduces the wave features distribution of the generated acoustic waves (AW). Simulation modelling of the AW propagation and deposition experiments carried out without plasma and under alternative experimental conditions reveal that patterning is not driven by the collision of ad-species with mechanically excited lattice atoms of the substrate, but emerges from their interaction with plasma sheath ions locally accelerated by the AW-induced electrical polarization field developed at the substrate surface and growing film. The possibilities of the AW activation as a general approach for the tailored control of nanostructure, pattern size, and properties of thin films are demonstrated through the systematic variation of deposition conditions and the adjustment of AW operating parameters.

2021 | 15.72

Herein we report an experimental analysis of the performance of photonic crystal based dye solar cells (PC-DSCs) as the incident light angle moves away from the normal with respect to the cell surface. Nanoparticle multilayers operating at different wavelength ranges were coupled to the working electrode of a dye solar cell for this study. The interplay between optical and photovoltaic properties with the incident light angle is discussed. We demonstrate that an efficiency enhancement is attained for PC-DSCs at all angles measured, and that rational design of the photonic crystal back mirror leads to a reduction of the photocurrent losses related to the tilt angle of the cell, usually labeled as cosine losses. Angular variations of the cell transparency are also reported and discussed. These angular properties are relevant to the application of these solar devices in building integrated photovoltaics as potential window modules.

2013 | 15.49

Optimization of Pt-promoted TiO2-based is key to promote the photocatalytic production of hydrogen using sacrificial alcohol molecules. Combination of doping and surface decoration of the mentioned base photoactive material is here exploited to maximize hydrogen yield. Using the quantum efficiency parameter, it is shown that the resulting composite system can boost activity up to 7.3 times within the whole methanol:water mixture ratio, yielding quantum efficiencies in the ca. 13-16 % range. The key role of the different components in generating charge carrier species and their use to trigger the sacrificial molecule evolution and control reaction kinetics are examined through an in-situ spectroscopic study. The study unveils the complex reaction mechanism, with generation of C1 to C3 molecules from different carbon-containing radicals, and interprets the physical origin of the huge H2 production enhancement occurring in doped-composite titania-based catalysts.

2022 | 15.10

Large-scale thermochemical energy storage (TCES) is gaining relevance as an alternative to current thermal energy storage systems in Concentrated Solar Power plants. Among the different systems, the reversible reaction between CaO and CO2 stands out due to the wide availability and low cost of the raw material: limestone. Direct solar absorption of the storage media would improve the efficiency of solar-to-thermal energy storage due to reduced thermal transfer barriers, but the solar optical absorption of CaCO3 is poor. In this work, we propose the use of a Ca-rich calcarenite sedimentary rock so-called albem as an alternative to limestone. We demonstrate that this reddish material exhibits an average solar absorptance that is approximately ten times larger than limestone. Moreover, the multicycle carbonation/calcination performance under different experimental conditions has been studied by thermogravimetry, and similar values to those exhibited for limestone have been obtained. Besides, the material is cheap (6 Elton), and simulations showed that the use of this material would significantly improve the overall CaL-CSP efficiency at the industrial level.

2022 | 15.10

The active forms of Au and Pt in CeO2-based catalysts for the water-gas shift (WGS) reaction are an issue that remains unclear, although it has been widely studied. On one hand, ionic species might be responsible for weakening the Ce-O bonds, thus increasing the oxygen mobility and WGS activity. On the other hand, the close contact of Au or Pt atoms with CeO2 oxygen vacancies at the metal-CeO2 interface might provide the active sites for an efficient reaction. In this work, using in situ X-ray absorption spectroscopy, we demonstrate that both Au and Pt remain unoxidized during the reaction. Remarkable differences involving the dynamics established by both species under WGS atmospheres were recognized. For the prereduced Pt catalyst, the increase of the conversion coincided with a restructuration of the Pt atoms into cuboctahedrical metallic particles without significant variations on the overall particle size. Contrary to the relatively static behavior of Pt-0, Au-0 nanoparticles exhibited a sequence of particle splitting and agglomeration while maintaining a zero oxidation state despite not being located in a metallic environment during the process. High WGS activity was obtained when Au atoms were surrounded by oxygen. The fact that Au preserves its unoxidized state indicates that the chemical interaction between Au and oxygen must be necessarily electrostatic and that such an electrostatic interaction is fundamental for a top performance in the WGS process.

2022 | 15.00

Next-generation light-emitting applications such as displays and opticalcommunications require judicious control over emitted light, includingintensity and angular dispersion. To date, this remains a challenge as con-ventional methods require cumbersome optics. Here, we report highly direc-tional and enhanced electroluminescence from a solution-processed quasi-2-dimensional halide perovskite light-emitting diode by building a devicearchitecture to exploit hybrid plasmonic-photonic Tamm plasmon modes. Byexploiting the processing and bandgap tunability of the halide perovskitedevice layers, we construct the device stack to optimise both optical andcharge-injection properties, leading to narrow forward electroluminescencewith an angular full-width half-maximum of 36.6° compared with the con-ventional isotropic control device of 143.9°, and narrow electroluminescencespectral full-width half-maximum of 12.1 nm. The device design is versatile andtunable to work with emission lines covering the visible spectrum with desireddirectionality, thus providing a promising route to modular, inexpensive, anddirectional operating light-emitting devices.

2024 | 14.70

Active and selective structured RuO2/Al2O3 catalysts for CO methanation using a flow simulating CO2-rich reformate gases from WGS and PROX units (H-2 excess, CO2 presence and 300 ppm CO concentration) were prepared. Both, the RuO2/Al2O3 powder and the slurry prepared from it for its structuration by washcoating of the metallic micromonolithic structure, were also active and selective. Both the slurry (S-RuAl) and micro monoliths (M-RuAl) were able to completely and selectively methanate CO at much lower temperatures than the parent RuAI powder. The optimal working temperature in which the CO conversion is maximum and the CO2 conversion is minimized was determined to be from 149 degrees C to 239 degrees C for S-RuAl and from 165 degrees C to 232 degrees C for M-RuAl, whilst it was from 217 degrees C to 226 degrees C for RuAI powder. TPR, XRD and TEM measurements confirmed that the changes in the activity and selectivity for CO methanation among the considered catalysts can be related with modifications in the surface particle size of ruthenium and its reducibility. These were ascribed to the metallic substrate, the presence of PVA and colloidal alumina in the slurry preparation, the aqueous and acidic media and the thermal treatment used, resulting in a more active and selective catalysts than the parent powder.

2018 | 14.23

Carbon formation and sintering remain the main culprits regarding catalyst deactivation in the dry and bi-reforming of methane reactions (DRM and BRM, respectively). Nickel based catalysts (10 wt.%) supported on alumina (Al2O3) have shown no exception in this study, but can be improved by the addition of tin and ceria. The effect of two different Sn loadings on this base have been examined for the DRM reaction over 20 h, before selecting the most appropriate Sn/Ni ratio and promoting the alumina base with 20 wt.% of CeO2. This catalyst then underwent activity measurements over a range of temperatures and space velocities, before undergoing experimentation in BRM. It not only showed good levels of conversions for DRM, but exhibited stable conversions towards BRM, reaching an equilibrium H-2/CO product ratio in the process. In fact, this work reveals how multicomponent Ni catalysts can be effectively utilised to produce flexible syngas streams from CO2/CH4 mixtures as an efficient route for CO2 utilisation.

2018 | 14.23

Eu-doped ZrO2 solid solutions have been synthesized in order to prepare proton conductors as water-enhancer additives for the WGS reaction. Elemental characterization has been carried out revealing homogeneous dopant distribution resulting in fluorite-type solid solutions for Eu2O3 contents up to similar to 9 mol.%. Representative samples of the Eu-doped ZrO2 series have been analysed by Impedance Spectroscopy (IS) in inert, oxygen and wet conditions. The solid solution with 5 mol.% of Eu2O3 has presented the highest conductivity values for all tested conditions indicating an optimal amount of dopant. Moreover, the presence of vapour pressure results in an increment of the conductivity at temperatures lower than 300 degrees C, meanwhile at higher temperatures the conductivity is the same than that in inert conditions. To elucidate these results, in situ DRIFTS studies were carried out. These experiments evidenced the existence of water dissociation at oxygen vacancies (band at 3724 cm(-1)) as well as the presence of physisorbed water at temperatures up to similar to 300 degrees C where the band at 5248 cm(-1) characteristic of these species disappeared. These results points to a layer model where the physisorbed water interacts with surface hydroxyls generated by dissociated water that improves the proton conductivity through Grotthuss' mechanism in the RT-300 degrees C temperature range. These samples were successfully tested in WGS reaction as additive to a typical Pt-based catalyst. The presence of the mixed oxide reveals an increase of the catalyst' activity assisted by the proton conductor, since improves the water activation step.

2018 | 14.23

Water presence and concentration strongly influence CO conversion and CS+ selectivity in the Fischer Tropsch reaction. In this work, the influence of the water concentration was investigated using a model Ru/Al2O3 (5 wt. %) catalyst. The surface species formed after CO and H-2 adsorption in dry and wet (different water concentrations) conditions were analyzed by FTIR. Firstly, water adsorption was carried out up to complete filling of the pores and then CO was put in contact with the catalyst. The absence of adsorbed CO species in these conditions evidences that CO diffusion in water controls the access of the gas to the active sites and explains the negative effect of high water concentrations reported by some authors. Moreover, the adsorption of a mixture of CO + H-2 + H2O, being the water concentration close to that needed to have a monolayer, and a dry mixture of CO + H-2 were carried out and compared. Results evidence that water in this low concentration, is able to gasify the surface carbon species formed by CO dissociation on the metallic sites. This cleaning effect is related to the positive effect of water on CO conversion detected by some authors.

2018 | 14.23

Different photocatalysts based on commercial ZnO modified by silver photodeposition were prepared in this work. The samples were characterized by X-ray fluorescence spectrometry (XRF), specific surface area (SSA), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and UV–vis diffuse reflectance (UV–vis DRS). XRD and XPS showed that Ag/ZnO samples are composed of metallic Ag (Ag0) and ZnO structure was identified. Furthermore, TEM analysis evidenced that the number of silver particles increased with the Ag content. At last, UV–vis DRS results revealed a reflectance band for Ag/ZnO samples, ascribed to the surface plasmon resonance (SPR) absorption of metal silver particles. Commercial ZnO and Ag/ZnO samples were evaluated in the phenol removal under UV light irradiation. It was observed an enhancement of photocatalytic phenol removal from aqueous solutions by silver addition in comparison to commercial ZnO. In particular, the phenol removal increased with the silver content from 0.14 to 0.88 wt%, after this content (i.e 1.28 wt%) the phenol degradation significantly decreased indicating that the optimal Ag content was equal to 0.88 wt%. The influence of the best photocatalyst dosage and the change of the initial phenol concentration in solution were also investigated in this work and the best photocatalytic performance was obtained by using 50 mg L−1 of phenol initial concentration and 0.15 g L−1 of photocatalyst dosage. Finally, the optimized Ag/ZnO photocatalyst was employed for the treatment of a real drinking wastewater containing phenol in which the almost total phenol removal was achieved after 180 min of UV irradiation time.

2018 | 14.23

Bragg microcavities (BMs) formed by the successive stacking of nanocolumnar porous SiO2 and TiO2 layers with slanted, zigzag, chiral, and vertical configurations are prepared by physical vapor deposition at oblique angles while azimuthally varying the substrate orientation during the multilayer growth. The slanted and zigzag BMs act as wavelength-selective optical retarders when they are illuminated with linearly polarized light, while no polarization dependence is observed for the chiral and vertical cavities. This distinct optical behavior is attributed to a self-nanostructuration mechanism involving a fence-bundling association of nanocolumns as observed by focused ion beam scanning electron microscopy in the slanted and zigzag microcavities. The outstanding retarder response of the optically active BMs can be effectively modulated by dynamic infiltration of nano- and mesopores with liquids of different refraction indices acting as a switch of the polarization behavior. The unprecedented polarization and tunable optofluidic properties of these nanostructured photonic systems have been successfully simulated with a simple model that assumes a certain birefringence for the individual stacked layers and accounts for the light interference phenomena developed in the BMs. The possibilities of this type of self-arranged nanostructured and optically active BMs for liquid sensing and monitoring applications are discussed.

2016 | 13.94

A procedure to prepare porous photonic crystal resonators containing gold nanoparticles is reported. The optical absorption of the ensemble, resulting from the excitation of the localized surface plasmon of the metallic beads, is finely tuned by a gradual shift of the cavity mode. This is achieved by infiltration of the void network with different guest compounds.

2011 | 13.88

The performance of perovskite solar cells has been progressing over the past few years and efficiency is likely to continue to increase. However, a negative aspect for the integration of perovskite solar cells in the built environment is that the color gamut available in these materials is very limited and does not cover the green-to-blue region of the visible spectrum, which has been a big selling point for organic photovoltaics. Here, we integrate a porous photonic crystal (PC) scaffold within the photoactive layer of an opaque perovskite solar cell following a bottom-up approach employing inexpensive and scalable liquid processing techniques. The photovoltaic devices presented herein show high efficiency with tunable color across the visible spectrum. This now imbues the perovskite solar cells with highly desirable properties for cladding in the built environment and encourages design of sustainable colorful buildings and iridescent electric vehicles as future power generation sources.

2015 | 13.78

Ferroelectrics are important technological materials with wide-ranging applications in electronics, communication, health, and energy. While lead-based ferroelectrics have remained the predominant mainstay of industry for decades, environmentally friendly lead-free alternatives are limited due to relatively low Curie temperatures (T-C) and/or high cost in many cases. Efforts have been made to enhance T-C through strain engineering, often involving energy-intensive and expensive fabrication of thin epitaxial films on lattice-mismatched substrates. Here, a relatively simple and scalable sol-gel synthesis route to fabricate polycrystalline (Ba0.85Ca0.15)(Zr0.1Ti0.9)O-3 nanowires within porous templates is presented, with an observed enhancement of T-C up to similar to 300 degrees C as compared to similar to 90 degrees C in the bulk. By combining experiments and theoretical calculations, this effect is attributed to the volume reduction in the template-grown nanowires that modifies the balance between different structural instabilities. The results offer a cost-effective solution-based approach for strain-tuning in a promising lead-free ferroelectric system, thus widening their current applicability.

2017 | 13.33

There are multiple factors that influence the catalyst performance in the reaction of formic acid dehydrogena-tion: the nature of catalyst and/or support, the used solvent and reaction variables such as temperature, time, formic acid concentration, presence/absence of formates and pH of the solution. This work evaluates a series of important parameters like the influence of the pH by itself, the influence of the nature of used alkali agents and the effect of direct formate addition as reactive on hydrogen production via formic acid dehydrogenation over a commercially available catalyst. The catalytic performance appears to depend on the ionic radius of the cations of the used base which reflects consequently on the hydrogen selectivity. The best base to be used must have lower hydrated cationic radii and a starting pH around 4 to achieve important hydrogen selectivity for medium term formic acid conversion.

2023 | 13.30

During the last years, perovskite solar cells have gained increasing interest among the photovoltaic community, in particularly after reaching performances at par with mature thin film based PV. This rapid evolution has been fostered by the compositional engineering of perovskite and new device architectures. In the present work, we report the fabrication of perovskite solar cells based on highly ordered 1-dimensional vertically oriented TiO2 nano-forests. These vertically oriented porous TiO2 photoanodes were deposited by physical vapor deposition in an oblique angle configuration, a method which is scalable to fabricate large area devices. Mixed (MA0.15FA0.85)Pb(I0.85Br0.15)3 or triple cation Cs0.05(MA0.15FA0.85)0.95Pb(I0.85Br0.15)3 based perovskites were then infiltrated into these 1-dimensional nanostructures and power conversion efficiencies of 16.8% along with improved stability was obtained. The devices fabricated using 1D-TiO2 were found to be more stable compare to the classical 3-dimensional TiO2 photoanodes prepared by wet chemistry. These 1-D photoanodes will be of interest for scaling up the technology and in other opto-electrical devices as they can be easily fabricated utilizing industrially adapted methodologies.

2017 | 13.12

Scanning tunneling microscopy, temperature-programmed reaction, near-edge X-ray absorption fine structure spectroscopy, and density functional theory calculations were used to study the adsorption and reactions of phenylacetylene and chlorobenzene on Ag(100). In the absence of solvent molecules and additives, these molecules underwent homocoupling and Sonogashira cross-coupling in an unambiguously heterogeneous mode. Of particular interest is the use of silver, previously unexplored, and chlorobenzene—normally regarded as relatively inert in such reactions. Both molecules adopt an essentially flat-lying conformation for which the observed and calculated adsorption energies are in reasonable agreement. Their magnitudes indicate that in both cases adsorption is predominantly due to dispersion forces for which interaction nevertheless leads to chemical activation and reaction. Both adsorbates exhibited pronounced island formation, thought to limit chemical activity under the conditions used and posited to occur at island boundaries, as was indeed observed in the case of phenylacetylene. The implications of these findings for the development of practical catalytic systems are considered.

2015 | 13.04

We combine atomic layer lithography and glancing angle ion polishing to create wafer-scale metamaterials composed of dense arrays of ultrasmall coaxial nanocavities in gold films. This new fabrication scheme makes it possible to shrink the diameter and increase the packing density of 2 nm-gap coaxial resonators, an extreme subwavelength structure first manufactured via atomic layer lithography, both by a factor of 100 with respect to previous studies. We demonstrate that the nonpropagating zeroth-order Fabry-Perot mode, which possesses slow light-like properties at the cutoff resonance, traps infrared light inside 2 nm gaps (gap volume similar to lambda(3)/10(6)). Notably, the annular gaps cover only 3% or less of the metal surface, while open-area normalized transmission is as high as 1700% at the epsilon-near-zero (ENZ) condition. The resulting energy accumulation alongside extraordinary optical transmission can benefit applications in nonlinear optics, optical trapping, and surface-enhanced spectroscopies. Furthermore, because the resonance wavelength is independent of the cavity length and dramatically red shifts as the gap size is reduced, large-area arrays can be constructed with lambda(resonance) >> period, making this fabrication method ideal for manufacturing resonant metamaterials.

2016 | 12.71

Air pollution has become a significant challenge for both developing and developed nations. due to its close association with numerous fatal diseases such as cancer, respiratory, heart attack, and brain stroke. Over recent years, heterogeneous semiconductor photocatalysis has emerged as an effective approach to air remediation due to the ease of scale-up, ready application in the field, use of solar light and ready availability of a number of different effective photocatalysts. To date, most work in this area has been conducted using UV-absorbing photocatalysts, such as TiO2 and ZnO; However, recent studies have revealed Ag3PO4 as an attractive, visible-light-absorbing alternative, with a bandgap of 2.43 eV. In particular, this material has been shown to be an excellent photocatalyst for the removal of many types of pollutants in the gas phase. However, the widespread application of Ag3PO4 is restricted due to its tendency to undergo photoanodic corrosion and the poor reducing power of its photogenerated conductance band electrons, which are unable to reduce O2 to superoxide •O2 −. These limitations are critically evaluated in this review. In addition, recent studies on the modification of Ag3PO4 via combination with the conventional heterojunctions or Z-scheme junctions, as well as the photocatalytic mechanistic pathways for enhanced gas-pollutants removal, are summarized and discussed. Finally, an overview is given on the future developments that are required in order to overcome these challenges and so stimulate further research into this promising field.

2022 | 12.60

In this work, we show that multilayer graphene forms by methanol decomposition at 280 degrees C on an electrochemically promoted nickel catalyst film supported on a K-beta Al2O3 solid electrolyte. In operando near ambient pressure photoemission spectroscopy and electrochemical measurements have shown that polarizing negatively the Ni electrode induces the electrochemical reduction and migration of potassium to the nickel surface. This elemental potassium promotes the catalytic decomposition of methanol into graphene and also stabilizes the graphene formed via diffusion and direct K-C interaction. Experiments reveal that adsorbed methoxy radicals are intermediate species in this process and that, once formed, multilayer graphene remains stable after electrochemical oxidation and back migration of potassium to the solid electrolyte upon positive polarization. The reversible diffusion of ca. 100 equivalent monolayers of potassium through the carbon layers and the unprecedented low-temperature formation of graphene and other carbon forms are mechanistic pathways of high potential impact for applications where mild synthesis and operation conditions are required.

2019 | 12.35

A series of CexZr1-xO2 supports with different Ce/Zr molar ratios were utilized for the preparation of gold catalyst used in the selective oxidation of 5-hydroxymethyl-2-furfural to 2,5-furandicarboxylic acid. The used method of gold deposition allows the preparation of gold particles with homogeneous size and shape distribution, a formulation very useful for studies dedicated to revealing the support participation in the reaction. The supports are characterized by Fourier transform infrared spectroscopy using CO as probe molecule, and the sample catalytic activity is thereafter correlated to the support acid site distribution. The possible participation of its Lewis/Bronsted acidity in the reaction mechanism is also proposed.

2018 | 12.22

Herein, we demonstrate mechanically stable large-area thin films with a purely real refractive index (n) close to 1 in the optical range. At specific wavelengths, it can reach values as small as n = 1.02, the lowest reported for thin solid slabs. These are made of a random network of interwoven spherical silica shells, created by chemical vapour deposition of a thin layer of silica on the surface of randomly packed monodisperse polymer nanoparticles that form a film. Thermal processing of the composites results in highly porous silica-based transparent thin films. We demonstrate the potential of this approach by making novel photonic materials such as strong optical diffusers, built by integrating scattering centers within the ultralow n transparent films, or highly efficient light-emitting slabs, in which losses by total internal reflection are practically absent as a result of the almost null optical impedance at the film-air interface.

2024 | 12.20

Carbons are versatile and diverse materials that have numerous applications across energy and environmental sciences. Carbons with a graphitic structure are particularly appealing due to their high chemical stability, large surface areas and high thermal and electronic conductivity. Numerous methods exist to produce nanostructured graphitic carbons but some of these can be energy-intensive and/or have problems with scalability. One option that is being increasingly explored is the process of iron-catalyzed graphitization. This simply involves the pyrolysis of carbon-rich precursors in the presence of an iron catalyst and has been used to produce carbons with a wide range of structures and properties. This review will examine the current field of iron-catalyzed graphitization, with a focus on molecular organic or biomass precursors. Bio-derived precursors are particularly attractive as a potential option for sustainable production of graphitic carbons. We start with a brief introduction to some key carbon structures, the current applications in which they are employed and some of the key methods that have been developed to produce nanostructured graphitic carbons. We will then review the history of catalytic graphitization before evaluating the wide range of conditions and precursors that have been employed in catalytic graphitization. Finally, this review will investigate the current challenges facing iron-catalyzed graphitization, looking particularly at the limitations of the current understanding of the mechanistic aspects of graphitization, with a view to outlining where research in this field might progress.

2022 | 11.90

Deactivation of a Co catalyst prepared as thin film by magnetron sputtering was studied for the sodium borohydride (SB) hydrolysis reaction under different conditions. Under high SB concentration in single run experiments, the formation of a B-O passivating layer was observed after 1.5 and 24 h use. This layer was not responsible for the catalyst deactivation. Instead, a peeling-off mechanism produced the loss of cobalt. This peeling-off mechanism was further studied in cycling experiments (14 cycles) under low SB concentrations. Ex-situ study of catalyst surface after use and solid reaction products (precipitates) was performed by X-Ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM). The presence of cobalt hydroxide and oxyhydroxide was detected as major components on the catalyst surface after use and as precipitates in the supernatant solutions after washing. Cobalt borate, cobalt carbonate and oxycarbonate were also formed but in lesser amounts. These oxidized cobalt species were formed and further detached from the catalyst at the end of the reaction and/or during catalyst washing by decomposition of the unstable in-situ formed cobalt boride. Leaching of cobalt soluble species was negligible. Thin film mechanical detachment was also found but in a smaller extent. To study the influence of catalyst composition on deactivation processes, cycling experiments were performed with Co-B and Co-C catalysts, also prepared as thin films. We found that the deactivation mechanism proposed by us for the pure Co catalyst also occurred for a different pure Co (prepared at higher pressure) and the Co-B and Co-C samples in our experimental conditions. 

2017 | 11.70

We report the study of the catalytic hydrogen combustion over Pt-impregnated powdery silicon carbide (SiC) using H2PtCl6 as precursor. The reaction was conducted in excess of oxygen. beta-SiC was selected for the study because of its thermal conductivity, mechanical properties, chemical inertness and surface area. The obtained Pt particles over SiC were medium size (average particle diameter of 5 nm for 0.5 wt% Pt). The activity of the Pt-impregnated catalyst over SiC was compared to those obtained in oxidized form over TiO2 and Al2O3 commercial supports (Pt particles very small in size, average particle diameter of 1 nm for 0.5 wt% Pt in both cases). The case of a SiO2 support was also discussed. Those Pt/SiC particles were the most active because of their higher contribution of surface Pt, indicating that partially oxidized surfaces have better activity than those totally oxidized in these conditions. SiC was modified with an acid treatment and thus bigger (average particle diameter of 7 nm for 0.5 wt% Pt) and more active Pt particles were obtained. Durability of the SiC and TiO2 supported catalysts was tested upon 5 cycles and both have shown to be durable and even more active than initially. Exposure to the oxidative reaction mixture activates the catalysts and the effect is more pronounced for the completely oxidized particles. This is due to the surface oxygen chemisorption which activates catalystsi surface.

2017 | 11.70

In this study, a series of photocatalysts based on TiO2 was tested in the elimination of Escherichia coli (E. coli) from urban wastewater. Firstly, TiO2 obtained by sol-gel method was modified by sulfation, and then gold or platinum nanoparticles were photodeposited on sulfated titania surface. Platinized samples were also prepared with different Pt content of 0.5 and 2 wt.%. The samples thus obtained were extensively characterized and it was found that sulfation considerably increases the S-BET value of TiO2 and promotes the anatase phase formation; it was also found that 0.5 wt.% Pt-TiO2 sample presents the lowest noble metal particle size and the best particle dispersion. All the photocatalysts synthesized have shown bactericidal effect and the results obtained by using bare and metalized TiO2 were considerably better than the results obtained with the commercial TiO2 P25 Evonic. Different light intensities were also evaluated in the photocatalytic tests and it was found that 120 W/m(2) leads to obtain the highest E. coli elimination from wastewater samples; however no total elimination of E. coli or other species of bacteria was achieved even after 5 h of photocatalytic treatment without catalyst. Total elimination of the E. coli was achieved after 3 h of photocatalytic reaction by using 120 Wim(2) of light intensity and 2 wt.% Pt-TiO2 as photocatalyst; no bacterial regrowth was observed even after 72 h. 

2017 | 11.70

In this piece, we explore the transformative potential of sustainable biofuel production as a solution to the energy crisis and a pivotal element in realizing the environmental and societal ambitions of Society 5.0. Through a critical examination of "bottom-up"and "topdown"strategies for converting bio-feedstocks sourced from anthropogenic activities into renewable fuels, the work underscores the need for innovation in catalysts and process intensification. By highlighting the advances and challenges in harnessing unconventional feedstocks and integrating renewable energy, this work points to a future where biofuels stand as a cornerstone of a sustainable energy landscape. The significance of this discussion extends beyond the technical realm, offering a vision for a circular economy that reduces dependence on fossil fuels, addresses climate change, and promotes global energy security. It calls for a united front among researchers, industry leaders, and policymakers to drive the biofuel sector toward efficiency, scalability, and widespread adoption.

2024 | 11.50

Two cobalt catalysts, Co/SBA-15 and Co/SiO2, have been studied in steam reforming of ethanol (SRE). Besides the steam reforming products, ethoxide dehydrogenation to acetaldehyde is observed as one of the main reactions. Although by hydrogen treatment cobalt is reduced to the metallic state, under SRE conditions, a phase appears that has been identified as cobalt carbide and correlates with acetaldehyde production. These findings provide insights about the catalytic sites, for SRE, in cobalt catalysts. Comparison with previous results shows that these conclusions are not translatable to other cobalt catalysts, stressing the importance of the support on the catalytic behavior of cobalt.

2017 | 11.38

The reliance of a future carbon-free horizon is strongly aligned with the long-term energy storage avenues which are completely derived from renewable energy resources. Ammonia with its high energy content and density can perform as a decent candidate for buffering the short-term storage options. However, the current NH3 production majorly feeding the current huge desire for ammonia is dominated by the conventional nonrenewable Haber–Bosch (H–B) process route, thus continuously damaging the target of carbon neutrality goals. High-purity hydrogen (H2) gas is an essential precursor for the H–B process; however, it is a significant energy consumer (about 2% of the global energy supply) and contributes over 420 million tons of CO2/annum. Therefore, the research on the renewable synthesis of nitrogen-based energy carriers (such as ammonia) from the direct electrochemical, photocatalytic, or plasma catalytic processes; its conversion; and utilization to the potential derivatives has been a hot topic in the past few decades. A prospective analysis of the highly appealing processes has been summarized in this study, which could facilitate the adaption of renewable alternatives as an effective approach for zero carbon emission, paving the excellent pathways along the road to the development of nitrogen-based energy technologies, especially the targeted development of ammonia. Further, this Review covers the current and future impacts of the H–B process, the development of aspiring ammonia synthesis routes (via electro, photo, bio, chemical loop, or plasma catalysis), and its conversion and utilization to the renewable derivatives in terms of fabrication of model catalysts, advanced characterization technology, and efficient device design.

2023 | 11.30

The Calcium-Looping (CaL) process, based on the multicyclic calcination-carbonation of CaCO3/CaO, is considered a promising Thermochemical Energy Storage (TCES) technology to be integrated into Concentrating Solar Power (CSP) plants. This work proposes a novel CaL integration that operates at low-pressure calcination under pure CO2 and a moderated temperature. Low-pressure calcination (0.01 bar) provides a suitable solution to mitigate CaO sintering and its consequent loss of reactivity in the carbonation stage. Since the temperature for quick calcination in a pure CO2 atmosphere is decreased (from around 950 °C at 1 bar to 765 °C at 0.01 bar), the energy losses at the receiver are minimised. In addition, a reduced calcination temperature allows for the use of metallic receivers already tested at the MW-scale, which significantly increases the CSP-CaL integration reliability. Moreover, multicycle CaO reactivity is promoted in short residence times, allowing the use of a simpler reactor design. Furthermore, there is an increase of 85% in the energy storage density of the system. The proposed plant proposes a smooth integration of the CaL process in CSP plants, with a moderate storage level and supported by a natural gas backup system (solar share higher than 50%). The results show that the solar thermal-to electric efficiency is above 30%. 

2022 | 11.10

The increasing accumulation of toxic heavy metals in the environment has generated the need of efficient removal systems, being the adsorption method the most popular one applied in aqueous solutions. Of particular concern is the case of Pb2+, Cd2+ and Hg2+ due to their high potential hazard. In this paper, we describe the feasibility of a new family of nanomaterials, swelling high charge micas, in the removal of these cations from aqueous solutions. Batch adsorption experiments were carried out in the as-made micas, NaMn, and after functionalization with ethylammonium, EA-Mn, and mercaptoethylammonium, MEA-Mn. The results have demonstrated that all of them are efficient heavy metal adsorbents, being Na-M2 the best adsorbent for Pb2+ and Cd2+, and, MEA-M2 for Hg2+.

2021 | 10.75

Mixed powders of Bi2O3 and Fe2O3 are shown to yield single-phase, dense nanostructured polycrystals of BiFeO3 in reaction flash sintering experiments, carried out by applying a field of 50 V cm(-1) and with the current limit set to 35 mA mm(-2). The furnace was heated at a constant rate with the reaction sintering taking place abruptly upon reaching 625 degrees C. Remarkably, an intermediate bismuth-rich phase of the oxide that forms just before reaching the flash temperature transforms, and at the same time sinters, into singlephase BiFeO3 within a few seconds after the onset of the flash. The BiFeO3 so produced is electrically insulating, a property that is critical to its applications. This one-step synthesis of single-phase polycrystals of complex oxides from their basic constituents, by reaction flash sintering, is a significant development in the processing of complex oxides, which are normally difficult to sinter by conventional methods.

2018 | 10.73

Cellulose ester films were prepared by esterification of cellulose with a multibranched fluorinated carboxylic acid, "BRFA" (BRanched Fluorinated Acid), at different anhydroglucose unit:BRFA molar ratios (i.e., 1:0, 10:1, 5:1, and 1:1). Morphological and optical analyses showed that cellulose-BRFA materials at molar ratios 10:1 and 5:1 formed flat and transparent films, while the one at 1:1 M ratio formed rough and translucent films. Degrees of substitution (DS) of 0.06, 0.09, and 0.23 were calculated by NMR for the samples at molar ratios 10:1, 5:1, and 1:1, respectively. ATR-FTIR spectroscopy confirmed the esterification. DSC thermograms showed a single glass transition, typical of amorphous polymers, at -11 degrees C. The presence of BRFA groups shifted the mechanical behavior from rigid to ductile and soft with increasing DS. Wettability was similar to standard fluoropolymers such as PTFE and PVDF. Finally, breathability and water uptake were characterized and found comparable to materials typically used in textiles.

2021 | 10.72

The RWGS reaction is gathering momentum as an effective route for CO2 valorisation and given its endothermic nature the challenge lies in the design of active low-temperature catalysts. Herein we have designed two catalysts based on subnanometric Pt clusters providing effective CO2 conversion and, more importantly, high CO selectivity in the low-temperature range. The impact of Cs as a dopant in the catalyst's formulation is crucial leading to full selectivity at 300 °C. The reaction mechanisms for the studied systems namely Pt/TiO2 and PtCs/TiO2 are significantly different due to the presence of the alkali promoter. The presence of Cs neutralises the hydroxide groups of the TiO2 surface, changing the reaction pathway. The Pt/TiO2 catalyst follows a redox mechanism where CO2 dissociates to CO in the oxygen vacancies, and then these vacancies are recovered by the migration of H2 by spill over phenomena. On the other hand, the Cs doped catalyst has two possible mechanism pathways: the (ii) formyl/acyl pathway, where –CHO species are formed and, depending on the reaction conditions, evolve to CO gas or oxygenated compounds, and (ii) frustrated Lewis pair (FLP) assisted CO2 reduction route, in which the FLP induces the heterolytic dissociation of H2 and the subsequent hydrogenation of CO2 to CO. The latter route enabled by Cs-doping combined with the subnanometric Pt domains seems to be responsible for the excellent catalytic behaviour leading to fully selective low-temperature RWGS systems and thus unlocking new possibilities for less energy demanding CO2 valorisation units based on RWGS.

2024 | 10.70

Tridecafluorononanoic acid (TFNA), a C6-fluorinated carboxylic acid, was esterified with cellulose at different molar ratios (0:1, 1:1, 2:1, and 3:1) in a trifluoroacetic acid (TFA):trifluoroacetic anhydride (TFAA):CHCl3 (2:1:1, v:v:v) solvent mixture. Free-standing films were obtained for all formulations and are presented as alternatives to composites and blends of paper with fluorinated molecules. Mechanical properties were investigated by tensile tests, and a plasticizer effect of fluorinated chains was observed. Interestingly, the wettability of these new cellulose derivatives was similar or even better than other common cellulose derivatives and fluorinated poly-mers employed in food packaging. Hydrodynamic properties were also improved by addition of TFNA, resulting in materials with water vapor permeability values comparable to other cellulose-based food packaging materials. In addition, films with the higher amounts of TFNA showed the required oil resistance for papers used in food packaging applications, as determined by the Kit Test. Finally, the biodegradation of these C6-fluorinated cel-lulose esters, assessed by biological oxygen demand (BOD) in seawater, was higher than typical bio-based polymers used in food packaging. The bioplastic synthesized at a molar ratio 1:1 (TFNA:cellulose) showed excellent performances in terms of greaseproof, hydrophobicity, ductility, and biodegradability, representing a sustainable alternative to typical plastics used in food packaging.

2022 | 10.70

Routinely, it seems assumed that the catalytic layer coated on monoliths and microchannel reactors preserve the properties of the initial powder catalyst. However, this assumption should be reasonably demonstrated since the set of chemical and physical manipulations involved in the preparation of these catalytic devices hardly does not alter the surface of the starting catalyst powders. This work aims to evaluate the transformations that takes place in a model Ru/Al2O3 catalyst during a typical slurry preparation procedure and their impact on the catalytic performance for the CO methanation reaction and the selective methanation of CO in CO2-rich reformate gases. For this purpose, we have conducted an in situ comprehensive study by means of Fourier Transform Infrared Spectroscopy (FTIR) in which the nature of the species present on the surface of the catalyst during CO hydrogenation was analyzed. This study reveals that during the preparation of the slurry the starting Ru/Al2O3 catalyst suffers a redispersion of metallic Ru particles and more surface hydroxyls are created by the incorporation of additional alumina. These modifications have a noticeable influence in the catalytic performance and despite their importance, these aspects have been poorly considered in other studies.

2019 | 10.65

The essential role of oxygen in enabling heterogeneously catalyzed Glaser–Hay coupling of phenylacetylene on Ag(100) was elucidated by STM, laboratory and synchrotron photoemission, and DFT calculations. In the absence of coadsorbed oxygen, phenylacetylene formed well-ordered dense overlayers which, with increasing temperature, desorbed without reaction. In striking contrast, even at 120 K, the presence of oxygen led to immediate and complete disruption of the organic layer due to abstraction of acetylenic hydrogen with formation of a disordered mixed layer containing immobile adsorbed phenylacetylide. At higher temperatures phenylacetylide underwent Glaser–Hay coupling to form highly ordered domains of diphenyldiacetylene that eventually desorbed without decomposition, leaving the bare metal surface. DFT calculations showed that, while acetylenic H abstraction was otherwise an endothermic process, oxygen adatoms triggered a reaction-initiating exothermic pathway leading to OH(a) + phenylacetylide, consistent with the experimental observations. Moreover, it was found that, with a solution of phenylacetylene in nonane and in the presence of O2, Ag particles catalyzed Glaser–Hay coupling with high selectivity. Rigorous exclusion of oxygen from the reactor strongly suppressed the catalytic reaction. Interestingly, too much oxygen lowers the selectivity toward diphenyldiacetylene. Thus, vacuum studies and theoretical calculations revealed the key role of oxygen in the reaction mechanism, subsequently borne out by catalytic studies with Ag particles that confirmed the presence of oxygen as a necessary and sufficient condition for the coupling reaction to occur. The direct relevance of model studies to a mechanistic understanding of coupling reactions under conditions of practical catalysis was reaffirmed.

2017 | 10.61

The calcium looping process, based on the reversible reaction between CaCO3 and CaO, is recently attracting a great deal of interest as a promising thermochemical energy storage system to be integrated in Concentrated Solar Power plants (CaL-CSP). The main drawbacks of the system are the incomplete conversion of CaO and its sintering-induced deactivation. In this work, the influence of particle size in these deactivation mechanisms has been assessed by performing experimental multicycle tests using standard limestone particles of well-defined and narrow particle size distributions. The results indicate that CaO multicycle conversion benefits from the use of small particles mainly when the calcination is carried out in helium at low temperature. Yet, the enhancement is only significant for particles below 15 μm. On the other hand, the strong sintering induced by calcining in CO2 at high temperatures makes particle size much less relevant for the multicycle performance. Finally, SEM imaging reveals that the mechanism responsible for the loss of activity is mainly pore-plugging when calcination is performed in helium, whereas extensive loss of surface area due to sintering is responsible for the deactivation when calcination is carried out in CO2 at high temperature.

2020 | 10.48

A family of 1D organic/inorganic core/shell materials formed by an inner organic nanowire (ONW) conformally covered with an inorganic wide band gap semiconductor (ZnO or TiO2) layer is presented. The developed procedure is a two-steps vacuum methodology involving the formation of supported single crystal small-molecule nanowires by physical vapor deposition and plasma enhance chemical vapor deposition (PECVD) of the inorganic shell. Critical characteristics of the last technique are the possibilities of low temperature and remote configuration deposition. Additionally, an initial step has to be included in order to create nucleation centers for the growth of the ONWs. The procedure and its general character in terms of the variability in organic core and inorganic shells composition and the applicability of the technique to different substrates are presented. The formation of the inorganic shell with no damage of the organic core single-crystalline structure is demonstrated by high resolution transmission electron microscopy. The vertical alignment of the hybrid nanostructure is achieved thanks to the interaction of the 1D organic nanostructured surfaces and the glow discharge during the deposition of the inorganic shell by PECVD. The optical properties of these core/shell NWs are studied by fluorescence spectroscopy and microscopy, and their application as nanoscale waveguides in the 550–750 nm range addressed.

2013 | 10.44

This work investigates the CO2 methanation rate of structured catalysts by tuning the geometr y of 3D-printed metal Fluid Guiding Elements (FGEs) structures based on periodically variable pseudo-gyroid geometries. The enhanced performance showed by the structured catalytic systems is mostly associated with the capability of the FGEs substrate geometries for efficient heat usages. Thus, variations on the channels diameter resulted in ca. 25% greater CO2 conversions values at intermediate temperature ranges. The highest void fraction evidenced in the best performing catalyst (3D-1) favored the radial heat transfer and resulted in significantly enhanced catalytic activity, achieving close to equilibrium (75%) conversions at 400 ? and 120 mL/min. For the 3D-1 catalyst, a mathematical model based on an experimental design was developed thus enabling the estimation of its behavior as a function of temperature, spatial velocity, hydrogen to carbon dioxide (H-2/CO2) ratio, and inlet CO2 concentration. Its optimal operating conditions were established under 3 different scenarios: 1) no restrictions, 2) minimum H-2:CO2 ratios, and 3) minimum temperatures and H-2/CO2 ratio. For instance, for the lattest scenario, the best CO2 methanation conditions require operating at 431 ?, 200 mL/min, H-2/CO2 = 3 M ratio, and inlet CO2 concentration = 10 %.

2022 | 10.40

In this work, we have developed a new kind of nanocolumnar birefringent Bragg microcavity (BBM) that, tailored by oblique angle deposition, behaves as a selective transducer of volatile organic compounds (VOCs). Unlike the atomic lattice origin of birefringence in anisotropic single crystals, in the BBM, it stems from an anisotropic self-organization at the nanoscale of the voids and structural elements of the layers. The optical adsorption isotherms recorded upon exposure of these nanostructured systems to water vapor and VOCs have revealed a rich yet unexplored phenomenology linked to their optical activity that provides both capacity for vapor identification and partial pressure determination. This photonic response has been reproduced with a theoretical model accounting for the evolution of the form birefringence of the individual layers upon vapor condensation in nanopores and internanocolumnar voids. BBMs that repel water vapor but are accessible to VOCs have been also developed through grafting of their internal surfaces with perfluorooctyltriethoxysilane molecules. These nanostructured photonic systems are proposed for the development of transducers that, operating under environmental conditions, may respond specifically to VOCs without any influence by the degree of humidity of the medium.

2021 | 10.38

In this article we show for the first time the formation of magnetic supported organic nanowires (ONWs) driven by self-assembly of a nonplanar Fe(III) phthalocyanine chloride (FePcCl) molecule. The ONWs grow by a crystallization mechanism on roughness-tailored substrates. The growth methodology consists of a vapor deposition under low vacuum and mild temperature conditions. The structure, microstructure, and chemical composition of the FePcCl NWs are thoroughly elucidated and compared with those of Fe(II) phthalocyanine NWs by a consistent and complementary combination of advanced electron microscopies and X-ray spectroscopies. In a further step, we vertically align the NWs by conformal deposition of a SiO2 shell. Such orientation is critical to analyze the magnetic properties of the FePcCl and FePc supported NWs. A ferromagnetic behavior below 30 K with an easy axis perpendicular to the phthalocyanine plane was observed in the two cases with the FePcCl nanowires presenting a wider hysteresis. These results open the path to the fabrication of nanostructured one-dimensional small-molecule spintronic devices.

2018 | 10.16

Lead halide perovskite (LHP) nanocrystals (NCs) have gained attention over the past decade due to their outstanding optoelectronic properties, making them a suitable material for efficient photovoltaic and light emitting devices. Due to its soft nature, these nanostructures undergo strong structural changes upon irradiation, where these light-induced processes are strongly influenced by the environment. Since most processing routes for LHP NCs are based on colloidal approaches, the role of factors such as stabilizing ligands or solvents is usually hard to disentangle from the interaction of external radiation with the perovskite material. Employing a recently proposed synthetic approach, where ligand-free NCs can be grown within metal-oxide-based insulating nanoporous matrices, it has been feasible to perform a clean study of the effect of the surrounding atmosphere on the photophysical properties of perovskite NCs, avoiding the interference of protective capping layers or solvents. Simultaneous light-induced photo-activation and darkening processes are monitored and disentangled, and their relation with bulk and surface processes, respectively, demonstrated.

2021 | 10.05

The combination of light‐emitting diodes (LEDs) and rare earth (RE) phosphors as color‐converting layers comprises the basis of solid‐state lighting. Indeed, most LED lamps include a photoluminescent coating made of phosphor material, i.e., crystalline matrix suitably doped with RE elements, to produce white light from a blue or ultraviolet LED chip. Transparent phosphor‐based films constitute starting materials for new refined emitters that allow different photonic designs to be implemented. Among the different photonic strategies typically employed to tune or enhance emission, surface texturing has proved its versatility and feasibility in a wide range of materials and devices. However, most of the nanofabrication techniques cannot be applied to RE phosphors directly because of their chemical stability or because of their cost. The first monolithic patterned structure of down‐shifting nanophosphors with square arrays of nanoholes with different lattice parameters is reported in this study. It is shown that a low‐cost soft‐nanolithography procedure can be applied to red‐emitting nanophosphors (GdVO4:Eu3+ nanocrystals) to tune their emission properties, attaining a twofold directional enhancement of the emitted light at predesigned emission wavelengths in specific directions.

2021 | 10.05

The present study describes the preparation of a novel 1,2,4,5-benzene tetracarboxylic acid doped polyaniline@zinc phosphate (BTCA-PANI@ZnP) nanocomposite via a facile two-step procedure. Thereafter, the as-prepared composite material adsorption characteristics for Cr(VI) ions removal were evaluated under batch adsorption. Kinetic approach studies for Cr(VI) removal, clearly demonstrated that the results of the adsorption process followed the pseudo second order and Langmuir models. The thermodynamic study indicated a spontaneous and endothermic process. Furthermore, higher monolayer adsorption was determined to be 933.88 mg g1 . In addition, the capability study regarding Cr(VI) ions adsorption over BTCA-PANI@ZnP nanocomposite clearly revealed that our method is suitable for large scale application. X-ray photoelectron spectroscopy (XPS) analysis confirmed Cr(VI) adsorption on the BTCA-PANI@ZnP surface, followed by its subsequent reduction to Cr(III). Thus, the occurrence of external mass transfer, electrostatic attraction and reduction phenomenon were considered as main mechanistic pathways of Cr(VI) ions removal. The superior adsorption performance of the material, the multidimensional characteristics of the surface and the involvement of multiple removal mechanisms clearly demonstrated the potential applicability of the BTCA-PANI@ZnP material as an effective alternative for the removal of Cr(VI) ions from wastewater.

2021 | 9.97

Moisture-induced degradation in perovskite solar cells was thoroughly investigated by structural (SEM, EDS, XRD and XPS) and device characterization (impedance and intensity modulated photocurrent spectroscopy) techniques. Both the influence of the perovskite composition and the nature of the hole selective material were analyzed. The degradation rate was found to be significantly slower for mixed perovskites and P3HT-based devices. However, for a fixed degradation degree (defined as a 50% drop from the initial photocurrent), all configurations show similar features in small-perturbation analysis. Thus, a new mid-frequency signal appears in the impedance response, which seems to be related to charge accumulation at the interfaces. In addition, faster recombination, with a more important surface contribution, and slower transport were clearly inferred from our results. Both features can be associated with the deterioration of the contacts and the formation of a higher number of grain boundaries.

2017 | 9.93

The conversion of biogas, mainly formed of CO2 and CH4, into high-value platform chemicals is increasing attention in a context of low-carbon societies. In this new paradigm, acetic acid (AA) is deemed as an interesting product for the chemical industry. Herein we present a fresh overview of the current manufacturing approaches, compared to potential low-carbon alternatives. The use of biogas as primary feedstock to produce acetic acid is an auspicious alternative, representing a step-ahead on carbon-neutral industrial processes. Within the spirit of a circular economy, we propose and analyse a new BIO-strategy with two noteworthy pathways to potentially lower the environmental impact. The generation of syngas via dry reforming (DRM) combined with CO2 utilisation offers a way to produce acetic acid in a two-step approach (BIO-Indirect route), replacing the conventional, petroleum-derived steam reforming process. The most recent advances on catalyst design and technology are discussed. On the other hand, the BIO-Direct route offers a ground-breaking, atom-efficient way to directly generate acetic acid from biogas. Nevertheless, due to thermodynamic restrictions, the use of plasma technology is needed to directly produce acetic acid. This very promising approach is still in an early stage. Particularly, progress in catalyst design is mandatory to enable low-carbon routes for acetic acid production.

2022 | 9.80

A working electrode design based on a highly porous 1D photonic crystal structure that opens the path towards high photocurrents in thin, transparent, dye-sensitized solar cells is presented. By enlarging the average pore size with respect to previous photonic crystal designs, the new working electrode not only increases the device photocurrent, as predicted by theoretical models, but also allows the observation of an unprecedented boost of the cell photovoltage, which can be attributed to structural modifications caused during the integration of the photonic crystal. These synergic effects yield conversion efficiencies of around 3.5% by using just 2 mu m thick electrodes, with enhancements between 100% and 150% with respect to reference cells of the same thickness.

2012 | 9.77

Integrating bioenergy and carbon capture and storage (BECCS) presents a great opportunity for power produc-tion with negative global CO2 emissions. This work explores a novel synergetic system that integrates mem-branes, partial biomass oxycombustion and the calcium looping (CaL) process. Polymeric membranes generate oxygen-enriched air (OEA) with an O2 concentration of 39%v/v, which is used for partial oxycombustion of biomass waste. The CO2-enriched flue gas evolves from the waste-to-energy plant to the CaL unit, where CO2 concentration is increased up to 90-95%v/v, ready for purification and sequestration. Compared to only oxy-combustion systems, the proposed concept presents fewer technological challenges in retrofitting boilers to waste-to-energy plants. Moreover, this new approach is highly efficient as integrating membranes to produce OEA instead of cryogenic distillation systems significantly reduces energy consumption. A novel integration concept is modelled to evaluate the whole process efficiency and the effect of key parameters on the system performance, such as the temperature of the reactors, the membrane surface area, and the partial oxy-combustion degree. The results show that the so-called mOxy-CaL system has an energy consumption associ-ated with CO2 capture below 4 MJ/kg CO2 (a 31% lower than that for a conventional CaL process), with a higher CO2 capture efficiency than oxycombustion and the CaL process separately. On the other hand, the economic analysis shows a higher CO2 capture cost for the novel configuration than for the typical CaL configuration due to the additional investment cost of the membrane system. Improvements in membrane performance by increasing its permeance and diminishing the required surface area would significantly reduce the economic cost of this novel integration. Using membranes with permeance over 400 GPU would boost the system's competitiveness.

2023 | 9.70

Transparent thin film electrodes made of vertically aligned nanocolumns of TiO2 with well-controlled oblique angles were grown by physical vapor deposition at glancing incidence (PVD-GLAD). For an electrode thickness of 500 nm, we report a 40% variation on solar cell efficiency (from 0.6% to 1.04%) when the deposition angle was modified between 60° and 85°. Transparent thicker films with higher surface area deposited at the optimal angle of 70° were grown with a zigzag morphology which confers high mechanical strength to the thin films. Using this topology, the application of an electrode thickness of 3 m in a DSC resulted in a power conversion efficiency of 2.78% maintaining electrode transparency.

2011 | 9.61

The catalytic performance is highly related to the catalyst structure. Herein, a series of Ni nanoparticles supported on Y2O3 with different morphologies were successfully synthesized via hydrothermal process screening different pH environments. These Ni/Y2O3 catalysts were applied to efficiently produce COx-free H-2 through ammonia decomposition. We identify a significant impact of Y2O3 supports on nickel nanoclusters sizes and dispersion. The experimental results show that Ni/Y11 catalyst achieves 100% ammonia decomposition conversion under a gas hour space velocity (GHSV) of 12,000 ml.h(-1).g(cat)(-1) and temperature of 650 degrees C. Such a high level of activity over Ni/Y11 catalyst was attributed to a large specific surface area, appropriate alkalinity, and small Ni nanoparticles diameter with high dispersion.

2023 | 9.60

Hard carbons are the material of choice as negative electrode in sodium ion batteries. Despite being extensively studied, there is still debate regarding the mechanisms responsible for storage in low- and high-potential regions. This work presents a comprehensive approach to elucidate the involved storage mechanisms when Na ions insert into such disordered structures. Synchrotron X-ray total scattering experiments were performed to access quantitative information on atomic ordering in these materials at the nanoscale. Results prove that hard carbons undergo an atomic rearrangement as the graphene layers cross-link at intermediate temperatures (1200-1600 degrees C), resulting in an increase of the average interplanar distance up to 1400 degrees C, followed by a progressive decrease. This increase correlates with the positive trend in the reversible capacity of biomass-derived carbons when processed up to 1200-1600 degrees C due to an increased capacity at low potential (<= 0.1 V vs Na/Na+). A decrease in achievable sloping capacity with increasing heat-treatment temperature arises from larger crystalline domains and a lower concentration of defects. The observed correlation between structural parameters and electrochemical properties clearly supports that the main storage of Na ions into a hard-carbon structure is based on an adsorption-intercalation mechanism.

2019 | 9.57

Swelling layered clay minerals form an important sub-group of the phyllosilicate family. They are characterized by their ability to expand or contract in the presence or absence of water. This property makes them useful for a variety of applications, ranging from environmental technologies to heteroge-neous catalysis, and including pharmaceutical and industrial applications. Solid State Nuclear Magnetic Resonance (SS-NMR) has been extensively applied in the characterization of these materials, providing useful information on their dynamics and structure that is inaccessible using other characterization methods such as X-ray diffraction. In this review, we present the key contributions of SS-NMR to the understanding of the mechanisms that govern some of the main applications associated to swelling clay minerals. The article is divided in two parts. The first part presents SS-NMR conventional applications to layered clay minerals, while the second part comprises an in-depth review of the information that SS-NMR can provide about the different properties of swelling layered clay minerals.

2021 | 9.45

Iridium nanoparticles deposited on a variety of surfaces exhibited thermal sintering characteristics that were very strongly correlated with the lability of lattice oxygen in the supporting oxide materials. Specifically, the higher the lability of oxygen ions in the support, the greater the resistance of the nanoparticles to sintering in an oxidative environment. Thus with gamma-Al2O3 as the support, rapid and extensive sintering occurred. In striking contrast, when supported on gadolinia-ceria and alumina-ceria-zirconia composite, the Ir nanoparticles underwent negligible sintering. In keeping with this trend, the behavior found with yttria-stabilized zirconia was an intermediate between the two extremes. This resistance, or lack of resistance, to sintering is considered in terms of oxygen spillover from support to nanoparticles and discussed with respect to the alternative mechanisms of Ostwald ripening versus nanoparticle diffusion. Activity towards the decomposition of N2O, a reaction that displays pronounced sensitivity to catalyst particle size (large particles more active than small particles), was used to confirm that catalytic behavior was consistent with the independently measured sintering characteristics. It was found that the nanoparticle active phase was Ir oxide, which is metallic, possibly present as a capping layer. Moreover, observed turnover frequencies indicated that catalyst-support interactions were important in the cases of the sinter-resistant systems, an effect that may itself be linked to the phenomena that gave rise to materials with a strong resistance to nanoparticle sintering. 

2016 | 9.45

Platinum and gold structured catalysts were compared as active phases in classical and O2-assisted Water Gas Shift (WGS) reaction. Both metals were supported on iron-doped ceria mixed oxide and then, structured on metallic micromonolithic devices. As expected the WGS activity of both micromonoliths is conditioned by the nature of the noble metals being Pt the most active metal in traditional conditions. However, the addition of oxygen to the classical water gas feed turns the balance in favor of the gold based catalysts, being the presence of gold responsible for an excessive improvement of the catalytic activity.

2016 | 9.45

The WGS reaction over multicomponent Au/Ce1-xCuxO2/Al2O3 catalysts is studied in this work. The systems are carefully designed aiming to take advantage of every active phase included in the formulation: gold, ceria and copper. Special emphasis is given to the CeO2-CuO synergy and its influence on the displayed catalytic performance with and without gold. To this aim a meaningful correlation between the physicochemical properties of the mixed materials and their activity/stability is proposed. In general terms the developed catalysts present high activity under realistic WGS reaction conditions, with fairly good long term stability. In addition, the systems successfully withstand start-up/shut-downs situations, indispensable requisite for real applications in the field of pure hydrogen production for fuel cell goals. 

2016 | 9.45

The influence of the crystal structure and chemical nature of some ionic liquid/phosphomolybdate hybrids on their catalytic activity in the epimerization of glucose was studied. A clear evidence of structure-activity relationship was found. The inorganic part of the hybrid ensured the availability of active sites for the reaction, while the organic cation part organized the structure and controled the diffusion of the reactants. This study can be used as a first approach to predict the symmetry, long range order and availability of active sites in the presented class of imidazolium based polyoxometalate hybrids.

2018 | 9.41

We have developed a trimodal bioimaging probe for near-infrared luminescent imaging, high-field magnetic resonance imaging, and X-ray computed tomography using Dy3+ as the paramagnetic component and Nd3+ as the luminescent cation, both of them incorporated in a vanadate matrix. Among different essayed architectures (single phase and core-shell nanoparticles) the one showing the best luminescent properties is that consisting of uniform DyVO4 nanoparticles coated with a first uniform layer of LaVO4 and a second layer of Nd3+-doped LaVO4. The magnetic relaxivity (r2) at high field (9.4 T) of these nanoparticles was among the highest values ever reported for this kind of probes and their X-ray attenuation properties, due to the presence of lanthanide cations, were also better than those of a commercial contrast agent (iohexol) commonly used for X-ray computed to-mography. In addition, they were chemically stable in a physiological medium in which they could be easily dispersed owing to their one-pot functionalization with polyacrylic acid, and, finally, they were non-toxic for human fibroblast cells. Such a probe is, therefore, an excellent multimodal contrast agent for near-infrared luminescent imaging, high-field magnetic resonance imaging, and X-ray computed tomography.

2023 | 9.40

Heating decarbonisation through electrification requires the development of novel heat batteries. They should be suitable for the specific application and match the operation conditions of domestic renewable energy sources. Supercooled liquids, often considered a drawback of phase change materials, are among the most promising technologies supporting heating decarbonisation. Although some studies have shed light on stable supercooling, the fundamentals and stability remain open problems not always accompanied by relevant experimental in-vestigations. This research critically analyses the physic and chemistry of sodium acetate (SA, NaCH3COO) aqueous solution, a low-cost, non-toxic, and abundant compound with stable supercooling for long-term heat storage. It has an appropriate phase change temperature for high-density heat storage using heat pumps or solar thermal technologies in residential applications. The existing discrepancies in literature are critically discussed through a systematic experimental evaluation, providing novel insights into efficient material design and appropriate boundary conditions for reliable material use in long-term heat batteries. Despite previous studies showing that the thermal reliability and stability of sodium acetate aqueous solution as a supercooled liquid for heat storage cannot be guaranteed, this study demonstrates that through an appropriate encapsulation and sealing method, the peritectic composition of sodium acetate solution (p-SA 58 wt%) can be used as a super-cooled liquid for long-term heat storage with a stable melting temperature of 57 degrees C, appropriate for domestic heat technologies. It is demonstrated that energy storage efficiency can be maintained under cycling, with a constant latent heat storage capacity of 245 kJ/kg and a volumetric storage density of 314 MJ/m3. It was confirmed that the material should achieve a fully-melted state for stable supercooling. Finally, local cooling and retaining seed crystals through high pressure were highlighted as the most suitable basic principles for successful crystallization and heat release. This promising material can store energy for long periods without latent heat losses due to its stable subcooling. Latent heat can be released when required at any selected time and tem-perature just by a simple activation process.

2022 | 9.40

Plasma-assisted catalysis of the reaction between CO2 and C2H6 in a single-pass, ferroelectrically moderated dielectric barrier discharge reactor has been studied at near ambient temperature as a function of physicochemical and electrical reaction variables. The presence of small amounts of a vanadia/alumina catalyst dispersed on the BaTiO3 ferroelectric markedly enhanced the production of formaldehyde, the focus of this work. A maximum HCOH selectivity of 11.4% (defined with respect to the number of ethane carbon atoms consumed) at 100% ethane conversion was achieved, the other products being CO, H2O, H2, CH4 and a small amount of C3H8. N2O was also an effective partial oxidant (HCOH selectivity 8.9%) whereas use of O2 led to complete combustion, behavior that may be rationalized in terms of the electron impact excitation cross sections of the three oxidants. Control experiments with the coproducts CH4 and C3H8 showed that these species were not intermediates in HCOH formation from C2H6. Analysis of reactor performance as a function of discharge characteristics revealed that formaldehyde formation was strongly favored at low frequencies where the zero-current fraction of the duty cycle was greatest, the implication being that plasma processes also acted to destroy previously formed products. A tentative reaction mechanism is proposed that accounts for the broad features of formaldehyde production.

2014 | 9.31

Chemical CO2 recycling in the gas phase constitutes a straightforward approach for effective CO2 conversion to added-value products like syngas or synthetic methane. In this scenario, some traditional processes such as the dry and bi-reforming of methane, the CO2 methanation and the reverse water-gas shift have gained a renewed interest from the CO2 utilisation perspective. Indeed, these reactions represent flexible routes to upgrade CO2 and their application at an industrial scale could substantially reduce CO2 emissions. The bottleneck for the implementation of these processes at the commercial level is the development of highly active and robust heterogeneous catalysts able to overcome CO2 activation and deliver sufficient amounts of the upgrading products (i.e. syngas or synthetic natural gas) at the desired operating conditions. This review paper gathers the most recent advances in the design of new catalytic formulations for chemical CO2 recycling in the gas phase and constitutes an overview for experts and newcomers in the field to get fundamental insights into this emerging branch of low-carbon technologies.

2022 | 9.30

We devise a unique heteronanostructure array to overcome a persistent issue of simultaneously utilizing the surface-enhanced Raman scattering, inexpensive, Earth-abundant materials, large surface areas, and multifunctionality to demonstrate near single-molecule detection. Room-temperature plasma-enhanced chemical vapor deposition and thermal evaporation provide high-density arrays of vertical TiO2 nanotubes decorated with Ag nanoparticles. The role of the TiO2 nanotubes is 3-fold: (i) providing a high surface area for the homogeneous distribution of supported Ag nanoparticles, (ii) increasing the water contact angle to achieve superhydrophobic limits, and (iii) enhancing the Raman signal by synergizing the localized electromagnetic field enhancement (Ag plasmons) and charge transfer chemical enhancement mechanisms (amorphous TiO2) and by increasing the light scattering because of the formation of vertically aligned nanoarchitectures. As a result, we reach a Raman enhancement factor of up to 9.4 × 107, satisfying the key practical device requirements. The enhancement mechanism is optimized through the interplay of the optimum microstructure, nanotube/shell thickness, Ag nanoparticles size distribution, and density. Vertically aligned amorphous TiO2 nanotubes decorated with Ag nanoparticles with a mean diameter of 10–12 nm provide enough sensitivity for near-instant concentration analysis with an ultralow few-molecule detection limit of 10–12 M (Rh6G in water) and the possibility to scale up device fabrication.

2020 | 9.23

Sustainable coatings for metal food packaging were prepared from ZnO nanoparticles (obtained by the thermal decomposition of zinc acetate) and a naturally occurring polyhydroxylated fatty acid named aleuritic (or 9,10,16-trihydroxy-hexadecanoic) acid. Both components reacted, originating under specific conditions zinc polyaleuritate ionomers. The polymerization of aleuritic acid into polyaleuritate by a solvent-free, melt polycondensation reaction was investigated at different times (15, 30, 45, and 60 min), temperatures (140, 160, 180, and 200 degrees C), and proportions of zinc oxide and aleuritic acid (0:100, 5:95, 10:90, and 50:50, w/w). Kinetic rate constants calculated by infrared spectroscopy decreased with the amount of Zn due to the consumption of reactive carboxyl groups, while the activation energy of the polymerization decreased as a consequence of the catalyst effect of the metal. The adhesion and hardness of coatings were determined from scratch tests, obtaining values similar to robust polymers with high adherence. Water contact angles were typical of hydrophobic materials with values >= 94 degrees. Both mechanical properties and wettability were better than those of bisphenol A (BPA)-based resins and most likely are related to the low migration values determined using a hydrophilic food simulant. The presence of zinc provided a certain degree of antibacterial properties. The performance of the coatings against corrosion was studied by electrochemical impedance spectroscopy at different immersion times in an aqueous solution of NaCl. Considering the features of these biobased lacquers, they can be potential materials for bisphenol A-free metal packaging.

2021 | 9.22

The stability, either chemical or thermal, and performance of colloidal quantum dot (CQD) devices are typically limited by the presence of surface-bonded organic ligands required to stabilize the nanocrystals. In addition, optimization of charge transport implies lengthy ligand exchange processing. Herein, evidence of efficient charge transport through a network of ligand-free perovskite quantum dots (PQDs) embedded in an insulating porous matrix made of monodisperse SiO2 nanoparticles is shown. Methylammonium lead iodide (CH3NH3PbI3 or MAPbI(3)) QDs are prepared in situ by infiltration of precursors within the matrix pores, which act both as nanoreactors for the synthetic reaction and as supporting scaffolds, hence reducing the number of synthetic and postprocessing steps usually required in CQD solar cells. Above a certain nanocrystal load, charge percolation is reached and dot-to-dot transport achieved without compromising quantum confinement effects. Solar cells based on MAPbI(3) QDs prepared in this way present a 9.3% efficiency, the highest reported for a scaffold-supported PQD solar cell, and significantly improved stability under solar illumination with respect to their bulk counterparts. Therefore, adequately designed networks of ligand-free PQDs can be used as both light harvesters and photocarrier conductors, in an alternative configuration to that used in previously developed QD solar cells.

2021 | 9.17

Composites (AgBr/SnO2) comprised of AgBr and SnO2 with different molar % of bare SnO2, have been synthesized by simple precipitation methods; the bare SnO2 used, was synthesized by hydrothermal procedure. Samples have been characterized by X-ray diffraction (XRD), N2-adsorption, UV–vis diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Photocatalytic activity of the as-prepared photocatalysts was evaluated through photocatalytic degradation of rhodamine B (RhB) and caffeic acid (CAFA) under UV and Visible illumination. In photocatalytic degradation studies, for both substrates, conversion rates of around 95% were found in 45 min of both UV-illumination and 85% under visible lighting. These conversion rates were superior than the conversion rates of pure parental components, AgBr and SnO2 under the same experimental conditions. At least, for RhB no loss of photocatalytic activity has been observed after five recycles although the mineralization degree progressively diminished along the recycles. The enhanced photocatalytic degradation of AgBr/SnO2 compounds was attributed, in part, to a synergistic increase in adsorption viability, as well as to the effective separation of photoinduced load carriers that resulted from the formation of a heterojunction according to the type II junction. Radical scavengers’ experiments indicated that active oxidant species as O2.−, ·OH and h+ all are involved in this photocatalytic system, although it seems that O2.− played the major role in the photocatalytic degrading of RhB by AgBr/SnO2 composites. In summary, coupling AgBr with SnO2 remarkably improves the photocatalytic activity under both UV and visible-illumination with respect to the parental components. These features open the route to future applications of this material in the field of environmental remediation.

2021 | 9.14

Two-dimensional materials present exceptional crystal elasticity and provide an ideal platform to tune electrical and optical properties through the application of strain. Here we extend recent research on strain engineering in monolayer molybdenum disulfide using an adamantane plasma polymer pinning layer to achieve unprecedented crystal strains of 2.8%. Using micro-reflectance spectroscopy, we report maximum strain gauge factors of -99.5 meV/% and -63.5 meV/% for the A and B exciton of monolayer MoS2, respectively, with a 50 nm adamantane capping layer. These results are corroborated with photoluminescence and Raman measurements on the same samples. Taken together, our results indicate that adamantane polymer is an exceptional capping layer to transfer substrate-induced strain to a 2D layer and achieve higher levels of crystal strain.

2023 | 9.10

The development of efficient strategies to tune the CO2RR selectivity of Cu-based catalytic interfaces, especially on specific domains, such as Cu (200) facets with high activity toward competitive hydrogenation evolution reaction (HER), remains a challenging task. In this work, Cu-based catalytic layers with thiocyanate (-SCN), cyanide (-CN), or ethylenediamine (-NH2R) coordination linkages are prepared on Cu nanocolumns arrays (Cu NCAs) with predominant (200) exposed facets. The coordination of these ligands induces more Cu+ species and inhibits the adsorption of H & lowast; on the Cu (200) facet, leading to enhanced CO2RR performance and substantially suppressing the competitive HER. The faradaic efficiency (FE) of Cu-SCN, Cu-CN, and Cu-NH2R NWAs for producing HCOOH, C2H4, and C1 mixture products (HCOOH and CO) reach to 66.5%, 21.1%, and 57.1%, respectively. In situ spectroscopic studies reveal Cu-SCN, Cu-CN, and Cu-NH2R exhibit more reasonable adsorption energy toward & lowast;OCHO, *CO, and *COOH intermediates, promoting the HCOOH, C2H4, and C1 mixture generation, respectively. This study might provide a new perspective for the development of high-performance Cu-based CO2RR catalytic electrodes based on the combination of various commercial free-standing Cu substrates and organic/inorganic ligands. (c) 2024 Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

2024 | 9.00

Bloch surface waves sustained by truncated 1D photonic crystals (1DPCs) are well known tools for surface-enhanced spectroscopy. They provide strongly confined fields with uniform distribution over a large surface area, a characteristic exploited in standard refractometric sensing. However, their application to polarization-sensitive investigations is not straightforward because the transverse electric (TE) and magnetic (TM) surface modes possess distinct dispersion relations, therefore their relative phase is not conserved along propagation and the polarization state of any wave obtained by combining these modes is ill-defined. In this work, a novel design of a 1DPC is realized in which the TE and TM modes exhibit the same phase velocity over a broadband spectral range and thus their dispersion relations overlap. The capability to simultaneously excite TE and TM modes with a well-defined phase relation allows the generation of surface waves with a controlled polarization state. This paves the way to polarization-resolved surface-enhanced analysis, including, for example, linear and circular dichroism spectroscopy of grafted molecular layers at the photonic crystal surface.

2022 | 9.00

The optoelectronic properties of lead halide perovskites are intimately related to their crystalline phase. For the case of cesium lead iodide (CsPbI3) several polymorphs meet the Goldschmidt tolerance factor, which determines their stability, and form broad band absorber and luminescent phases. However, at room temperature none of them are stable, which prevents their use in optoelectronics. In this work, bare CsPbI3 nanocrystals are synthesized in the sub-10 nm range in the "black", light emitting, crystalline phase, using a pore controlled SiO2 matrix that limits crystal size and confers a certain degree of strain that favors their stability. Quantum confinement effects allow the tuning of the optical properties of the CsPbI3 nanocrystals by means of the crystal size. Their suitability as optoelectronic materials is demonstrated by building scaffold supported CsPbI3 quantum dot based photovoltaic and light emitting devices.

2022 | 9.00

Heating decarbonisation through electrification is a difficult challenge due to the considerable increase in peak power demand. This research proposes a novel modelling approach that utilises easily accessible national-level data to identify the required heat storage volume in buildings to decrease peak power demand and maximises carbon reductions associated with electrified heating technologies through smart demand-side response. The approach assesses the optimal shifting of heat pump operation to meet thermal heating demand according to different heat storage capacities in buildings, which are defined in relation to the time (in hours) in which the heating demand can be provided directly from the heat battery, without heat pump operation. Ten scenarios (S) are analysed: two baselines (S1-S2) and eight load shifting strategies (S3-S10) based on hourly and daily demand-side responses. Moreover, they are compared with a reference scenario (S0), with heating currently based on fossil fuels. The approach was demonstrated in two different regions, Spain and the United Kingdom. The optimal heat storage capacity was found on the order of 12 and 24 h of heating demand in both countries, reducing additional power capacity by 30-37% and 40-46%, respectively. However, the environmental benefits of heat storage alternatives were similar to the baseline scenario due to higher energy consumption and marginal power generation based on fossil fuels. It was also found that load shifting capability below 4 h presents limited benefits, reducing additional power capacity by 10% at the national scale. The results highlight the importance of integrated heat storage technologies with the electrification of heat in highly gas-dependent regions. They can mitigate the need for an additional fossil-based dispatchable generation to meet high peak demand. The modelling approach provides a high-level strategy with regional specificity that, due to common datasets, can be easily replicated globally. For reproducibility, the code base and datasets are found on GitHub.

2023 | 9.00

Energy storage is a key factor in the development of renewables-based electrical power systems. In recent years, the thermochemical energy storage system based on calcium-looping has emerged as an alternative to molten salts for energy storage in high-temperature concentrated solar power plants. This technology still presents some challenges that could be solved by integrating the thermochemical energy storage system based on calcium hydroxide. This work studies a novel concentrated solar power system integrating calcium-looping and calcium hydroxide thermochemical energy storage systems. The results show that the combined use of hydration -dehydration cycles in the calcination-carbonation processes of the calcium looping for energy storage could partially solve the issue related to the multicyclic deactivation of calcium oxide. The improvement in the con-version of calcium oxide during carbonation is demonstrated experimentally when hydration-dehydration cycles are combined. Numerical simulations demonstrate the technical feasibility of the integrated process, with effi-ciencies ranging between 38-46%, improved with the increase in calcium oxide conversion in the carbonator, showing the potential of the proposed integration.

2023 | 9.00

Phase change materials (PCM) have been widely investigated for heat storage and transfer applications. Numerous numerical simulation approaches have been proposed for modelling their behaviour and predicting their performance in thermal applications. However, simulation approaches do not consider the kinetics of the phase transition processes, compromising the accuracy of their predictions. The phase change is a kinetically driven process in which both the reaction rate and the reaction progress depend on the heating schedule. This work evaluates and parametrises the influence of kinetics in the melting and crystallisation behaviour of a well-known PCM, PEG1500, and compares potential discrepancies with common phase change parametrisation alternatives. The kinetic dependence was experimentally evaluated through differential scanning calorimetry (DSC). The kinetic parameters required for modelling the kinetics of the processes were determined by both model-free and model-fitting procedures following ICTAC (International Confederation for Thermal Analysis and Calorimetry) recommendations. Then, the phase transition was parametrised through a kinetic model and compared with three conventional phase transition models: linear without hysteresis, non-linear without hysteresis, and non-linear with hysteresis. The statistical comparison between models demonstrates the higher accuracy of the kinetic approach to correctly represent the partial enthalpy distribution of latent heat storage materials during alternative phase change rates, obtaining a coefficient of determination (R-2) of 0.80. On the other hand, the accuracy of kinetic-independent models is limited to the range from 0.40 to 0.61. The results highlight the high discrepancies of conventional models compared to the kinetic approach and provide criteria and guidelines for efficient kinetic modelling of phase change in heat transfer evaluations.

2021 | 8.91

The calcium looping multicycle performance of CaO-based materials, derived from calcium magnesium acetates with different Mg content were tested under experimental conditions compatible with thermochemical energy storage. In order to reduce the sintering-induced decay in performance, calcination at an absolute CO2 pressure of 0.1 bar and 0.01 bar is implemented. CaO carbonation is performed at standard 1 bar CO2 conditions. The samples can be fully calcined in short residence times. Samples with MgO present high cycling stability, even when the MgO content is as low as 5 mol%. The effective conversion values lie within the range 0.88-0.84 over ten calcination/carbonation cycles, which provides an accumulated energy storage density of 90.9 GJ/m3. This outstanding reactivity is related with the microstructure of the sample after calcination composed of CaO nanoparticles that are highly reactive for carbonation.

2023 | 8.90

Herein we realize an optical design that optimizes the performance of bifacial solar cells without modifying any of the usually employed components. In order to do so, dielectric scatterers of controlled size and shape have been successfully integrated in the working electrodes of dye-sensitized solar cells (DSSCs), resulting in bifacial devices of outstanding performance. Power conversion efficiencies (PCEs) as high as 6.7% and 5.4% have been attained under front and rear illumination, respectively, which represent a 25% and a 33% PCE enhancement with respect to an 8 μm-thick standard solar cell electrode using platinum as the catalytic material. The remarkable bifacial character of our approach is demonstrated by the high rear/front efficiency ratio attained, around 80%, which is among the largest reported for this sort of device. The proposed optimized design is based on a Monte Carlo approach in which the multiple scattering of light within the cell is fully accounted for. We identified that the spherical shape of the scatterers is the key parameter controlling the angular distribution of the scattering, the most efficient devices being those in which the inclusions provide a narrow forward-oriented angular distribution of the scattered light.

2016 | 8.87

High energy density, cycling stability, low cost and scalability are the main features required for thermochemical energy storage systems to achieve a feasible integration in Concentrating Solar Power plants (CSP). While no system has been found to fully satisfy all these requirements, the reversible CaO/CaCO3 carbonation reaction (CaL) is one of the most promising since CaO natural precursors are affordable and earth-abundant. However, CaO particles progressively deactivate due to sintering-induced morphological changes during repeated carbonation and calcinations cycles. In this work, we have prepared acicular calcium and magnesium acetate precursors using a simple, cost-effective and easily scalable technique that requires just the natural minerals and acetic acid, thereby avoiding expensive reactants and environmentally unfriendly solvents. Upon thermal decomposition, these precursors yield a stable porous structure comprised of well dispersed MgO nanoparticles coating the CaO/CaCO3 grains that is resistant to pore-plugging and sintering while at the same time exhibits high long term effective conversion. Process simulations show that the employment of these materials could significantly improve the overall CSP-CaL efficiency at the industrial level.

2019 | 8.85

Bright luminescence in rare-earth (RE) nanocrystals, the so-called nanophosphors, is generally achieved by choosing a host that enables an effective excitation of the RE activator through charge or energy transfer. Although tungstate, molybdate, or vanadate compounds provide the aforementioned transfer, a comparative analysis of the efficiency of such emitters remains elusive. Herein, we perform a combined structural and optical analysis, which reveals that the tetragonal GdVO4 matrix gives rise to the highest efficiency among the different transparent nanophosphor films compared. Then, we demonstrate that by a sequential stacking of optical quality layers made of Eu3+- and Dy3+-doped nanocrystals, it is possible to attain highly transparent white-light-emitting coatings of tunable shade with photoluminescence quantum yields above 35%. Layering provides a precise dynamic tuning of the chromaticity based on the photoexcitation wavelength dependence of the emission of the nanophosphor ensemble without altering the chemical composition of the emitters or degrading their efficiency. The total extinction of the incoming radiation along with the high quantum yields achieved makes these thin-layered phosphors one of the most efficient transparent white converter coatings ever developed.

2019 | 8.76

Isolation of high-level radioactive waste (HLW) in deep geological repositories (DGR) through a multibarrier concept is the most accepted approach to ensure long-term safety. Clay minerals are one of the most promising materials to be used as engineered barriers. In particular, high charge micas, as components of the engineered barrier, show superselectivity for some radioactive isotopes and a large adsorption capacity, which is almost twice that of the other low charge aluminosilicates. In addition, high charge micas are optimum candidates for decontamination of nuclear waste through two different mechanisms; namely an ion exchange reaction and a nonreversible mechanism involving the formation of new stable crystalline phases under hydrothermal conditions. In this work, we report a new in situ optical sensor based on the incorporation of Eu3+ in these high charge micas for tracking the long-term physical-chemical behavior of HLW contaminants in DRG under mild hydrothermal conditions. The incorporation of Eu3+ into the interlayer space of the mica originates a well resolved green and red luminescence, from both the 5D1 and 5D0 excited states, respectively. The formation of new crystalline phases under hydrothermal conditions involves important changes in the Eu3+ emission spectra and lifetime. The most interesting features of Eu3+ luminescence to be used as an optical sensor are (1) the presence or absence of the Eu3+ green emission from the 5D1 excited state, (2) the energy shift of the 5D0 → 7F0 transition, (3) the crystal-field splitting of the 7F1 Eu3+ level, and (4) the observed luminescence lifetimes, which are directly related to the interaction mechanisms between the lanthanide ions and the silicate network.

2019 | 8.76

This work is carried out in the context of the anion exchange membrane water electrolysis (AEMWE) and pursuits to determine the influence of different cell components on the global electrochemical performance. Ionomer-free electrodes consisting of anodic Ni-Fe and cathodic Ni electrocatalysts deposited by magnetron sputtering in an oblique angle deposition configuration were utilized for this study. In addition to the characteristics and equivalent thickness of the electrocatalysts, other factors affecting the efficiency that have been considered in this study encompass the type of gas diffusion layer (GDLs), including carbon paper and stainless-steel fiber paper supports, and several commercial anion exchange membranes. The electrocatalytic performances in both a threeelectrode and complete single cell AEMWE set-ups, together with the physico-chemical characterization of the electrodes before and after operation, have served to select the optimum components for the utilized cell configuration. Thus, current densities of 670 mA cm-2, at polarization voltage of 2.2 V, 1.0 M KOH electrolyte and 40 degrees C were obtained in a membrane electrode assembly. A seven days chronopotentiometry experiment at a fixed current of 400 mA cm-2 demonstrated a noticeable stability of this type of AEMWE cells incorporating ionomer-free electrodes.

2022 | 8.70

The photophysical properties of films of organic-inorganic lead halide perovskites under different ambient conditions are herein reported. We demonstrate that their luminescent properties are determined by the interplay between photoinduced activation and darkening processes, which strongly depend on the atmosphere surrounding the samples. We have isolated oxygen and moisture as the key elements in each process, activation and darkening, both of which involve the interaction with photogenerated carriers. These findings show that environmental factors play a key role in the performance of lead halide perovskites as efficient luminescent materials.

2015 | 8.54

The highly visible and infrared (up to 6 mu m) transparent Sr3Al2O6 polycrystalline ceramic was obtained by full crystallization of the corresponding glass composition. The glass synthesis and the direct congruent crystallization processes are described, and the material transparency is discussed in light of its microstructure. This new transparent ceramic exhibits a high density (i.e., complete absence of porosity) and micrometer-scale crystallites with very thin grain boundaries. These microstructural characteristics, inherent to the preparation method, minimize light scattering and demonstrate the advantages of this synthesis route compared to the high-pressure process used for the few reported transparent polycrystalline materials. This Sr3Al2O6 ceramic shows a H = 10.5 GPa hardness, a E-r = 150 GPa reduced elasticity modulus, and a 9.6 x 10(-6) K-1 thermal expansion coefficient. Such a transparent strontium aluminate ceramic opens the way to a wide range of applications, especially photonics when doped by various doping agents. As examples, the luminescence of Sr3Al2O6:Eu3+ and Sr3Al2O6:Er3+, which show strong emissions in the visible and infrared ranges, respectively, is presented. Moreover, the Sr3Al2O6:Ce3+ material was found to exhibit scintillation properties under X-ray excitation. Interestingly, the analogous Sr3Ga2O6 transparent polycrystalline ceramic material could equally be prepared using the same elaboration method, although its hygroscopicity prevents the preservation of its high transparency under normal conditions. The establishment of the key factors for the transparency of this economical and innovative synthesis method should enable the prediction of new classes of technologically relevant transparent ceramics.

2013 | 8.54

Reinforced films were fabricated by impregnating paper in ethyl cellulose solutions. After solvent evaporation, the infused ethyl cellulose acted as binder of the paper microfibres and occupied the pores and cavities, thus improving the mechanical and barrier properties. To prepare active films, avocado by-products from guacamole industrial production were extracted in ethyl acetate. Then, the extract (optimized to be rich in phenolic compounds and flavonoids and mainly composed by lipids) was incorporated to the paper reinforced with the highest content of ethyl cellulose. In general, the addition of the avocado by-products extract decreased the water uptake and permeability, improved the wettability, and increased the biodegradability in seawater and the antioxidant capacity. In addition, these films acted as barriers and retainers for Escherichia coli and Bacillus cereus. The potentiality of these materials for food packaging was demonstrated by low overall migrations and a similar food preservation to common low-density polyethylene.

2023 | 8.50

In this work, we demonstrate a synthetic route to attain methylammonium lead bromide (CH3NH3PbBr3) perovskite nanocrystals (nc-MAPbBr(3), 1.5 nm < size < 3 nm) and provide them with functionality as highly efficient flexible, transparent, environmentally stable, and adaptable color converting films. We use nanoparticle metal oxide (MOx) thin films as porous scaffolds of controlled nanopores size distribution to synthesize nc-MAPbBr(3) through the infiltration of perovskite liquid precursors. We find that the control over the reaction volume imposed by the nanoporous scaffold gives rise to a strict control of the nanocrystal size, which allows us to observe well-defined quantum confinement effects on the photo-emission, being the luminescence maximum tunable with precision between lambda = 530 nm (green) and lambda = 490 nm (blue). This hybrid nc-MAPbBr(3)/MOx structure presents high mechanical stability and permits subsequent infiltration with an elastomer to achieve a self-standing flexible film, which not only maintains the photo-emission efficiency of the nc-MAPbBr(3) unaltered but also prevents their environmental degradation. Applications as adaptable color-converting layers for light-emitting devices are envisaged and demonstrated.

2018 | 8.46

Analyte-sensitive fluorophores are a common tool in analytical chemistry. In case they are conjugated to the surface of colloidal nanoparticles new or improved applications are possible. An overview of the potential of such fluorophore-particle conjugates is given by means of several examples. First, using pH-sensitive fluorophores attached to particles are a helpful tool for investigating particle uptake by cells, as they can indicate whether particles are in the neutral slightly alkaline extracellular medium, or in acidic intracellular vesicles after endocytosis. Second, relating to lifetime-based methodologies, the fluorescence resonance energy transfer between fluorophores attached to quantum dots leads to longer lifetimes, improving their performance and expanding the possibilities of methods, such as lifetime imaging for in vivo applications. It also can be exploited for multiplexing approaches, in which the effective lifetime of the fluorophores can be tuned, allowing thus for the detection of several analytes based on temporal discrimination. Attention is focused to these three areas of application, because they are among the most reported in recent literature, and therefore of particular interest.

2016 | 8.44

This study explores the effect of steam addition during carbonation on the multicyclic performance of limestone under calcium looping conditions compatible with (i) CO2 capture from postcombustion gases (CCS) and with (ii) thermochemical energy storage (TCES). Steam injection has been proposed to improve the CO2 uptake capacity of CaO-based sorbents when the calcination and carbonation loops are carried out in CCS conditions: at moderate carbonation temperatures (similar to 650 degrees C) under low CO2 concentration (typically similar to 15% at atmospheric pressure). However, the recent proposal of calcium-looping as a TCES system for integration into concentrated solar power (CSP) plants has aroused interest in higher carbonation temperatures (similar to 800-850 degrees C) in pure CO2. Here, we show that steam benefits the multicyclic behavior in the milder conditions required for CCS. However, at the more aggressive conditions required in TCES, steam essentially has a neutral net effect as the CO2 uptake promoted by the reduced CO2 partial pressure but also is offset by the substantial steam-promoted mineralization in the high temperature range. Finally, we also demonstrate that the carbonation rate depends exclusively on the partial pressure of CO2, regardless of the diluting gas employed.

2022 | 8.40

This work analyzes the relevant influence of milling on the CO2 capture performance of CaO derived from natural limestone. Diverse types of milling mechanisms produce contrasting effects on the microstructure of the CaO formed after calcination of the milled limestone samples, which affects crucially the kinetics of carbonation at conditions for CO2 capture. The capture capacity of CaO derived from limestone samples milled using either shear or impact based mills is impaired compared to as-received limestone. After calcination of the milled samples, the resulting CaO porosity is increased while crystallinity is enhanced, which hinders carbonation. Conversely, if the material is simultaneously subjected to intense impact and shear stresses, CaO porosity is promoted whereas CaO cristanillity is reduced, which enhances carbonation in both the reaction and solid-state diffusion controlled regimes.

2018 | 8.36

The CO oxidation activity of 1 wt.% gold catalysts prepared by deposition-precipitation on a series of ceria doped with Zr supports was studied. The supports (10, 25 and 50 Zr at.%) were synthesized by a pseudo sol-gel method through the thermal decomposition of the corresponding metallic propionates. All the prepared solids were characterized by means of XRF, BET, XRD, Raman spectroscopy, SEM, and H-2-TPR. Solid solution was obtained in all mixed systems, while the segregation of different Ce-Zr oxides was observed for the solid with the 50 Zr at.%. The oxygen vacancies population and the amount of easier reducible Ce4+ species in the solids increase with the Zr content. No major textural or structural modifications were detected after gold deposition, although a strong Au-support interaction was generated. Such interaction is strongly influenced by the nucleation of gold deposits on the oxygen vacancies and consequently the amount of Zr inserted in the ceria network also determines the dispersion of gold. The presence of gold eases the surface reduction at lower temperatures, and as higher the amount of Zr in the gold catalysts, higher the CO conversion at low temperatures, probably due to the enhancement of the electronic transfer at the surface of the catalysts. 

2015 | 8.33

This study proposes a direct synthetic route to single titanate sheets through the mild and versatile conditions of the “chimie douce”. The stages of the production include the complexation of the titanium alkoxide precursor by benzoic acid, the formation of titanium oxo-clusters and their controlled transformation into single sheet titanates during the hydrolysis stage. The resulted material appears to be an excellent precursor for self-organized TiO2 nanotubes formation which presents an excellent activity as photocatalyst in the photo-degradation of phenol.

2015 | 8.33

The influence of different TiO2 supports on the Cu active species has been studied. It was found that the photocatalytic H2 evolution is highly affected by the structural and electronic features of surface Cu species. Thus, metal dispersion and oxidation state appears strongly conditioned by the structural and surface properties of the TiO2 support. We have examined three TiO2 supports prepared by different synthetic methods; sol–gel, hydrothermal and microemulsion. In addition, we have induced structural and surface modifications by sulfate pretreatment over freshly prepared TiO2 precursors and subsequent calcination. Notably different copper dispersion and oxidation state is obtained by using these different TiO2 supports. From the wide structural and surface analysis of the catalysts we are able to propose that the occurrence of highly disperse Cu2+ species, the sample surface area as well as the crystallinity of the TiO2 support are directly related to the photocatalytic activity for H2 production reaction.

2015 | 8.33

This work analyses the catalytic activity displayed by Cu/SiO2, Cu-Fe/SiO2 and Cu/FSN (Fe-SiO2 nanocomposite) catalysts for the Reverse Water Gas Shift reaction. Compared to Cu/SiO2 catalyst, the presence of Fe resulted on higher CO?s selectivity and boosted resistances against the constitution of the deactivation carbonaceous species. Regarding the catalytic performance however, the extent of improvement attained through incorporation Fe species strongly relied on the catalysts' configuration. At 30 L/gh and H-2:CO2 ratios = 3, the performance of the catalysts? series increased according to the sequence: Cu/SiO2 < Cu-Fe/SiO2 << Cu/FSN. The remarkable catalytic enhancements provided by Fe-SiO2 nanocomposites under different RWGS reaction atmospheres were associated to enhanced catalyst surface basicity's and stronger Cu-support interactions. The catalytic promotion achieved by Fe-SiO2 nanocomposites argue an optimistic prospective for nanocomposite catalysts within future CO2-valorising technologies.

2021 | 8.32

The eventual exploitation of one-dimensional nanomaterials needs the development of scalable, high yield, homogeneous and environmentally friendly methods capable of meeting the requirements for fabrication of functional nanomaterials with properties on demand. In this article, we demonstrate a vacuum and plasma one-reactor approach for the synthesis of fundamental common elements in solar energy and optoelectronics, i.e. the transparent conducting electrode but in the form of nanotube and nanotree architectures. Although the process is generic and can be used for a variety of TCOs and wide-bandgap semiconductors, we focus herein on indium doped tin oxide (ITO) as the most previously researched in previous applications. This protocol combines widely applied deposition techniques such as thermal evaporation for the formation of organic nanowires serving as 1D and 3D soft templates, deposition of polycrystalline layers by magnetron sputtering, and removal of the templates by simply annealing under mild vacuum conditions. The process variables are tuned to control the stoichiometry, morphology, and alignment of the ITO nanotubes and nanotrees. Four-probe characterization reveals the improved lateral connectivity of the ITO nanotrees and applied on individual nanotubes shows resistivities as low as 3.5 +/- 0.9 x 10(-4) omega cm, a value comparable to that of single-crystalline counterparts. The assessment of diffuse reflectance and transmittance in the UV-Vis range confirms the viability of the supported ITO nanotubes as random optical media working as strong scattering layers. Their further ability to form ITO nanotrees opens a path for practical applications as ultra-broadband absorbers in the NIR. The demonstrated low resistivity and optical properties of these ITO nanostructures open a way for their use in LEDs, IR shields, energy harvesting, nanosensors, and photoelectrochemical applications.

2021 | 8.31

Zinc germanate doped with Mn2+ (Zn2GeO4:Mn2+) is known to be a persistent luminescence green phosphor with potential applications in biosensing and bioimaging. Such applications demand nanoparticulated phosphors with a uniform shape and size, good dispersibility in aqueous media, high chemical stability, and surfacefunctionalization. These characteristics could be major bottlenecks and hence limit their practical applications. This work describes a one-pot, microwave-assisted hydrothermal method to synthesize highly uniform Zn2GeO4:Mn2+ nanoparticles (NPs) using polyacrylic acid (PAA) as an additive. A thorough characterization of the NPs showed that the PAA molecules were essential to realizing uniform NPs as they were responsible for the ordered aggregation of their building blocks. In addition, PAA remained attached to the NPs surface, which conferred high colloidal stability to the NPs through electrostatic and steric interactions, and provided carboxylate groups that can act as anchor sites for the eventual conjugation of biomolecules to the surface. In addition, it was demonstrated that the as-synthesized NPs were chemically stable for, at least, 1 week in phosphate buffer saline (pH range = 6.0-7.4). The luminescence properties of Zn2GeO4 NPs doped with different contents of Mn2+ (0.25-3.00 mol %) were evaluated to find the optimum doping level for the highest photoluminescence (2.50% Mn) and the longest persistent luminescence (0.50% Mn). The NPs with the best persistent luminescence properties were photostable for at least 1 week. Finally, taking advantage of such properties and the presence of surface carboxylate groups, the Zn2GeO4:0.50%Mn2+ sample was successfully used to develop a persistent luminescence-based sandwich immunoassay for the autofluorescence-free detection of interleukin-6 in undiluted human serum and undiluted human plasma samples. This study demonstrates that our persistent Mndoped Zn2GeO4 nanophosphors are ideal candidates for biosensing applications.

2023 | 8.30

The plant cuticle is located at the interface of the plant with the environment, thus acting as a protective barrier against biotic and abiotic external stress factors, and regulating water loss. Additionally, it modulates mechanical stresses derived from internal tissues and also from the environment. Recent advances in the understanding of the hydric, mechanical, thermal, and, to a lower extent, optical and electric properties of the cuticle, as well as their phenomenological connections and relationships are reviewed. An equilibrium based on the interaction among the different biophysical properties is essential to ensure plant growth and development. The notable variability reported in cuticle geometry, surface topography, and microchemistry affects the analysis of some biophysical properties of the cuticle. This review aimed to provide an updated view of the plant cuticle, understood as a modification of the cell wall, in order to establish the state-of-the-art biophysics of the plant cuticle, and to serve as an inspiration for future research in the field.

2024 | 8.30

NiFe electrocatalysts are among the most active phases for water splitting with regard to the alkaline oxygen evolution reaction (OER). The interplay between Ni and Fe, both at the surface and in the subsurface of the catalyst, is crucial to understanding such outstanding properties and remains a subject of debate. Various phenomena, ranging from the formation of oxides/(oxy)hydroxides to the associated segregation of certain species, occur during the electrochemical reactions and add another dimension of complexity that hinders the rational design of electrodes for water splitting. In this work, we have developed the procedure for the quantification of chemical depth profiling by XPS/HAXPES measurements and applied it to two NiFe electrodes with different porosities. The main outcome of this study is related to the surface reconstruction of the electrodes during the OER, followed at two different depths by means of X-ray photoelectron spectroscopy. We find that Fe initially segregates at the surface when exposed to ambient conditions, resulting in the formation of an inactive FeOx phase. In addition, the porosity of the catalyst plays a significant role in the segregation process and thus in the performance of the electrode. In particular, the higher porosity of the nanostructured sample is responsible for a more pronounced diffusion of Fe from the subsurface to the surface with a more effective suppression of the activity of the Ni1–xFexOOH phase. These results highlight the importance of the fact that the chemical state of the surface of a multielement system is a snapshot in time, dependent on both external parameters, such as the applied potential and the adjacent electrolyte, and the underlying bulk properties accessible with HAXPES.

2024 | 8.30

Seeking for advanced catalytic systems for the CO2 methanation reaction, the use of Ni supported catalysts over redox materials is often proposed. Profiting the superior redox properties described for layered perovskite systems, this work has investigated a series Ni supported YMn1-xAlxO3 (x = 0, 0.2, 0.5, 0.8, 1) perovskite catalysts. The obtained results evidenced the impact of the support nature on the systems redox properties and Ni-support interactions. Within the catalysts series, the greater methanation rates displayed by Ni/YMn0.5Al0.5O3 catalyst (0.748 mmol(CO2,conv.)s(-1) g(Ni)(-1) at 400 ? and 60 L/gh) were associated to the interplay between the support redox properties and superior Ni dispersion. The improved redox behavior attained through the Al-incorporation (up to x = 0.5) was associated to the layered perovskite structures which, being distorted and constituted by smaller crystal sizes, facilitated the behavior of Mn redox couples as surface species readily interconverted. Exhibiting catalytic performances comparable to precious metals based catalysts, this work proposes the Ni/YMn0.5Al0.5O3 catalyst as an effective system for the CO2 methanation reaction.

2022 | 8.30

A common approach for the photoelectrochemical (PEC) splitting of water relies on the application of WO3 porous electrodes sensitized with BiVO4 acting as a visible photoanode semiconductor. In this work, we propose a new architecture of photoelectrodes consisting of supported multishell nanotubes (NTs) fabricated by a soft-template approach. These NTs are formed by a concentric layered structure of indium tin oxide (ITO), WO3, and BiVO4, together with a final thin layer of cobalt phosphate (CoPi) co-catalyst. The photoelectrode manufacturing procedure is easily implementable at a large scale and successively combines the thermal evaporation of single crystalline organic nanowires (ONWs), the magnetron sputtering deposition of ITO and WO3, and the solution dripping and electrochemical deposition of, respectively, BiVO4 and CoPi, plus the annealing in air under mild conditions. The obtained NT electrodes depict a large electrochemically active surface and outperform the efficiency of equivalent planar-layered electrodes by more than one order of magnitude. A thorough electrochemical analysis of the electrodes illuminated with blue and solar lights demonstrates that the characteristics of the WO3/BiVO4 Schottky barrier heterojunction control the NT electrode efficiency, which depended on the BiVO4 outer layer thickness and the incorporation of the CoPi electrocatalyst. These results support the high potential of the proposed soft-template methodology for the large-area fabrication of highly efficient multishell ITO/WO3/BiVO4/CoPi NT electrodes for the PEC splitting of water.

2023 | 8.30

Perovskite solar cells have attracted increasing interest among the photovoltaic community in the last few years owing to their unique properties and high efficiency. In the present work, we report the fabrication of perovskite solar cells based on highly ordered 1-dimensional porous TiO2 photoanodes, which are uniform on a large area. These nanocolumnar porous TiO2 photoanodes were deposited by physical vapor deposition in an oblique angle configuration (PVD-OAD) by varying the zenithal angle between the target and the substrate normal. Perovskite infiltration into these 1-dimensional nanocolumnar structures was homogeneous through the entire thickness of the porous layer as revealed by secondary ion mass spectroscopy studies. The fabricated solar cells, with an optimized thickness of the photoanode and with industrially accepted methods, will pave the way for easy implementation on a large scale.

2015 | 8.26

Understanding the viability of the RWGS from a thermodynamic and techno-economic angle opens new horizons within CO2 conversion technologies. Unfortunately, profitability studies of this technology are scarce in literature and mainly focused on overall conversion and selectivity trends with tangential remarks on energy demands and pro-cess costs. To address this research gap, herein we present a comprehensive techno-economic study of the RWGS reac-tion when coupling with Fischer-Tropsch synthesis is envisaged to produced fuels and chemicals using CO2 as building block. We showcase a remarkable impact of operating conditions in the final syngas product and both CAPEX and OPEX. From a capital investment perspective, optimal situations involve RWGS unit running at low temperatures and high pressures as evidenced by our results. However, from the running cost angle, operating at 4 bar is the most favorable alternative within the studied scenarios. Our findings showcase that, no matter the selected temperature the RWGS unit should be preferentially run at intermediate pressures. Ultimately, our work maps out multiple operat-ing scenarios in terms of energy demand and process cost serving as guideline to set optimal reaction conditions to un-lock the potential of the RWGS for chemical CO2 recycling.

2023 | 8.20

Current studies on ammonia synthesis by means of atmospheric pressure plasmas respond to the urgent need of developing less environmentally aggressive processes than the conventional Haber-Bosch catalytic reaction. Herein, we systematically study the plasma synthesis of ammonia and the much less investigated reverse reaction (decomposition of ammonia into nitrogen and hydrogen). Besides analyzing the efficiency of both processes in a packed-bed plasma reactor, we apply an isotope-exchange approach (using D-2 instead of H-2) to study the reaction mechanisms. Isotope labeling has been rarely applied to investigate atmospheric plasma reactions, and we demonstrate that this methodology may provide unique information about intermediate reactions that, consuming energy and diminishing the process efficiency, do not effectively contribute to the overall synthesis/decomposition of ammonia. In addition, the same methodology has demonstrated the active participation of the interelectrode material surface in the plasma-activated synthesis/decomposition of ammonia. These results about the involvement of surface reactions in packed-bed plasma processes, complemented with data obtained by optical emission spectroscopy analysis of the plasma phase, have evidenced the occurrence of inefficient intermediate reaction mechanisms that limit the efficiency and shown that the rate-limiting step for the ammonia synthesis and decomposition reactions are the formation of NH* species in the plasma phase and the electron impact dissociation of the molecule, respectively.

2020 | 8.20

The combination of different bioimaging techniques, mainly in the field of oncology, allows circumventing the defects associated with the individual imaging modalities, thus providing a more reliable diagnosis. The development of multimodal endogenous probes that are simultaneously suitable for various imaging modalities, such as magnetic resonance imaging (MRI), X-ray computed tomography (CT) and luminescent imaging (LI) is, therefore, highly recommended. Such probes should operate in the conditions imposed by the newest imaging equipment, such as MRI operating at high magnetic fields and dual-energy CT. They should show, as well, high photoluminescence emission intensity for their use in optical imaging and present good biocompatibility. In this context, we have designed a single nanoprobe, based on a core-shell architecture, composed of a luminescent Eu3+:Ba0.3Lu0.7F2.7 core surrounded by an external HoF3 shell that confers the probe with very high magnetic transverse relaxivity at high field. An intermediate, optically inert Ba0.3Lu0.7F2.7 layer was interposed between the core and the shell to hinder Eu3+-Ho3+ cross-relaxation and avoid luminescence quenching. The presence of Ba and Lu, with different K-edges, allows for good X-ray attenuation at high and low voltages. The core-shell nanoparticles synthesized are good potential candidates as trimodal bioprobes for MRI at high field, dual-energy CT and luminescent imaging. 

2020 | 8.13

Well-crystallized Ca3(PO4)2 doped and un-doped nano-particles with the maximum strontium content (40 wt% Sr) followed by calcination at 800 °C for 3 h were synthesized via facile co-precipitation method. DTA/TGA, X-ray diffraction (XRD), energy dispersive scanning electron microscopy (SEM/EDX), UV–vis diffuse reflectance spectrum (UV–vis DRS), Raman spectroscopy and photoluminescence (PL) techniques were used for material characterization. The (XRD) patterns of as-synthesized Sr-doped Ca3(PO4)2 solid solution samples exhibited a systematic shift toward lower angles by possessing a single rhombohedral crystal structure without any secondary phases. The UV light driven photocatalytic activity was assessed for rhodamine B (RhB) degradation. As a result, ultrafast photodegradation activity was observed after Sr doping. Moreover, the 30 wt% Sr-Ca3(PO4)2 sample showed the highest photocatalytic degradation among the Sr-doped Ca3(PO4)2 samples toward RhB. It was further suggested that as-synthesized 30 wt% Sr-Ca3(PO4)2 superior photocatalytic performance is ascribed to the more proficient partition of photogenerated electron-hole pairs. Furthermore, the involved mechanism of superior photocatalytic performance of the 30 wt% Sr-Ca3(PO4)2 solid solution was also investigated. In addition, regeneration cycles indicated the higher stability of the photocatalyst to be effectively recycled up to four times without any considerable reduction in photocatalytic performance. Thus, these informations further provides us a scalable pathway to fabricate Sr doped Ca3(PO4)2 and its consequent use as an efficient photocatalyst for rhodamine B (RhB) contaminated wastewater treatment.

2020 | 8.13

Doped-PrBaMn2-xTMxO5+delta samples with TM = Co and/or Ni were synthesized by a mechanochemical route from stoichiometric oxide precursor mixtures (Pr6O11, BaO2, MnO, NiO and CoO) using a planetary mill at 600 rpm for 150 min. A disordered ABO(3) pseudocubic perovskite phase was obtained after the milling process that was transformed, as established by XRD, into the double layered AA'B2O5+delta perovskite phase after annealing at 900 degrees C in a reducing atmosphere (10%H-2/Ar). The microstructural characterization by SEM, TEM, and HRTEM ascertained that this reducing treatment induced the exsolution of Ni and Co metallic nanoparticles from the doped samples. Ni-Co alloys were even exsolved when the layered manganite phase was co-doped with both transition metals. It was confirmed that the exsolution process was reversible by switching the working atmosphere from reducing to oxidizing. Polarization resistance values of the doped samples determined in symmetrical cells in air and H-2, as well as the electrochemical performance of electrolyte LSGM-supported planar cells suggested that these samples can be used as symmetrical electrodes in SOFCs.

2024 | 8.10

Yttrium-doped BaZrO3 is a promising electrolyte for intermediate-temperature protonic ceramic fuel cells. In the anode-supported configuration, a slurry containing the electrolyte is deposited on the surface of a calcined porous anode and sintered. Differences in sintering behaviour and thermal expansion coefficients for the anode and electrolyte result in elastic residual stresses that can impact the long-term stability of the cell during cyclic operation. Half-cells using BaZr0.8Y0.2O3-δ as the electrolyte were fabricated using the solid-state reaction sintering method under various sintering conditions. Comprehensive microstructure and residual stress analyses as a function of processing parameters were performed using two-dimensional X-ray diffraction, Rietveld refinement, and scanning electron microscopy, before and after the half-cells were reduced under hydrogen, giving a complete picture of phase, microstructure, and stress evolution under thermal and reduction cycles like the actual operation of the cell. Our results reveal that a temperature of 1400 °C and shorter soaking times might be advantageous for obtaining phase-pure and thin yttrium-doped BaZrO3 electrolytes with improved microstructure and the presence of compressive residual stress. These findings offer valuable insights into optimising the fabrication process of BaZrO3-based electrolytes, leading to enhanced performance and long-term stability of anode-supported protonic ceramic fuel cells operating at intermediate temperatures. 

2024 | 8.10

In this work, we have prepared a series of Pd catalysts on a CNx support for the liquid phase decomposition of formic acid. The structured CNx support was obtained through thermal pyrolysis of melamine foam and the pyrolysis conditions were optimized to achieve high surface area. The resulting support contains high amount of nitrogen with a contribution of pyridinic component. Several Pd catalysts were prepared and under optimized condi-tions, we were able to obtain small (2.7 +/- 0.9) nm Pd particles by using the oxidized support in powdery form. The activity of the optimized catalyst was studied under different con-ditions in the fresh and the used form. The fresh catalyst did not show significant activity. However, we found that the catalyst activated after use. Activation was understood in terms of the variation of surface Pd oxidation states under the effect of formic acid/sodium formate solutions. We found that the best activity is achieved under an optimal proportion of Pd0/PdII surface states according to previous reports. Under the best conditions, the activity of the best catalyst (8.6Pd/CN0.3) was as high as 9245 h-1, attributable to the small particle size, the Pd0/PdII ratio, the amount of pyridinic nitrogen, and the testing conditions, which included the preadsorption of sodium formate

2023 | 8.10

The reduction, storage, and reuse of greenhouse gas carbon dioxide (CO2) is a crucial concern in modern society. Bio-waste adsorbents have recently aroused the investigator's attention as auspicious materials for CO2 capture. However, the adsorption capacity decaying and poor fluidizability during carbonation/calcination cycles of all natural adsorbents used in the calcium-looping process (CaL) are important challenges. The current study ex-plores the performance of a novel SiO2-decorated calcium-based adsorbent recovered from eggshell waste in terms of both CO2 capture capacity and fluidity. Two preparation methods of hydration and sol-gel were used to obtain Ca-based adsorbents with different pore configurations and volumes. Modification of the adsorbents was applied by dry physically mixing with different weight percentages of hydrophobic SiO2 nanoparticles (NPs), in order to maintain stability and fluidity. The adsorbent prepared by the sol-gel method exhibited a fluffier structure with smaller grain sizes and higher porosity than that of prepared by the hydration method, leading to a 6.9 % increase in conversion at the end of the 20th cycle. Also, with the optimal amount of SiO2 nanoparticles, i. e. 7.5 wt%, the amount of CaO conversion obtained by sol-gel derived adsorbent was 27.59 % higher than that by pristine eggshell at the end of the 20th carbonation/calcination cycles. The fluidizability tests showed that the highest bed expansion ratio (2.29) was achieved for sol-gel derived adsorbent in the presence of 7.5 wt% silica nanoparticles which was considerably higher than the amount of 1.8 and 1.6 belonged to sol-gel derived adsorbent and pristine eggshell without silica at the gas velocity of approximate to 6.5 cm/s, respectively. The high adsorption capacity and proper fluidity of this novel and green calcium-based adsorbent promise its wide application.

2023 | 8.10

In this work, a series of Pd catalysts supported on commercially available activated carbon (Norit (R)) were prepared by employing different metal precursors (Pd(NO3)2 and Na2PdCl4) by the impregnation-reduction method at different pH. Catalysts were tested for the liquid phase decomposition of formic acid to generate hydrogen. The best results, in terms of small particle size and high catalytic activity were achieved for the Pd/C sample prepared by using Pd(NO3)2 salt impregnated at pH = 2.5, and reduced with sodium borohydride. The particle size of the best Pd/C catalyst is (4.1 +/- 1.4) nm with initial TOFs of 2929 and 683 h-1 at 60 and 30 degrees C respectively and an apparent activation energy of 40 kJ mol-1. Samples prepared by using Na2PdCl4 precursor, consisted of particles with higher size and thus lower activity than the ones prepared with Pd(NO3)2. Regardless the Pd precursor employed, the best results in terms of particle size and activity were achieved at the point of zero charge of the support when the Pd species and the carbon surface were both neutral. The impregnation pH not only determines the particle size, but also the nature of the reducing agent does. The catalytic activity was shown to be size-dependent and it was shown that a mixture of surface Pd0 and PdII oxidation states is beneficial for the activity. When comparing with literature catalysts with similar composition, we found that our best catalyst is competitive enough and that Norit (R) support could be promising for future studies on this reaction.

2023 | 8.10

A multilayer luminescent design concept is presented to develop energy sensitive radiation-beam monitors on the basis of colorimetric analysis. Each luminescent layer within the stack consists of rare-earth-doped transparent oxides of optical quality and a characteristic luminescent emission under excitation with electron or ion beams. For a given type of particle beam (electron, protons, alpha particles, etc.), its penetration depth and therefore its energy loss at a particular buried layer within the multilayer stack depend on the energy of the initial beam. The intensity of the luminescent response of each layer is proportional to the energy deposited by the radiation beam within the layer, so characteristic color emission will be achieved if different phosphors are considered in the layers of the luminescent stack. Phosphor doping, emission efficiency, layer thickness, and multilayer structure design are key parameters relevant to achieving a broad colorimetric response. Two case examples are designed and fabricated to illustrate the capabilities of these new types of detector to evaluate the kinetic energy of either electron beams of a few kilo-electron volts or a particles of alpha few mega-electron volts.

2017 | 8.10

We present a low-temperature versatile protocol for the fabrication of plasma nanocomposite thin films to act as tunable emitters and optical gain media. The films are obtained by the remote plasma-assisted deposition of a 4-(dicyano-methylene)-2-methy1-6-(4-dimethylamino-styry1)-4Hpyran (DCM) laser dye alongside adamantane. The experimental parameters that determine the concentration of the dye in the films and their optical properties, including light absorption, the refractive index, and luminescence, are evaluated. Amplified spontaneous emission experiments in the DCM/adamantane nano composite waveguides show the improvement of the copolymerized nano composites' properties compared to films that were deposited with DCM as the sole precursor. Moreover, one-dimensional distributed feed-back laser emission is demonstrated and characterized in some of the nanocomposite films that are studied. These results open new paths for the optimization of the optical and lasing properties of plasma nanocomposite polymers, which can be straightforwardly integrated as active components in optoelectronic devices.

2017 | 8.10

Small solid biomass combustion systems are among the main contributors to the global particulate emissions share, and cheap, efficient abatement systems are not yet available for them. The placement of inert porous material to confine the combustion region is being recently explored as a possible mitigation system for this kind of pollution. However, given the complexity of biomass thermochemical decomposition processes, it is challenging to justify the performance of these systems on the basis of a physicochemical understanding. A foundational experiment-based study is carried out in this work to understand how combustion confinement affects the particulate emissions production mechanisms. A combustion unit was designed and built to systematically test ceramic foams with different porosities: keeping constant airflow and fuel feed rates. A comprehensive characterisation study was carried out on the solid biomass fuel, the temperature profile, the particulate emissions, and the remaining solid residue. The results evidenced that the use of foams has a substantial impact on the temperature distribution in the combustion chamber. The higher the cell density of the foam, the higher and more homogeneous are the temperatures reached in the combustion bed. This fact improved the thermal decomposition process of the pellets due to a better air-fuel mixture, leading to a reduction of the solid particulate matter emissions by more than 70%. These findings suggest that the use of an inert porous material above the combustion region might be a feasible solution for particulate emission control in small-size biomass combustion technology.

2021 | 8.04

Novel catalytic systems should be tested for the valorization of CO2 through the Sabatier reaction, since this process is gaining great importance within strategic sectors of the chemical industry. Therefore, this work explores the feasibility of structuring a catalyst (0.5%Ru-15%Ni/MgAl2O4) for CO2 methanation using metal micromonoliths. The coating of the catalyst over the surface of the micromonoliths is carried out by means of the washcoating procedure and different characterization techniques are applied to establish possible changes in the catalyst during structuring. Regarding the performance in the Sabatier reaction, the structured systems are tested as well as the powder catalyst in order to establish the possible effects of the structuring processes. For this, variables such as catalyst loading, space velocity, inclusion of water in the feed-stream and the pressurization of the process were studied. In general, the structuring of the proposed catalyst by the reported procedure is absolutely feasible. There are no substantial changes in the main features of the catalyst and this means that its catalytic performance is not altered after the structuring process either. Furthermore, the structured system exhibits high stability in a long-term test and is comparable with other CO2 methanation catalysts reported in research to date. 

2020 | 8.00

Persistent luminescence phosphor nanoparticles (PersLNPs) offer exciting opportunities for anticounterfeiting, data storage, imaging displays, or AC-driven lighting applications owing to the possibility to process them as shapable thin coatings. However, despite unique delayed and long-lasting luminescence, the relatively low storage capacity of persistent phosphor nanoparticles combined with the difficulty of harvesting photons from transparent thin layers drastically hinder the perceived afterglow. In order to enhance persistent luminescence (PersL) of thin coatings, herein a novel approach is proposed based on resonant optical nanostructures. In particular, it is demonstrated that the integration of TiO2 scattering spheres in films (with thickness comprised between 1 and 10 mu m) made of ZnGa2O4:Cr3+ PersLNPs enables a significant increase in afterglow intensity due to the combination of effective charging and enhanced outcoupling. As a result, a approximate to 3.5-fold enhancement of the PersL is observed in 2 mu m-thick films stuffed with scattering centers using low-light illumination conditions. Furthermore, inclusion of scattering centers leads to an unprecedented acceleration of the PersL charging speed. These results constitute the first example of photonic engineering applied to enhance the properties of PersL materials coatings.

2024 | 8.00

Nanoporous solids that stabilize trapped gas nanobubbles open new possibilities to fabricate solid targets for nuclear reactions. A methodology is described based on the magnetron sputtering (MS) technique operated under quasistatic flux conditions to produce such nanocomposites films with He-3 contents of up to 16 at.% in an amorphous-silicon matrix. In addition to the characteristic low pressure (3-6 Pa) needed for the gas discharge, the method ensures almost complete reduction of the process gas flow during film fabrication. The method could produce similar materials to those obtained under classical dynamic flux conditions for MS. The drastic reduction (>99.5%) of the gas consumption is fundamental for the fabrication of targets with scarce and expensive gases. Si:He-3 and W:He-3 targets are presented together with their microstructural (scanning and transmission electron microscopy, SEM and TEM respectively) and compositional (Ion Beam Analysis, IBA) characterization. The He-3 content achieved was over 1 x 10(18) at/cm(2) for film thicknesses between 1.5 and 3 mu m for both Si and W matrices. First experiments to probe the stability of the targets for nuclear reaction studies in inverse kinematics configurations are presented. 

2020 | 7.99

Interface engineering is an effective approach to decrease nonradiative recombination and the energy barrier at the perovskite/hole transporting layer (HTL) interfaces. To overcome such limitations, an organic semiconductor (DTT-EHDI2) is proposed, which is, composed of dithienothiophene (DTT) as the core and a planar triazatruxene incorporating an alkyl chain as the side group. This is noted to be an effective interfacial layer for inverted planar perovskite solar cells (PSCs). The altered interface effectively minimizes the detrimental charge recombination and tailors the photoinduced charge transfer dynamics at the interface of the inorganic HTL/perovskite. The pi-conjugation in DTT-EHDI2 induces high hole mobility and electrical conductivity via electron-donating properties and strong pi-pi intermolecular interaction. The synergetic approach leads to a substantial performance enhancement in dopant-free DTT-EHDI2-based inverted planar PSCs, achieving 18.15% power conversion efficiency with negligible hysteresis effect. The present approach provides an effective direction of the cost-effective thiophene derivative as an interfacial agent to escalate the optoelectronic performances in photovoltaics.

2022 | 7.90

Graphitized carbon materials from biomass resources were successfully synthesized with an iron catalyst, and their electrochemical performance as anode materials for lithium-ion batteries (LIBs) was investigated. Peak pyrolysis temperatures between 850 and 2000 degrees C were covered to study the effect of crystallinity and microstructural parameters on the anodic behavior, with a focus on the first-cycle Coulombic efficiency, reversible specific capacity, and rate performance. In terms of capacity, results at the highest temperatures are comparable to those of commercially used synthetic graphite derived from a petroleum coke precursor at higher temperatures, and up to twice as much as that of uncatalyzed biomass-derived carbons. The opportunity to graphitize low-cost biomass resources at moderate temperatures through this one-step environmentally friendly process, and the positive effects on the specific capacity, make it interesting to develop more sustainable graphite-based anodes for LIBs.

2018 | 7.80

Micro/nanoplastics have sparked attention in recent years due to their widespread presence in the environment. Currently, several waste valorization approaches are under development in order to upcycle micro/nanoplastics. Thermal conversion technologies such as pyrolysis, gasification, liquefaction, or hydrothermal carbonization can yield high-value solid products, oil, and gases from plastics waste. The common thermal conversion technologies investigated focus on maximizing the production of oil and gases (such as H2 and CH4) for use as fuel. Except for hydrogen, when these products are used to generate energy, the carbon emissions generated are comparable to those produced by traditional fossil fuels. Herein, we present a review of the current efforts to capture and convert plastic waste into valuable products with an emphasis on identifying the need to develop processes specifically for micro/nano-plastics while also preventing the release of CO2 emissions. We identify the development of efficient catalytic materials as a critical research need for achieving economically viable thermochemical con-version of micro/nanoplastics.

2022 | 7.80

Herein we show a solution based synthetic pathway to obtain a resonant optical cavity with embedded colloidal semiconductor quantum dots (CSQDs). The optical cavity pore network, surrounded by two dense Bragg mirrors, was designed ad hoc to selectively host the quantum dots, while uncontrolled infiltration of those in the rest of the layered structure was prevented. Coupling between the optical resonant modes of the host and the natural emission of the embedded nanoparticles gives rise to the fine tuning of the luminescence spectrum extracted from the ensemble. Our approach overcomes, without the need for an encapsulating agent and exclusively by solution processing, the difficulties that arise from the low thermal and chemical stability of the CSQDs. It opens the route to achieving precise control over their location and hence over the spectral properties of light emitted by these widely employed nanomaterials. Furthermore, as the porosity of the cavity is preserved after infiltration, the system remains responsive to environmental changes, which provides an added value to the proposed structure.

2015 | 7.76

{0 0 1} faceted TiO2 catalysts are hydrothermally synthesized by using titanium(IV) isopropoxide and butoxide precursors (ISO and BUT TiO2samples) together with HF addition. Their activity and stability are evaluated in the catalytic condensation of light oxygenated organic compounds present in an aqueous model mixture simulating a real bio-refinery effluent, under moderate operation conditions. High {0 0 1} faceted TiO2 catalysts show organic products yields superior to those attained with other TiO2 samples (anatase, rutile, and P25). This enhanced catalytic activity relates to their physico-chemical and textural properties, such as high surface area (≈100 m2/g), regular morphology (platelets conformed by partially agglomerated TiO2 nanoparticles), and adequate Lewis acidity. XRD and Raman measurements evidence the unique presence of anatase crystalline phase in both ISO and BUT materials, in which the use of HF during synthesis produces the preferential growth of TiO2 crystals mainly exposing the {0 0 1} plane. This effective {0 0 1} facet exposition directly determines catalytic results. Moreover, TiO2 ISO catalyst shows outstanding stability under reaction conditions, maintaining practically unaltered their activity after several re-uses. In particular, Lewis acid sites present in TiO2 faceted materials are more stable in the presence of organic acids under aqueous environments. This opens new possibilities for the application of these materials in the valorization of light oxygenated compounds present in biomass-derived aqueous effluents.

2018 | 7.72

Free-standing films have been obtained by drop-casting cellulose-glycerol mixtures (up to 50 wt% glycerol) dissolved in trifluoroacetic acid and trifluoroacetic anhydride (TFA:TFAA, 2:1, v:v). A comprehensive examination of the optical, structural, mechanical, thermal, hydrodynamic, barrier, migration, greaseproof, and biodegradation characteristics of the films was conducted. The resulting cellulose-glycerol blends exhibited an amorphous molecular structure and a reinforced H-bond network, as evidenced by X-ray diffraction analysis and infrared spectroscopy, respectively. The inclusion of glycerol exerted a plasticizing influence on the mechanical properties of the films, while keeping their transparency. Hydrodynamic and barrier properties were assessed through water uptake and water vapor/oxygen transmission rates, respectively, and obtained values were consistent with those of other cellulose-based materials. Furthermore, overall migration levels were below European regulation limits, as stated by using Tenax as a dry food simulant. In addition, these bioplastics demonstrated good greaseproof performance, particularly at high glycerol content, and potential as packaging materials for bakery products. Biodegradability assessments were carried out by measuring the biological oxygen demand in seawater and high biodegradation rates induced by glycerol were observed.

2024 | 7.70

Within the syngas production from biomass gasification, tar removal constitutes a chief issue to overcome for advanced catalytic systems. This work investigates the performance of Ni and Ni-K catalysts for reforming of derived-biomass producer gas using toluene as model tar. At 750 degrees C and 60Lg(-1)h(-1), the stability test (70 h) revealed stable performances (CO2, CH4 and C7H8 conversions of 60, 95 and 100%, correspondingly) uniquely for the Ni-K catalyst. Although the efficient protection towards coking let by K was demonstrated, TPO studies over the post-reacted systems still evidenced the presence of carbon deposits for both samples. Conducting three successive reaction/regeneration cycles with different gasifying agents (air, steam and CO2) at 800 C for 1h, the capability towards regeneration of both catalytic systems was assessed and the spent catalysts were characterized by XRD, SEM and TEM. While none of the regeneration treatments recovered the performance of the unpromoted catalyst, the Ni-K catalysts demonstrated the capability of being fully regenerated by air and CO2 and exhibited analogous catalytic performances after a series of reaction/regeneration cycles. Hence, it is proved that the addition of K into Ni catalysts not only enhances the resistance against deactivation but enables rather facile regenerative procedures under certain atmospheres (air and CO2).

2024 | 7.70

Although calcium-based materials are the most promising adsorbents used in calcium looping process for carbon dioxide removing, their CO2 capture capacity decaying besides poor fluidization, still are the important challenges. In the present investigation, eggshell as a cheap, easily available and unpolluted source of calcium carbonate was used for CO2 capturing in calcium looping process. Eggshell particles were treated with various volume concentrations of acetic acid to improve its sorption capacity. According to the TGA results after 20 carbonation/calcination cycles, the effective carbonation conversion of modified eggshell with 5%, 20%, 30% and 40%. v/v acetic acid was 21.33%, 24.26%, 25.97% and 28.97%, respectively, which is considerable compared to 20.54% for untreated eggshell. The effect of initial eggshell particle size on the adsorption behavior of final adsorbent was also investigated by using two different sizes including dp < 45 mu m and dp > 320 mu m. The results showed that the effective conversion of the adsorbent containing 40%. v/v acetic acid derived from small particle size eggshells was 9.32% higher than that from larger particle size eggshells. In terms of fluidization behavior, surprisingly the addition of acetic acid to the eggshell particles also increased the bed expansion ratio as 8% and 36.2% at gas velocities of 0.27 and 6.67 cm/s, respectively. Further improvement in the fluidity of eggshell modified with 40% acid was performed by manually mixing of SiO2 nanoparticles at different weight percentages. According to the results, adding 7.5 wt% SiO2 leaded to the homogeneous and agglomerate particulate fluidization.

2022 | 7.70

Keywords: attenuated total reflectance–Fourier transform infrared (ATR-FTIR);biomechanics;cuticle;cutin;flavonoids;tomato (Solanum lycopersicum) fruit Summary - In this study, growth-dependent changes in the mechanical properties of the tomato (Solanum lycopersicum) cuticle during fruit development were investigated in two cultivars with different patterns of cuticle growth and accumulation. - The mechanical properties were determined in uniaxial tensile tests using strips of isolated cuticles. Changes in the functional groups of the cuticle chemical components were analysed by attenuated total reflectance–Fourier transform infrared (ATR-FTIR). - The early stages of fruit growth are characterized by an elastic cuticle, and viscoelastic behaviour only appeared at the beginning of cell enlargement. Changes in the cutin:polysaccharide ratio during development affected the strength required to achieve viscoelastic deformation. The increase in stiffness and decrease in extensibility during ripening, related to flavonoid accumulation, were accompanied by an increase in cutin depolymerization as a result of a reduction in the overall number of ester bonds. - Quantitative changes in cuticle components influence the elastic/viscoelastic behaviour of the cuticle. The cutin:polysaccharide ratio modulates the stress required to permanently deform the cuticle and allow cell enlargement. Flavonoids stiffen the elastic phase and reduce permanent viscoelastic deformation. Ripening is accompanied by a chemical cleavage of cutin ester bonds. An infrared (IR) band related to phenolic accumulation can be used to monitor changes in the cutin esterification index.

2014 | 7.67

  Despite the dramatic change that Tissue Engineering or stem cell therapies have brought to current therapeutic strategies, there is a lack of functionalities in the available biomaterials for manufacturing scaffolds to treat several highly prevalent osseous diseases (osteochondral defects, osteoporosis, etc.). One promising approach to fill this gap involves the development of innovative piezoelectric scaffolds for improved bone regeneration. Scaffolds with the appropriate piezoelectricity can positively influence the proliferation and differentiation of mesenchymal stem cells to regenerate bone tissue, since surface electrical charges play a key role in the mechanotransduction process. In this work, polymeric-based composite scaffolds with piezoelectric properties intended for bone tissue engineering are reviewed. Special attention is paid to biocompatible, piezoelectric polymers that show suitable properties to be pro-cessed by additive manufacturing techniques. Previous works on composite scaffolds based of these poly-meric matrices and containing piezoceramic additives are summarized. The use of piezoelectric nanostructured composite formulations containing lead-free ceramic oxide nanoparticles with per-ovskite structure is highlighted. Also, different commonly applied mechanical stimuli to activate the piezoelectric effect of the developed materials are presented. Finally, other applications of such scaffolds are mentioned, including their capabilities for real-time monitoring

2023 | 7.60

We report here on the controlled synthesis, characterization, and electrochemical properties of different polymorphs of niobium pentoxide grown by CVD of new single-source precursors. Nb2O5 films deposited at different temperatures showed systematic phase evolution from low-temperature tetragonal (TT-Nb2O5, T-Nb2O5) to high temperature monoclinic modifications (H–Nb2O5). Optimization of the precursor flux and substrate temperature enabled phase-selective growth of Nb2O5 nanorods and films on conductive mesoporous biomorphic carbon matrices (BioC). Nb2O5 thin films deposited on monolithic BioC scaffolds produced composite materials integrating the high surface area and conductivity of the carbonaceous matrix with the intrinsically high capacitance of nanostructured niobium oxide. Heterojunctions in Nb2O5/BioC composites were found to be beneficial in electrochemical capacitance. Electrochemical characterization of Nb2O5/BioC composites showed that small amounts of Nb2O5 (as low as 5%) in conjunction with BioCarbon resulted in a 7-fold increase in the electrode capacitance, from 15 to 104 F g–1, while imparting good cycling stability, making these materials ideally suited for electrochemical energy storage applications.

2016 | 7.50

This paper presents a new method for the fabrication of metal-like decorative layers on glazed ceramic tiles. It consists of the laser treatment of Cu thin films prepared by electron-beam evaporation at glancing angles. A thin film of discontinuous Cu nanoparticles was electron-beam-evaporated in an oblique angle configuration onto ceramic tiles and an ample palette of colors obtained by laser treatment both in air and in vacuum. Scanning electron microscopy along with UV–vis–near-IR spectroscopy and time-of-flight secondary ion mass spectrometry analysis were used to characterize the differently colored layers. On the basis of these analyses, color development has been accounted for by a simple model considering surface melting phenomena and different microstructural and chemical transformations of the outmost surface layers of the samples.

2016 | 7.50

A flexible and robust piezoelectric nanogenerator (NG) based on a polymer-ceramic nanocomposite structure has been successfully fabricated via a cost-effective and scalable template assisted hydrothermal synthesis method. Vertically aligned arrays of dense and uniform zinc oxide (ZnO) nanowires (NWs) with high aspect ratio (diameter similar to 250 nm, length similar to 12 mu m) were grown within nanoporous polycarbonate (PC) templates. The energy conversion efficiency was found to be similar to 4.2%, which is comparable to previously reported values for ZnO NWs. The resulting NG is found to have excellent fatigue performance, being relatively immune to detrimental environmental factors and mechanical failure, as the constituent ZnO NWs remain embedded and protected inside the polymer matrix.

2016 | 7.50

A one-pot simple procedure for the synthesis of uniform, ellipsoidal Eu3+-doped sodium lanthanum tungstate and molybdate (NaLa(XO4)(2), X = W, Mo) nanophosphors, functionalized with carboxylate groups, is described. The method is based on a homogeneous precipitation process at 120 degrees C from appropriate Na+ Ln(3+) and tungstate or molybdate precursors dissolved in ethylene glycol/water mixtures containing poly acrylic acid. A comparative study of the luminescent properties of both luminescent materials as a function of the Eu3+ doping level has been performed to find the optimum nanophosphor, whose efficiency as X-ray computed tomography contrast agent is also evaluated and compared with that of a commercial probe. Finally, the cell viability and colloidal stability in physiological pH medium of the optimum samples have also been studied to assess their suitability for biomedical applications.

2019 | 7.49

This work presents an evaluation of a high performance series of water gas shift (WGS) catalysts in the preferential CO oxidation reaction (PrOx) in order to examine the applicability of the same catalyst for both processes as a first step for coupling both reactions in a single process. Gold based catalysts are applied in an extensive study of the CO-PrOx reaction parameters, such as λ, WHSV, CO concentration and [H2O]/[CO2] ratio in order to obtain the best activity/selectivity balance. CO and H2 oxidation reactions were treated separately in order to establish the degree of CO/H2 oxidation competition. Additionally the catalysts behavior in the CO-PrOx parallel reactions such a WGS and RWGS have been also carried out to analyze their effect on product composition.

2014 | 7.44

Er-BiVO4 has been synthesized by means of mw-assisted hydrothermal method having good photoactivity under sun-like excitation. It is stated that the precursor addition sequence plays a critical role which determine the further structural feature of BiVO4. From the structural and morphological characterization, it can be demonstrated that the presence of Er3+ would induce the stabilization of the tetragonal phase probably due to the formation of tetragonal-ErVO4 seeds previous to BiVO4 formation. The best photocatalytic performance is attained for the sample with 0.75 at% Er3+ content. At this dopant loading a mixture of tetragonal and monoclinic phase (70% tetragonal) is obtained. The dramatic increase in the photocatalytic activity for 0.75 at% Er-BiVO4 is related to the occurrence of such heterostructure. For this system, the MB degradation rate constant appears drastically higher as bare m-BiVO4. Furthermore, activities of photocatalysts for visible-light-driven O2 evolution have been evaluated, demonstrating that the photocatalytic activity of this Er-doped system (O2 evolution rate, 1014 μmol g−1 h−1) is 20 times as that of undoped m-BiVO4 (O2 evolution rate, 54 μmol g−1 h−1). From the obtained results, the cooperative conjunction of electronic and luminescence mechanism involved in the reaction is proposed to be the origin of the enhanced photocatalytic efficiencies of such systems.

2014 | 7.44

H2 production from methanol/water photo-splitting was compared using various commercial photocatalysts (Evonik P25 (P25), Hombikat UV-100 (HB) and Kronos vlp7000 (KR)) and others synthesised with a sol–gel-hydrothermal (HT) process and a sol–gel method followed by calcination (SG400 and SG750). All photocatalysts had been surface modified with Au at different concentrations, from 0.2 to 6.0 wt.%, using the photodeposition method. A complete characterisation study of the different photocatalysts was performed (BET, XRD, TEM, SEM-EDX, FTIR, UV–vis Reflectance Diffuse Spectra and aggregate size). The experiments were conducted for 3.5 h using 1 g L−1 of photocatalyst with methanol (25 vol.%) as sacrificial agent. In addition to H2 generation, production of the main intermediates, formaldehyde and formic acid, and of CO2 was also evaluated. The commercial photocatalyst KR at 0.8 wt.% Au had the highest H2 production of all the photocatalysts studied with 1542.9 μmol h−1. Of the photocatalysts synthesised by our group, SG750 at Au loading of 2.0 wt.% gave the highest H2 production of 723.1 μmol h−1. The SG750 photocatalyst at Au loading of 2.0 wt.% also had the highest H2 production yield per unit of surface area at 45.5 μmol g h−1 m−2.

2014 | 7.44

The effect of gold addition to a supported Ni SRM catalyst has been studied in this work in order to determine the influence of gold on both the amount and type of carbon species formed during the reaction. The structure of the support, a mixed La–Al perovskite, determines the catalyst reducibility and Ni particle size. Gold addition affects the metal particle size increasing metal dispersion on increasing the gold content. Therefore, although gold blocks step Ni sites, the more active sites for Csingle bondH activation, and increases electron density on nickel, the higher dispersion results in an apparently higher activity upon gold addition. Moreover, gold addition increases the catalyst stability by decreasing the rate of growth of carbon nanotubes.

2014 | 7.44

Some nickel catalysts supported on natural phosphate (NP) have been tested for the dry methane reforming reaction. Although the original impregnated 15%Ni/NP catalyst has no activity at all, the modification of the support by mechano-chemical and/or acid treatment strongly improved the catalytic performance, yielding a series of very active and stable catalysts. The chemical and physical characterization by X-ray diffraction (XRD), temperature programmed reduction (TPR), in situ X-ray absorption spectroscopy (XAS) and other techniques have shown that these treatments mainly modify the interaction between the nickel phase and the support surface. The nickel ions occupy calcium position in the surface of the phosphate phase, which stabilizes and improves the dispersion of nickel species. The final reduced catalysts present a much better dispersed metallic phase interacting with the NP surface, which has been identified as responsible for the observed outstanding catalytic performances.

2014 | 7.44

Among the different approaches to humidity sensing available, those based on fluorescent signals are gathering a great deal of attention due to their fast response and versatility of detection and design. So far, all proposals have focused on the use of luminescent probes whose emission is either triggered or inhibited by the presence of water that reacts or alters their chemical environment, hence inducing the signal change. Here, a novel concept in fluorescent humidity sensing based on combining stimuli-responsive photonic resonators with molecular fluorescent probes is introduced. The resonator is assembled from humidity-swellable antimony phosphate nanosheets embedding a planar light-emitting probe, whose emission is dramatically modified by the changes that ambient humidity causes in its photonic environment. Guided by "in silico" optical design of the resonator architecture and subsequent experimental realization, two embodiments of fluorescent photonic humidity sensors featuring turn-on and turn-off detection schemes are presented. The interplay between the luminescent properties of an emitter and its photonic environment implies a fundamental advantage as the emitters are not chemically altered during the detection process. At the same time, it paves the way toward a new generation of photonic humidity sensors which can conveniently be interfaced with common fluorescence detection schemes.

2017 | 7.43

Photonics offers new possibilities to tailor the photoluminescence process in phosphor-converted light emitting diodes. Herein, it is demonstrated that the emission color of thin layers of rare-earth doped nanocrystals can be strongly modulated in tunable spectral ranges using optical resonators specifically designed to this end. GdVO4:Dy3+ nanoparticles of controlled size and shape are synthesized using a solvothermal method with which highly transparent nanophosphor thin films are prepared. This paper designs and fabricates optical multilayers, which are transparent in the UV and resonant at the frequencies where the Dy3+ ions emit, to prove that the color coordinates of this emitter can be tuned from green to blue or yellow with unprecedented precision. Key to the achievement herein reported is the careful analysis of the structural and optical properties of thin nanophosphor layers with the processing temperature in order to achieve efficient photoluminescence while preserving the transparency of the film. The results open a new path for fundamental and applied research in solid-state lighting in which photonic nanostructures allow controlling the emission properties of state-of-the-art materials without altering their structure or chemical composition.

2017 | 7.43

In this work, the reforming of model biogas was investigated on a Rh/MgAl2O4 catalyst. In situ transient and steady-state diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements were used to gain insight into the reaction mechanism involved in the activation of CH4 and CO2. It was found that the reaction proceeds through of an initial pathway in which methane and CO2 are both dissociated on Rh metallic sites and additionally a bifunctional mechanism in which methane is activated on Rh sites and CO2 is activated on the basic sites of the support surface via a formate intermediate by H-assisted CO2 decomposition. Moreover, this plausible mechanism is able to explain why the observed apparent activation energy of CO2 is much lower than that of CH4. Our results suggest that CO2 dissociation facilitates CH4activation, because the oxygen-adsorbed species formed in the decomposition of CO2 are capable of reacting with the CHx species derived from methane decomposition.

2017 | 7.41

Fischer-Tropsch (FTS) reaction is a well-known catalytic process for the conversion of synthesis gas into liquid fuels. The addition of a water gas shift (WGS) catalyst to the FTS one has been postulate to notably increase the efficiency of the process. In order to investigate this issue, we conducted the FTS reaction over a Co-Re/Al2O3 catalyst combined with an optimal WGS Pt/CeO2 catalyst. We observed a notable increase of CO conversion in presence of the Pt/CeO2 catalyst that a priori could be attributed to the WGS reaction. However, the WGS reaction is unfavourable at pressures higher than 1 bar and CO/CO2 hydrogenation over Pt/CeO2 could be more favoured under FTS reaction conditions. In order to gain insights on this fact and elucidate the role of Pt/CeO2 in the FTS reaction we have performed an operando DRIFTS-MS study under close FTS reaction conditions at 4 bar over the Pt/CeO2 catalyst.

2022 | 7.40

To improve TiO2 for H2 generation, one strategy for the separation of photogenerated charges is the formation of heterostructures with other materials. In particular, NiO is a photocatalyst known for its good stability and low cost. However, no studies at pilot scale using solar energy have been described. Consequently, an evaluation of a physical NiO:TiO2 mixture at pilot scale (25 L) with natural irradiation (2.10 m2 of sun-exposed surface) and with simultaneous glycerol photoreforming was explored. NiO:TiO2 50 mg & sdot;L- 1 resulted in the highest hydrogen production, showing an STH = 1.44%, considering only the UV fraction of the solar irradiation. H2 and CO2 production were analysed by on-line GC; Glycerol, dissolved organic carbon, carboxylic acids and nickel leaching were also evaluated. The NiO:TiO2 mixtures rendered a systematically lower H2 production in natural water than in high-purity water. The increase of ionic strength increased the mean size of particle clusters, promoting rapid sedimentation. All this indicates the importance of testing under real field conditions for attaining reliable solar to hydrogen (STH) efficiency.

2023 | 7.40

Exploring available catalytic systems to understand their behavior is a must to properly design efficient catalysts aiming to definitively drive biomass from laboratory to industrial scale. Glucose transformation to levulinic acid involves cascade reactions with specific requirements, different active sites in each case and secondary reactions hard to avoid which are intrinsically linked to the catalyst's nature and reaction conditions. In the present work, homogeneous, heterogeneous and heterogeneous/homogeneous catalysts are considered with the unique goal of improving levulinic acid yield while understanding the catalytic behaviour of cost-effective catalysts. The choice of the catalytic systems and the effect of the main reaction parameters on activity and selectivity is studied and discussed.

2022 | 7.40

This work includes a complete study of the reaction of reforming a simulated producer gas stream comparing a Ni-based catalyst with another one promoted with potassium to enhance the resistance to coke formation. Although coke deposition is unavoidable in the presence of tars in the stream, the analysis of different reaction parameters revealed that operating at 750 degrees C, weight hourly space velocity (WHSV) of 60 L-1 g(-1) h(-1) and 10-20 vol% of steam is possible to minimize the accumulation of carbon deposits. Moreover, it was demonstrated that the addition of potassium helps to mitigate carbon formation, but a high concentration of steam leads to nickel sintering and/or partial oxidation of metallic nickel. On this basis, it was successfully evidenced that the Ni-K catalyst is an excellent candidate for obtaining clean syngas from producer gas reforming.

2022 | 7.40

Novel zinc-doped Metal-Organic Framework based on MIL53(Fe) (Zn-MIL53(Fe)) has been successfully synthesised in one-step, exhibiting dual applications as adsorbent and catalyst. Initially, the adsorption capacity of MIL53(Fe) and Zn-MIL53(Fe) for removing Rhodamine B was assessed through kinetic and isotherm studies. The bimetallic variant exhibited superior performance, showcasing enhanced adsorption capabilities, particularly in the context of its physical interaction under natural pH. After that, the catalytic activity of both synthesised materials was evaluated to generate sulphate radicals by activating PeroxyMonoSulphate (PMS). It was also demonstrated that Zn-MIL53(Fe) exhibited the best catalytic activity being optimised using response surface methodology for Rhodamine B degradation (0.11 mM PMS and 43.2 mg Zn-MIL53(Fe)). Under optimal conditions, favourable outcomes were attained, facilitating the degradation of Rhodamine B, Fluoxetine, and Sulfamethoxazole by 93, 99, and 75 %, respectively. Furthermore, the operational stability of the Zn-MIL53(Fe) was verified, as it remains structurally and catalytically intact after different cycles.

2024 | 7.40

We demonstrate an enhanced and tailor-made directional emission of light-emitting devices using nanoimprinted hexagonal arrays of aluminum nanoparticles. Fourier microscopy reveals that the, luminescence of the device is not only determined by the material properties of the organic dye molecules but is also strongly influenced by the coherent scattering resulting from periodically arranged metal nanoparticles. Emitters can couple to lattice-induced hybrid plasmonic-photonic modes sustained by plasmonic arrays. Such modes enhance the spatial coherence of an emitting layer, allowing the efficient beaming of the emission along narrow angular and spectral ranges. We show that tailoring the separation of the nanoparticles in the array yields an accurate angular distribution of the emission. This combination of large-area metal nanostructures fabricated by nanoimprint lithography and light-emitting devices is beneficial for the design and optimization of solid-state lighting systems.

2014 | 7.39

Herein we provide direct experimental evidence that proves that the photophysical properties of thin methylammonium lead iodide perovskite films are significantly enhanced by localized surface plasmon resonances (SPRs). Observations are well supported by rigorous calculations that prove that improved light harvesting can be unequivocally attributed to plasmonic scattering and near field reinforcement effects around silver nanoparticles embedded within the semiconductor layer. Adequate design of the localized SPR allows raising the absorptance of a 300 nm thick film at well-defined spectral regions while minimizing the parasitic absorption from the metallic inclusions. Measured enhancements can be as large as 80% at specific wavelengths and 20% when integrated over the whole range at which SPR occurs, in agreement with theoretical estimations. Simultaneously, the characteristic quenching effect that the vicinity of metals has on the photoluminescence of semiconductors is largely compensated for by the combined effect of the enhanced photoexcitation and the higher local density of photon states occurring at SPR frequencies, with a two fold increase of the perovskite photoemission efficiency being measured.

2020 | 7.39

Laser ablation is an effective method to clean Cu-based alloys. A novel procedure of characterisation was developed involving O-18 isotopes evaluated by ToF-SIMS spectroscopy to assess the driving mechanisms of laser-surface interactions. The presence of re-oxidised compounds was detected, discerning between the oxygen from the corrosion layer and the one introduced by the interaction with the laser (that was generated in a controlled atmosphere of O-18 diluted in N-2). A set of samples treated with different laser conditions were characterised by FESEM and mu Raman. The results have shown that re-oxidation phenomenon can occur and its selectivity depends on the laser conditions.

2021 | 7.39

Herein, we present a prototype of a photovoltaic module that combines a luminescent solar concentrator integrating one-dimensional photonic crystals and in-plane CuInGaSe2 (CIGS) solar cells. Highly uniform and wide-area nanostructured multilayers with photonic crystal properties were deposited by a cost-efficient and scalable liquid processing amenable to large-scale fabrication. Their role is to both maximize light absorption in the targeted spectral range, determined by the fluorophore employed, and minimize losses caused by emission at angles within the escape cone of the planar concentrator. From a structural perspective, the porous nature of the layers facilitates the integration with the thermoplastic polymers typically used to encapsulate and seal these modules. Judicious design of the module geometry, as well as of the optical properties of the dielectric mirrors employed, allows optimizing light guiding and hence photovoltaic performance while preserving a great deal of transparency. Optimized in-plane designs like the one herein proposed are of relevance for building integrated photovoltaics, as ease of fabrication, long-term stability and improved performance are simultaneously achieved.

2015 | 7.37

Acid and thermal treated sepiolite was organophilized by cationic exchange with several alkylammonium cations (octylammonium, hexadecylammonium, tetradecyltrimethylammonium, and hexadecyltrimethylammonium). The adsorption capacity of BTEX from aqueous solutions was evaluated through the adsorption isotherms performed in batch. The results were analysed using three isotherm models: Freundlich, Langmuir and Dubinin-Radushkevich (D-R model). The behaviour of adsorption isotherm suggested the multilayer coverage on a heterogeneous surface, which is according to the Freundlich isotherm model. The thermodynamic analyse using the D-R model show that physical mechanisms govern the process. The maximum adsorption capacity of BTEX on the obtained materials was in the range values of 81.19 mg g(-1) - 1448.42 mg g(-)(1), which are higher than those reported up to now. The organo-sepiolite materials exhibit a high potential in the adsorption of BTEX compounds from aqueous solutions.

2021 | 7.34

Maximizing the electrochromic response of tungsten oxide-based systems demands highly porous electrode layers that facilitate the incorporation of electrolyte cations during the reduction process. In this work, amorphous and porous WO3 thin films were grown on indium tin dioxide glass substrates by magnetron sputtering at oblique angles at two different plasma gas pressures. Remarkably, the film that showed higher porosity presented a worse electrochromic response in terms of durability, time response and charge density capacity. This result is analyzed and explained on the basis of the features of the porous structure of the films: While the typical nanostructure developed at low pressures possesses large and connected pore voids with few ramifications, the nanostructure generated at a higher pressure presents a rather sponge-like porous structure with numerous and small well-connected voids. A general discussion on the role of the porous structure and, particularly, on the accessible pore volume and area is carried out. It is concluded that not only the accessible pore volume, defining the volume of electrolyte that stays inside the layer, but also the accessible pore area, which defines the efficiency of the incorporation/release of Li+ cations within the electrode material, determine the efficiency and reversibility of the electrochromic response.

2021 | 7.34

Tailoring the interaction of electromagnetic radiation with matter is central to the development of optoelectronic devices. This becomes particularly relevant for a new generation of devices offering the possibility of solution processing with competitive efficiencies as well as new functionalities. These devices, containing novel materials such as inorganic colloidal quantum dots or hybrid organic-inorganic lead halide perovskites, commonly demand thin (tens of nanometers) active layers in order to perform optimally and thus maximizing the way electromagnetic radiation interacts with these layers is essential. In this Perspective, we discuss the relevance of tailoring the optical environment of the active layer in an optoelectronic device and illustrate it with two real-world systems comprising photovoltaic cells and light emitting devices.

2018 | 7.33

Herein we present a combined study of the evolution of both the photoluminescence (PL) and the surface chemical structure of organic metal halide perovskites as the environmental oxygen pressure rises from ultrahigh vacuum up to a few thousandths of an atmosphere. Analyzing the changes occurring at the semiconductor surface upon photoexcitation under a controlled oxygen atmosphere in an X-ray photoelectron spectroscopy (XPS) chamber, we can rationalize the rich variety of photophysical phenomena observed and provide a plausible explanation for light-induced ion migration, one of the most conspicuous and debated concomitant effects detected during photoexcitation. We find direct evidence of the formation of a superficial layer of negatively charged oxygen species capable of repelling the halide anions away from the surface and toward the bulk. The reported PL transient dynamics, the partial recovery of the initial state when photoexcitation stops, and the eventual degradation after intense exposure times can thus be rationalized.

2018 | 7.33

Two multilayer solar selective absorber coatings [Al/CrN0.95/Cr0.96Al0.04N1.08/Cr0.53Al0.47N1.12/Al2O3 (stack #1) and Cr0.96Al0.04N0.89/Cr0.62Al0.38N1.00/Cr0.53Al0.47N1.12/Al2O3 (stack #2)] were deposited on 316L steel by combining direct current (DC) and high power impulse magnetron sputtering (HiPIMS) technologies with the aim of increasing the working limit temperature. The composition and thickness of the constituent layers were optimized using CODE software to achieve a high solar absorptance (alpha) and low values of thermal emittance (epsilon) in the infrared region. The deposited multilayered stacks were heated during 2 h in air at 600, 700 and 800 degrees C to study their thermal stability and optical performance. Compositional, structural and optical characterization of the stacks (as-prepared and after thermal treatment) was performed. Both stacks presented a good solar selectivity with alpha > 95% and epsilon < 15%, were stable up to 600 degrees C and fulfilled the performance criterion PC < 5% after 600 and 700 degrees C treatments. Despite the stacks suffered chemical transformations above 600 degrees C, partial oxidation (stack #1) and Cr2N formation (stack #1 and #2), the optical properties were optimum up to 700 degrees C for stack #1 (alpha = 94%, epsilon((25 degrees C)) = 12%) and 600 degrees C for stack #2 (alpha = 93%, epsilon((25 degrees C)) = 13%). The solar-to-mechanical energy conversion efficiencies (eta) of the as-deposited and annealed (600 and 700 degrees C) samples were up to 20% points higher than the absorber paint commercially used (Pyromark). At 800 degrees C, they underwent a further structural transformation, provoked by the oxidation of the inner layers, and they consequently lost their solar selectivity.

2020 | 7.27

Carbon-based nanomaterials such as graphene are at a crucial point in application development, and their promising potential, which has been demonstrated at the laboratory scale, must be translated to an industrial setting for commercialization. Graphene nanoribbons in particular overcome one limitation of graphene in some electronic applications because they exhibit a sizeable bandgap. However, synthesis of bottom-up graphene nanoribbons is most commonly performed under ultra-high vacuum conditions, which are costly and difficult to maintain in a manufacturing environment. Additionally, little is known about the stability of graphene nanoribbons under ambient conditions or during transfer to technologically relevant substrates and subsequent device processing. This work addresses some of these challenges, first by synthesizing bottom-up graphene nanoribbons under easily obtained high vacuum conditions and identifying water and oxygen as the residual gases responsible for interfering with proper coupling during the polymerization step. And second, by using Raman spectroscopy to probe the stability of nanoribbons during storage under ambient conditions, after transfer to arbitrary substrates, and after fabrication of field-effect transistor devices, which shows structurally intact nanoribbons even several months after synthesis. These findings demonstrate the potential of graphene nanoribbon technologies by addressing some limitations which might arise in their commercialization.

2017 | 7.23

Plasma reactions of CO2 + CH4 mixtures have been proposed as a suitable process for the dry reforming of methane. Without specific catalysts, most studies report the formation of CO and H2 as main reaction products and arise the question whether CHx radicals coming from CH4 may interact with intermediate species formed by electron impact dissociation of CO2, a critical step for the formation of high added value oxygenated compounds. We have addressed this question studying the CO2 + CH4 plasma reaction in a ferroelectric-moderated packed -bed reactor varying the reactants ratio. Analysis of the reaction products by mass spectrometry and the plasma reaction intermediates by optical emission spectroscopy suggest that few direct cross-link interactions exist between intermediate plasma species issued from CH4 or CO2. This preliminary evidence is corroborated by experiments using 13CO2 instead 12CO2 as reactant. The isotope labeling procedure has proved that plasma re-action mechanisms of CO2 and CH4 molecules proceed almost independently, with the formation of small amounts of water and the removal of carbon deposits resulting CH4 plasma decomposition as sole evidences of cross reactions. These results highlight the need of using catalysts to promote specific surface reactions for a better control of the selectivity of the process.

2023 | 7.20

The oil and gas sector produces a considerable volume of greenhouse gas emissions, mainly generated from flaring and venting natural gas. Herein, a techno-economic analysis has been performed of a switchable catalytic process to convert the CH4 and CO2 in flared/vented natural gas into syngas or methanol. Specifically, it was shown that depending on greenhouse gas composition, dry methane reforming (DRM), reverse water-gas shift (RWGS), and CO2 methanation could be chosen to valorise emissions in an overall profitable and flexible operation scenario. The switchable process produced methanol and synthetic natural gas as its products, resulting in an annual income of €687m and annual operating expenses of €452m. The pre-tax profit was calculated at €234m, and at the end of the project, the net present value was calculated as €1.9b with a profitability index of 4.7€/€. The expected payback time of this process was ca. 4 years, and with a 35% internal rate of return (IRR). Most importantly, this process consumed 42.8m tonnes of CO2 annually. The sensitivity analysis revealed that variations in operation time, green hydrogen price, and products' prices significantly impacted the profitability of the process. Overall, this techno-economic analysis demonstrated that switchable catalysis in greenhouse gas utilisation processes is profitable, and thus it could play an important role in achieving net zero emissions.

2024 | 7.20

Achieving highly transparent and emissive films based on perovskite quantum dots (PQDs) is a challenging task since their photoluminescence quantum yield (PLQY) typically drops abruptly when they are used as building blocks to make a solid. In this work, we obtain highly transparent films containing FAPbBr(3) quantum dots that display a narrow green emission (lambda = 530 nm, full width at half-maximum (FWHM) = 23 nm) with a PLQY as high as 86%. The method employed makes use of porous matrices that act as arrays of nanoreactors to synthesize the targeted quantum dots within their void space, providing both a means to keep them dispersed and a protective environment. Further infiltration with poly(methyl methacrylate) (PMMA) increases the mechanical and chemical stability of the ensemble and serves to passivate surface defects, boosting the emission of the embedded PQD and significantly reducing the width of the emission peak, which fulfills the requirements established by the Commission Internationale de l'E ' clairage (CIE) to be considered an ultrapure green emitter. The versatility of this approach is demonstrated by fabricating a color-converting layer that can be easily transferred onto a light-emitting device surface to modify the spectral properties of the outgoing radiation.

2023 | 7.20

The production of CO via Reverse Water Gas Shift (RWGS) reaction is a suitable route for CO2 valorization. In this study a series of modified spinels AB2O4 (A site symbolscript Ni, Zn and Cu and B symbolscript are investigated as RWGS catalysts and their structure-to-function relationships derived from the changes on the A-site cation are ratio-nalized. For all ferrite systems, the RWGS reaction the process main activity and selectivity is governed by the B -site cation, but the variations on the A-site metals determines catalysts' structural features and stability in the reaction. Among the catalyst series, superior RWGS performance displayed the ferrites modified with Cu and Ni associated to the greater oxygen vacancy population for those spinels enabled by the partial allocation on symbolscript cations into the tetrahedral sites.

2023 | 7.20

With a high number of diesel vehicles worldwide, particulate emission control is an urgent issue with a global impact, from the health of citizens to commercial future of this technology in some transport segments. Particulate filters are widely used in automotive engines to comply emissions regulations, but current technologies have room for improvement as they add additional backpressure in the exhaust system, and efficient on-board regeneration process is challenging. The Fil-Bio-Diesel Project is a R&D initiative to improve current particle filtration systems, based on the development of novel biomorphic substrates. By replicating the biologic tissue of a wood precursor, a biomorphic silicon carbide with hierarchic orthotropic microstructure can be produced. The porosity, the pore size, and pore orientation of this bioceramic material can be tailored through the selection of a suitable precursor, widening the initially narrow relationship between filtration efficiency and pressure drop that characterizes granular ceramic materials. In this paper the methodology and main results of the Fil-Bio-Diesel Project are presented. This work shows the peculiar advantages of biomorphic silicon carbide through several experimental studies. The results show the potential of this novel filter substrate to be used in future particulate abatement systems.

2020 | 7.15

Transition metal chalcogenides with lamellar structure are known for their use in tribological applications although limited to vacuum due to their easy degradation in the presence of oxygen and/or moisture. Here we present a tailored WSex coating with low friction (0.07) and low wear rates (3 × 10–7 mm3 Nm–1) even in ambient air. To understand the low friction behavior and lower chemical reactivity a tribological study is carried out in a high-vacuum tribometer under variable pressure (atmospheric pressure to 1 × 10–8 mbar). A detailed investigation of the film nanostructure and composition by advanced transmission electron microscopy techniques with nanoscale resolution determined that the topmost layer is formed by nanocrystals of WSe2 embedded in an amorphous matrix richer in W, a-W(Se). After the friction test, an increased crystalline order and orientation of WSe2 lamellas along the sliding direction were observed in the interfacial region. On the basis of high angle annular dark field, scanning transmission electron microscopy, and energy dispersive X-ray analysis, the release of W atoms from the interstitial basal planes of the a-W(Se) phase is proposed. These W atoms reaching the surface, play a sacrificial role preventing the lubricant WSe2 phase from oxidation. The increase of the WSe2 crystalline order and the buffer effect of W capturing oxygen atoms would explain the enhanced chemical and tribological response of this designed nanocomposite material.

2015 | 7.15

The fabrication of single-material photonic-multilayer devices is explored using a new methodology to produce porous silicon layers by magnetron sputtering. Our bottom-up methodology produces highly stable amorphous porous silicon films with a controlled refractive index using magnetron sputtering and incorporating a large amount of deposition gas inside the closed pores. The influence of the substrate bias on the formation of the closed porosity was explored here for the first time when He was used as the deposition gas. We successfully simulated, designed, and characterized Bragg reflectors and an optical microcavity that integrates these porous layers. The sharp interfaces between the dense and porous layers combined with the adequate control of the refractive index and thickness allowed for excellent agreement between the simulation and the experiments. The versatility of the magnetron sputtering technique allowed for the preparation of these structures for a wide range of substrates such as polymers while also taking advantage of the oblique angle deposition to prepare Bragg reflectors with a controlled lateral gradient in the stop band wavelengths.

2015 | 7.15

This work presents a simple experimental procedure to probe light confinement effects in photonic structures. Two types of porous 1D Bragg microcavities with two resonant peaks in the reflection gap were prepared by physical vapor deposition at oblique angle configurations and then infiltrated with dye solutions of increasing concentrations. The unusual position shift and intensity drop of the transmitted resonant peak observed when it was scanned through the dye absorption band have been accounted for by the effect of the light trapped at their optical defect layer. An experimentally observed giant absorption of the dye molecules and a strong anomalous dispersion in the refractive index of the solution are claimed as the reasons for the observed variations in the Bragg microcavity resonant feature. Determining the giant absorption of infiltrated dye solutions is proposed as a general and simple methodology to experimentally assess light trapping effects in porous photonic structures.

2018 | 7.14

This study demonstrates a design that maximizes the power radiated into free space from a monolayer of nanoemitters embedded in a flexible distributed Bragg reflector conformably attached to a metal surface. This is achieved by positioning the light source at the precise depth within the multilayer for which optical Tamm states provide enhanced quantum yield and outcoupling efficiency, which are combined to optimize the luminous power radiated by the surface of the ensemble. This approach, based on the adhesion of flexible multilayer stacks onto metal surfaces with an arbitrary curvature, is versatile and permits the realization of spectrally narrow monodirectional or self-focusing light-emitting surfaces.

2018 | 7.13

Combinations of perovskite-type oxides with transition and precious metals exhibit remarkable regenerating properties that can be exploited for catalytic applications. The objective of the present work was to study the structural changes experienced by LaCo0.8Cu0.2O3 under reducing/oxidizing atmosphere (redox) and Preferential Oxidation of CO (PrOx, with high H2 concentration) conditions and their reversibility. LaCo0.8Cu0.2O3 was prepared by ultrasonic spray combustion and was characterized by X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Structural changes were followed by operando XRD and XAS. Metallic Co and Cu were segregated under both sets of reducing conditions and re-dissolved into the perovskite upon oxidation at 500 °C. Simultaneously, the perovskite-type oxide disappeared under reducing conditions and formed again upon high-temperature oxidation. The effects of this reversible reduction/dissolution of B-site metals on catalyst structure and activity were studied concerning the catalytic process of PrOx. The active phases of cobalt and copper oxides suffer a reduction during the PrOx reaction due to the high H2 concentration; thus, the application of an intermediate oxidation treatment can regenerate the catalytic system and the perovskite can be used for several cycles of reaction and regeneration. In contrast, when this intermediate oxidation treatment is not applied, the catalytic performance decreases in successive activity cycles.

2024 | 7.10

Iron (III) was incorporated, to the surface of a synthesized ZnO, using two nominal molar percentages of Fe (III): 1% and 5% Fe relative to ZnO. Samples dried and calcined at 200 °C and 400 °C for 2 h, were characterized by XRD, XPS, XRF, N2-adsorption-BET and (UV–vis)-DRS. Photocatalytic activities of the catalysts were assessed based on the degradation of rhodamine B (RhB) and caffeine (CAF) in aqueous solution under two irradiation conditions: UV and visible light illumination. Prior to the photocatalytic tests, the interaction of each one of the substrates with either Fe(III) or Fe(II) was studied in homogeneous medium under UV-illumination and oxygenated environment. It was found that Fe (III) can play an important role in homogeneous media in the photoassisted degradation, both of rhodamine B and caffeine, while Fe (II) does not exert a relevant role in the photoassisted degradation of the referred substrates. Fe–ZnO samples display similar or poorer performance than pure ZnO in the presence of UV light for both studied substrates. The phenomenon can be attributed to the formation of either goethite or ZnFe2O4 at the ZnO surface where the coupled Fe3+/Fe2+ can act as recombination centers for the photogenerated charges. On the contrary, all Fe–ZnO samples showed enhanced photocatalytic activity under visible illumination which seems to be independent of the iron content. In this context, the mechanisms for photoassisted degradation of both the substrates in homogeneous medium and photocatalytic degradation are discussed, as well as the role of Fe in the photodegradation processes.

2020 | 7.09

The rational design of electrodes mimicking the cellular structure of natural bio-resources has been a matter of increasing interest for applications in energy storage. Due to their anisotropic and hierarchical porosity, monolithic carbon materials from natural wood precursors are appealing as electrodes for supercapacitor applications due to their interconnected channels, relatively low cost and environmentally friendly synthesis process. In this work, a liquid-phase oxidative treatment with refluxing nitric acid at 100 degrees C for 8 h was performed to enhance the surface properties of beech-derived graphitized carbons treated with an iron catalyst. Microstructural, textural and surface investigations revealed that this strategy was successful in removing amorphous carbon and in functionalizing their surfaces. The crystallinity, accessible surface area, micropore volume and surface functionality of beech-derived carbons were increased upon the reflux treatment. The resulting porous carbon materials were evaluated as binderless monolithic electrodes for supercapacitors applications in aqueous KOH electrolyte. A maximum specific capacitance of 179 F.g(-1) and a volumetric capacitance of 89 Fcm(-3) in galvanostatic charge/discharge experiments were reached. Monolithic electrodes exhibited good cycling stability, with a capacitance retention over 95% after 10,000 cycles.

2020 | 7.03

Thermochemical energy storage (TCES) is considered as a promising technology to accomplish high energy storage efficiency in concentrating solar power (CSP) plants. Among the various possibilities, the calcium-looping (CaL) process, based on the reversible calcination–carbonation of CaCO3 stands as a main candidate due to the high energy density achievable and the extremely low price, nontoxicity, and wide availability of natural CaO precursors such as limestone. The CaL process is already widely studied for CO2 capture in fossil fuel power plants or to enhance H2 production from methane reforming. Either one of these applications requires particular reaction conditions to which the sorbent performance (reaction kinetics and multicycle conversion) is extremely sensitive. Therefore, specific models based on the conditions of any particular application are needed. To get a grip on the optimum conditions for the carbonation of limestone derived CaO in the CaL-CSP integration, in the present work is pursued a multidisciplinary approach that combines theoretical modeling on reaction kinetics, lab-scale experimental tests at relevant CaL conditions for TCES, process modeling, and simulations. A new analytic equation to estimate the carbonation reaction rate as a function of CO2 partial pressure and temperature is proposed and validated with experimental data. Using the kinetics analysis, a carbonator model is proposed to assess the average carbonation degree of the solids. After that, the carbonator model is incorporated into an overall process integration scheme to address the optimum operation conditions from thermodynamic and kinetics considerations. Results from process simulations show that the highest efficiencies for the CaL-CSP integration are achieved at carbonator absolute pressures of ∼3.5–4 bar, which leads to an overall plant efficiency (net electric power to net solar thermal power) around 41% when carbonation is carried out at 950 °C under pure CO2

2018 | 6.97

Plant cuticles have been used as models to produce hydrophobic films composed of sodium alginate, the fatty acid fraction of tomato pomace agrowaste, and beeswax. The fabrication process consisted of the blending of components in green solvents (water and ethanol) and a subsequent thermal treatment (150 degrees C, 8 h) to polymerize unsaturated and polyhydroxylated fatty acids from tomato pomace. When sodium alginate and tomato pomace fatty acids were blended, free-standing films were obtained. These films were characterized to evaluate their morphological (SEM), chemical (solid-state NMR, ATR-FTIR), mechanical (tensile tests), thermal (TGA), and hydrodynamic (water contact angle, uptake, and permeability) properties. A comparison between nonpolymerized and polymerized samples was carried out, revealing that the thermal treatment represents a sustainable route to create structured, composite networks of both components. Finally, beeswax was added to the blend with the same amounts of sodium alginate and tomato pomace fatty acids. The presence of the wax improved the hydrophobicity and the mechanical and water barrier properties as well as decreased the water uptake. These results indicate that polymerized plant cuticle-like films have valuable potential for packaging applications.

2018 | 6.97

This work presents a comparison of the gold- and platinum-based catalysts behavior in the water–gas shift (WGS) reaction. The influence of the support, e.g., its composition and electronic properties, studied in detail by means of UV–Vis spectroscopy, of the metal nature and dispersion and of the stream composition has been evaluated. The catalytic performance of the samples is directly correlated with the electronic properties modification as a function of metal and/or support. Both metals present high activity in the selected reaction although in a different operation temperature window.

2014 | 6.92

The complex electron–phonon interaction occurring in bulk lead halide perovskites gives rise to anomalous temperature dependences, like the widening of the electronic band gap as temperature increases. However, possible confinement effects on the electron–phonon coupling in the nanocrystalline version of these materials remain unexplored. Herein, we study the temperature (ranging from 80 K to ambient) and hydrostatic pressure (from atmospheric to 0.6 GPa) dependence of the photoluminescence of ligand-free methylammonium lead triiodide nanocrystals with controlled sizes embedded in a porous silica matrix. This analysis allowed us to disentangle the effects of thermal expansion and electron–phonon interaction. As the crystallite size decreases, the electron–phonon contribution to the gap renormalization gains in importance. We provide a plausible explanation for this observation in terms of quantum confinement effects, showing that neither thermal expansion nor electron–phonon coupling effects may be disregarded when analyzing the temperature dependence of the optoelectronic properties of perovskite lead halide nanocrystals.

2021 | 6.89

The recent development of organic polaritonic solar cells, in which sunlight absorbers and photon modes of a resonator are hybridized as a result of their strong coupling, has revealed the potential this interaction offers to control and enhance the performance of these devices. In this approach, the photovoltaic cell is built in such a way that it also behaves as an optical cavity supporting spectrally well-defined resonances, which match the broad absorption bands of the dyes employed. Herein we focus on the experimental and theoretical analysis of the specific spectral and angular optical absorption characteristics of a broadband light harvester, namely a subphthalocyanine, when operating in the ultrastrong coupling regime. We discuss the implications of having a broad distribution of oscillator strengths and demonstrate that rational design of the layered structure is needed to optimize both the spectral and the angular response of the sunlight harvester dye.

2021 | 6.89

A wide-range in situ tunable 1D Bragg microcavity including a hybrid layer as white light emitter defect is shown by J. R. Sanchez-Valencia, A. Borras, and co-workers on page 1124. White emission is obtained by Förster resonance energy transfer between blue (1,3,5-triphenyl-2-pyrazoline) and orange (rubrene) dyes homogeneously infiltrated within the host nanocolumnar SiO2film, which is formed by glancing angle deposition. Sequential physical vapor deposition at low temperatures provides the organic dyes localization within the porous nanostructure of the defect layer.

2016 | 6.88

The present work reports the renewable hydrogen production by photocatalytic degradation of glucose over commercial and home prepared TiO2 modified by the simultaneous presence of fluorine and Pt (Pt-F-TiO2). The obtained materials were widely characterized by different techniques (XRD, SBF, UV-Vis DRS, XRF, SEM and TEM) and it was found that surface area, anatase/rutile ratio and the distribution and size of the platinum particles are important factors influencing the effectiveness of these materials in the H-2 production. The photocatalytic H-2 production from the glucose solution was 97 mu mol of H-2 after 3 h of irradiation on home prepared TiO2 modified by F and Pt addition, while a lower value corresponding to 31 mu mol of H-2 was obtained on commercial TiO2 modified by F and Pt, after 3 h of irradiation. The hydrogen production rate increased by decreasing the initial pH of solution reaching the highest value of about 590 mu mol h(-1) g(-1) after 3 h of irradiation time at pH = 2. Accordingly, sugar containing wastewaters from food industry has the potential for producing hydrogen by photocatalytic process while removing organics before disposal or reuse. 

2016 | 6.84

A synthetic route to building photoconducting films of TiO2 nanoparticles that display bright structural color is presented. The color arises as a result of the periodic modulation of the refractive index, which is achieved by controlling the degree of porosity of each alternate layer through the particle size distribution of the precursor suspensions. The suspensions are cast in the shape of a film by spin-coating, which allows tailoring of the lattice parameter of the periodic multilayer, thus tuning the Bragg peak spectral position (i.e., its color) over the entire visible region. Photoelectrochemical measurements show that the Bragg mirrors are conductive and distort the photocurrent response as a result of the interplay between photon and electron transport.

2008 | 6.81

The bi-reforming of methane (BRM) has the advantage of utilising greenhouse gases and producing H2 rich syngas. In this work Ni stabilised in a pyrochlore-double perovskite structure is reported as a viable catalyst for both Dry Reforming of Methane (DRM) and BRM. A 10 wt.% Ni-doped La2Zr2O7 pyrochlore catalyst was synthesised, characterised and tested under both reaction conditions and its performance was compared to a supported Ni/La2Zr2O7. In particular the effect of steam addition is investigated revealing that steam increases the H2 content in the syngas but limits reactants conversions. The effect of temperature, space velocity and time on stream was studied under BRM conditions and brought out the performance of the material in terms of activity and stability. No deactivation was observed, in fact the addition of steam helped to mitigate carbon deposition. Small and well dispersed Ni clusters, possibly resulting from the progressive exsolution of Ni from the mixed oxide structure could explain the enhanced performance of the catalyst.

2020 | 6.77

Cobalt nanoparticles were synthesised via the thermal decomposition of Co2(CO)8 and were coated in iron oxide using Fe(CO)5. While previous work focused on the subsequent thermal alloying of these nanoparticles, this study fully elucidates their composition and core@shell structure. State-of-the-art electron microscopy and statistical data processing enabled chemical mapping of individual particles through the acquisition of energy-filtered transmission electron microscopy (EFTEM) images and detailed electron energy loss spectroscopy (EELS) analysis. Multivariate statistical analysis (MSA) has been used to greatly improve the quality of elemental mapping data from core@shell nanoparticles. Results from a combination of spatially resolved microanalysis reveal the shell as Fe3O4 and show that the core is composed of oxidatively stable metallic Co. For the first time, a region of lower atom density between the particle core and shell has been observed and identified as a trapped carbon residue attributable to the organic capping agents present in the initial Co nanoparticle synthesis.

2013 | 6.74

We present a straightforward procedure of self-surface patterning with potential applications as large area gratings, invisible labeling, optomechanical transducers, or smart windows. The methodology is based in the formation of parallel micrometric crack patterns when polydimethylsiloxane foils coated with tilted nanocolumnar SiO2 thin films are manually bent. The SiO2 thin films are grown by glancing angle deposition at room temperature. The results indicate that crack spacing is controlled by the film nanostructure independently of the film thickness and bending curvature. They also show that the in-plane microstructural anisotropy of the SiO2 films due to column association perpendicular to the growth direction determines the anisotropic formation of parallel cracks along two main axes. These self-organized patterned foils are completely transparent and work as customized reversible diffraction gratings under mechanical activation.

2014 | 6.72

We theoretically investigate the building of optical resonators based on the levitation properties of thin films subjected to strong repulsive Casimir-Lifshitz forces when immersed in an adequate medium and confronted with a planar substrate. We propose a design in which cavities supporting high Q-factor optical modes at visible frequencies can be achieved by means of combining commonly found materials, such as silicon oxide, polystyrene or gold, with glycerol as a mediating medium. We use the balance between flotation and repulsive Casimir-Lifshitz forces in the system to accurately tune the optical cavity thickness and hence its modes. The effects of other forces, such as electrostatic, that may come into play are also considered. Our results constitute a proof of concept that may open the route to the design of photonic architectures in environments in which dispersion forces play a substantial role and could be of particular relevance for devising novel microfluidic optical resonators.

2019 | 6.71

The modification of the wetting properties of marble surfaces upon multi-scale texturing induced by ultrafast laser processing (340 fs pulse duration, 1030 nm wavelength) has been investigated with the aim of evaluating its potential for surface protection. The contact angle (CA) of a water drop placed on the surface was used to assess the wettability of the processed areas. Although the surfaces are initially hydrophilic upon laser treatment, after a few days they develop a strong hydrophobic behavior. Marble surfaces have been irradiated with different scan line separations to elucidate the relative roles of multi-scale roughness (nano-and micro-texture) and chemical changes at the surface. The time evolution of the contact angle has been then monitored up to 11 months after treatment. A short and a long-term evolution, associated to the combined effect of multi-scale roughness and the attachment of chemical species at the surface over the time, have been observed. XPS and ATR measurements are consistent with the progressive hydroxylation of the laser treated surfaces although the additional contribution of hydrocarbon adsorbates to the wettability evolution cannot be ruled-out. The robustness of the results has been tested by CA measurements after cleaning in different conditions with very positive results.

2022 | 6.70

This study introduces a novel techno-economic approach to renewable ammonia production using landfill biogas. The proposed process involves bio-hydrogen generation from landfill biogas, nitrogen production via air separation, and the Haber-Bosch process. Building on our prior research, which demonstrated the economic competitiveness of renewable hydrogen production from landfill gas, we extend our investigation to analyze the feasibility of producing renewable ammonia from biogas-derived bio-hydrogen. However, the economic analysis for the baseline scenario reveals the current lack of profitability (net present value of −18.3 M€), with ammonia prices needing to quadruple to achieve profitability. Major costs, including investment, maintenance, overhead expenses, and electricity, collectively account for over 70%, suggesting the potential efficacy of investment subsidies as a political tool. Only cases with subsidies exceeding 50% of total investment costs, under current ammonia market prices, would render the green ammonia route profitable. Our findings underscore the significant techno-economic challenges in realizing renewable ammonia production, emphasizing the need for innovation in process engineering and catalytic technologies to enable competitive and scalable green ammonia production.

2024 | 6.70

Promoting the performance of catalytic systems by incorporating small amount of alkali has been proved effective for several reactions whilst controversial outcomes are reported for the synthetic natural gas production. This work studies a series of Ni catalysts for CO2 and CO methanation reactions. In-situ DRIFTS spectroscopy evidenced similar reaction intermediates for all evaluated systems and it is proposed a reaction mechanism based on: i) formate decomposition and ii) hydrogenation of lineal carbonyl species to methane. Compared to bare Ni, the enhanced CO2 methanation rates attained by NiFe/Al and NiFeK/Al systems are associated to promoted formates decomposition into lineal carbonyl species. Also for CO methanation, the differences in the catalysts' performances were associated to the relative concentration of lineal carbonyl species. Under CO methanation conditions and opposing the CO2 methanation results where the incorporation of K delivered promoted catalytic behaviours, worsened CO methanation rates were discerned for the NiFeK/Al system.

2023 | 6.70

The feasibility of a Dual Function Material (DFM) with a versatile catalyst offering switchable chemical synthesis from carbon dioxide (CO2) was demonstrated for the first time, showing evidence of the ability of these DFMs to passively capture CO2 directly from the air as well. These DFMs open up possibilities in flexible chemical production from dilute sources of CO2, through a combination of CO2 adsorption and subsequent chemical transformation (methanation, reverse water gas shift or dry reforming of methane). Combinations of Ni Ru bimetallic catalyst with Na2O, K2O or CaO adsorbent were supported on CeO2-Al2O3 to develop flexible DFMs. The designed multicomponent materials were shown to reversibly adsorb CO2 between the 350 and 650 degrees C temperature range and were easily regenerated by an inert gas purge stream. The components of the flexible DFMs showed a high degree of interaction with each other, which evidently enhanced their CO2 capture performance ranging from 0.14 to 0.49 mol kg(-1). It was shown that captured CO2 could be converted into useful products through either CO2 methanation, reverse water-gas shift (RWGS) or dry reforming of methane (DRM), which provides flexibility in terms of co-reactant (hydrogen vs. methane) and end product (synthetic natural gas, syngas or CO) by adjusting reaction conditions. The best DFM was the one containing CaO, producing 104 mu mol of CH4 per kg(DFM) in CO2 methanation, 58 mu mol of CO per kg(DFM) in RWGS and 338 mu mol of CO per kg(DFM) in DRM.

2022 | 6.70

The outer surfaces of epidermal cell walls are impregnated with an extracellular matrix called the cuticle. This composite matrix provides several functions at the interface level that enable plants to thrive in different habitats and withstand adverse environmental conditions. The lipid polymer cutin, which is the main constituent of the plant cuticle, has some unique biophysical properties resulting from its composition and structure. This review summarizes the progress made towards understanding the biophysical significance of this biopolymer with special focus on its structural, thermal, biomechanical, and hydric properties and relationships. The physiological relevance of such biophysical properties is discussed in light of existing knowledge on the plant cuticle.

2011 | 6.65

The osteogenic and angiogenic responses of organisms to the ionic products of degradation of bioactive glasses (BGs) are being intensively investigated. The promotion of angiogenesis by copper (Cu) has been known for more than three decades. This element can be incorporated to delivery carriers, such as BGs, and the materials used in biological assays. In this work, Cu-containing mesoporous bioactive glass (MBG) in the SiO2-CaO-P2O5compositional system was prepared incorporating 5% mol Cu (MBG-5Cu) by replacement of the corresponding amount of Ca. The biological effects of the ionic products of MBG biodegradation were evaluated on a well-known endothelial cell line, the bovine aorta endothelial cells (BAEC), as well as in an in vivo zebrafish (Danio rerio) embryo assay. The results suggest that ionic products of both MBG (Cu free) and MBG-5Cu materials promote angiogenesis. In vitro cell cultures show that the ionic dissolution products of these materials are not toxic and promote BAEC viability and migration. In addition, the in vivo assay indicates that both exposition and microinjection of zebrafish embryos with Cu free MBG material increase vessel number and thickness of the subintestinal venous plexus (SIVP), whereas assays using MBG-5Cu enhance this effect.

2018 | 6.64

A series of functionalized nanographitic carbons is prepared, characterized and tested in fructose dehydration reaction to 5-hydroxymethylfurfural. The functionalization treatment was selected to introduce various Bro?nsted acid sites and to modify the textural and catalytic properties of the initial carbon material. Within the series, the sulfonated carbons present the most interesting catalytic behavior resulting in important selectivity to the desired product once the reaction variables were properly adjusted.

2021 | 6.56

Surface defects engineered nano-Cu/TiO2 photocatalysts are synthesized through an easy and cost-effective microwave-assisted hydrothermal synthesis, mixing commercial P25 titania (TiO2) and oxalic acid (Ox), followed by 2.0 wt% Cu co-catalyst (labeled as Cu2.0) loading through in situ photodeposition during reaction. The hydrothermal treatment does not affect the catalyst crystalline structure, morphology, nor the surface area. However, depending on the Ox/TiO2 molar ratio used an influence on the optical properties and on the reactivity of the system is detected. The presence of surface defects leads to intraband states formation between valence band and conduction band of bare titania, inducing an important enhancement in the photoactivity. Thus, Cu2.0/gOx/P25 200 (where g is the weight of Ox and 200 the temperature in Celsius degrees used during the synthesis) have been successfully tested as efficient photocatalysts for hydrogen production through methanol (MeOH) reforming under UV light in a MeOH/ H2O solution (10% v/v) by fluxing the system with N2, showing an increased reactivity compared to the bare Cu2.0/P25 system.

2024 | 6.50

Mixed-halide perovskites represent a particularly relevant case within the family of lead-halide perovskites. Beyond their technological relevance for a variety of optoelectronic devices, photoinduced structural changes characteristic of this type of material lead to extreme photophysical changes that are currently the subject of intense debate. Herein we show that the conspicuous photoinduced phase segregation characteristic of these materials is primarily the result of the local and metastable rearrangement of the iodide sublattice. A local photophysical study comprising spectrally resolved laser scanning confocal microscopy is employed to find a correlation between the defect density and the dynamics of photoinduced changes, which extend far from the illuminated region. We observe that iodide-rich regions evolve much faster from highly defective regions. Also, by altering the material composition, we find evidence for the interplay between the iodide-related defect distribution and the intra- and interdomain migration dynamics giving rise to the complexity of this process.

2020 | 6.48