Scientific Papers in SCI

Abstract

The study explored the incorporation of Cu into Mg2Al1 hydrotalcite-like layered double hydroxides (LDH) and their derived mixed oxides for efficient methyl orange (MO) adsorption. MgAl -LDH (MA -LDH), MgCuAl - LDH(MCA - LDH), and their 500 degrees C thermally treated derivatives (MA - O and MCA-O) were successfully synthesized and comprehensively characterized. Copper doping notably enhanced the adsorption capacity by improving the textural properties and facilitating the formation of a more abundant MgAl2O4 spinel phase in the mixed oxide. The decomposition of both raw and modified LDHs promoted strong interactions with MO, overcoming the mass transfer limitations typically associated with diffusion. The pseudo-second-order (PSO) kinetic model was found to best describe the adsorption behavior of the mixed oxides. The effects of solid-liquid ratio and pH, along with response surface methodology (RSM) using a Box-Behnken design (BBD), were investigated to optimize the adsorption conditions of MO on the MCA -O mixed oxide. Equilibrium and thermodynamic studies revealed a high adsorption capacity for MO (qmax = 1297mg/g at 25 degrees C), with adsorption being both spontaneous and endothermic. Langmuir isotherm and advanced statistical modeling indicated that MO molecules adsorbed on MCA -O formed a monolayer with a general lateral arrangement. Post-adsorption characterization and DFT calculations were employed to gain deeper insight into the adsorption mechanism, which was primarily driven by ion exchange, hydrogen bonding, and pi - pi complexation. The mixed oxide derived from LDH demonstrated excellent stability and remained effective over multiple cycles without significant performance loss.

Abstract

Microplastics are an emerging pollutant of concern. Many microplastics in the waters arise from washing synthetic textiles in residential and commercial washing machines. The present research evaluated the upcycling of this waste to carbon materials by hydrothermal carbonization. Real microfiber waste was collected using clothes washer and dryer microfilters. Via temperature and residence time screening (200 degrees C, 250 degrees C, 300 degrees C and 1 h, 4 h, 8 h) two temperatures of interest were determined (250 degrees C and 300 degrees C) for hydrothermal carbonization, for a residence time of 4 h. The results obtained in this research demonstrated that by varying the reaction conditions carbon production can be tailored, producing amorphous carbon or graphene/graphite. To this end, Raman spectroscopy results indicated the production of carbon nanomaterials; smaller particle sizes were detected after 250 degrees C-4h and 300 degrees C-4h treatments, (29.6 nm and 33.1 nm, respectively). Transforming microfibers into useful carbon nanoparticles via hydrothermal carbonization prolongs their lifecycle and mitigates environmental pollution. This process is an intriguing method of incorporating textile residue (microfibers) into the circular economy, where resources are perpetually recycled, and waste is avoided.

Abstract

The thermal memory effect, TME, has been studied in Ni₅₅Fe₁₉Ga₂₆ shape memory alloys, fabricated as ribbons via melt-spinning and as pellets via arc-melting, to evaluate its dependence on the martensitic structure and the macrostructure of the samples. When the reverse martensitic transformation is interrupted, a kinetic delay in the subsequent complete transformation is only evident in the ribbon samples, where the 14M modulated structure is the dominant phase. In contrast, degradation of the modulated structure or the presence of the γ phase significantly reduces the observed TME. In such cases, the magnitude of the TME approaches the detection limits of commercial calorimeters, and only high-resolution calorimeter at very low heating rate (40 mK h⁻¹) can show the effect. Following the kinetic arrest and subsequent cooling, the reverse martensitic transformation was completed at several heating rates to confirm the athermal nature of the phenomenon.

Abstract

Dye Sensitized Solar Cells (DSSCs) have recently gained renewed interest for their potential in indoor light harvesting and powering wireless devices. However, to fully exploit their potential, crucial aspects require further attention, in particular, the improvement of spectral compatibility and low-light harvesting mechanisms, as well as the development of efficient photoanodes through high-yield scalable methods. In this article, we propose the use of nanocomposite photoanodes integrating mesoporous TiO2 nanoparticles, ITO nanotubes (NT), and anatase TiO2 shells (ITO@TiO2 NT) prepared by step-by-step method relying on mild temperature conditions and avoiding toxic precursors. These photoanodes outperform previous attempts to implement low-dimensional ITO and ITO@TiO2 nanowires and nanotubes for outdoor light conversion, demonstrating a power conversion efficiency under low artificial light intensity of 24 % for at 0.014 mW cm-2, a 166 % increase compared to the conventional architectures. Advanced microstructural, optical, and electrochemical characterizations have revealed that the strong scattering effect of the light in the visible range coupled with enhanced charge collection at low-intensity illumination are the essential mechanisms responsible for such enhanced energy conversion. Remarkably, our devices retain up to 90 % of the normal incidence efficiency even under glancing illumination, while conventional reference devices retain only 30 %.

Abstract

Exploring synergistic interactions between nanomaterials that can enhance their collective properties in ways that individual components cannot achieve represents an avenue for advancing beyond the current state of the art. This approach is particularly relevant in the context of ABX(3) nanocrystals, where pursuing cooperation could help to overcome current challenges associated with light generation. Transparent photoluminescent coatings are developed by combining perovskite nanomaterials and porous scaffolds of high optical quality phosphor nanoparticles. Fine tuning of the spectral content of the emission is achieved with the photoexcitation wavelength, allowing the demonstration of white light emission with tunable hues.

Abstract

This work presents a straightforward strategy for achieving specific overheating during flash experiments by adjusting the initial electrical parameters. To do that, an extensive experimental analysis was performed to evaluate the temperature evolution of dense ZnO specimens during controlled-current ramping at different furnace temperatures, which in turn modified the initial electrical resistance of the sample. A detailed electrical explanation of controlled-current ramp flash processes is provided and, for the first time, a practical equivalence between current-ramp and temperature-ramp flash methodologies is established. By parameterizing the experiments in terms of an effective power density, a consistent heating pattern following the blackbody radiation trend was identified, despite the different electrical characteristics of each experiment. Finally, a “flash heating map” is introduced, which can be used to determine the starting electrical parameters necessary to achieve a specific temperature increase, whether employing current or temperature ramps.

Abstract

The influence of the characteristic features and firing temperature on the ceramic properties of raw kaolin samples were examined studying a wide range of firing temperatures (1000–1500 ºC). The techniques of investigation have been particle size analysis, Transmission Electron Microscopy (TEM), X-ray powder Diffraction (XRD), X-ray Fluorescence analysis (XRF), and Thermal Analysis using Termodilatometry (TD), Thermalgravimetric analysis (TGA) and Differential Thermal Analysis (DTA). Uniaxial pressed cylindric bodies were obtained and fired from 1000 to 1500 °C/2 h. TEM allowed investigate morphological differences and identification of kaolinite and halloysite. The mineralogical analysis indicated that the kaolinite content is high (80–90 wt%). The contents of oxide impurities are relatively low although in a sample is 7.6 wt% on a calcined basis. The characteristic sharp DTA exothermic effect of kaolinite was observed in the range 900–1000 °C. The ceramic properties of the group of kaolin samples has been determined: linear firing shrinkage, water absorption capacity, apparent density and open porosity. Sintering diagrams allowed investigate the progressive decrease of water absorption and the increase of firing shrinkage. In some kaolin samples the water absorption reached zero at 1450–1500 ^ᵒC. High sintering temperatures have been observed when kaolinite is present in high contents and the fluxes content is low. The maximum values of apparent density were determined, with a sample with the highest value (2.75 ± 0.10 g/cm³). The open porosity changes from ∼ 34–38 % at 1000 ᵒC up to zero or minimum values (< 3 %) at 1500 ^ᵒC. This behaviour is associated to the progressive sintering of the particles and filling of pores by glassy phase originated by the presence of fluxes and the influence of a low particle size. The formation of mullite and cristobalite by firing have been studied by XRD. Mullite has been detected from 1000 to 1100 ᵒC and the crystals developed as increasing firing temperatures. Cristobalite (α-cristobalite) has been identified at 1200–1300 ºC. The presence of an alkaline melt could impede the crystallization of cristobalite. This study presents a comparative research because all these commercial kaolin samples have been examined under the same experimental conditions. Consequently, the results have allowed to provide new data about raw kaolin powders with high kaolinite content in the range 80–90 wt%.

Abstract

Plasma treatment of seeds is an efficient procedure to accelerate germination, to improve initial stages of plant growth, and for protection against pathogen infection. Most studies relate these beneficial effects with biochemical modifications affecting the metabolism and genetic growth factors of seeds and young plants. Using barley seeds, in this work, we investigate the redistribution of ions in the seed surface upon their treatment with cold air plasmas. In addition, we investigate the effect of plasma in the lixiviation of ions through the seeds' hull when they are immersed in water. Ion redistribution in the outer layers of air plasma-treated seeds has been experimentally determined through X-ray photoelectron spectroscopy analysis in combination with in-depth chemical profiling with gas cluster ion beams. The results show that in the shallowest layers of the seed hull (at least up to a depth of similar to 100 nm) there is an enrichment of K+ and Ca2+ ions, in addition to changes in the O/C and N/C atomic ratios. These data have been confirmed by the electron microscopy/fluorescence analysis of seed cuts. Observations have been accounted for by a Monte Carlo model, simulating the electrostatic interactions that develop between the negative charge accumulated at the seed surface due to the interaction with the plasma sheath and the positive ions existing in the interior. Furthermore, it is shown that upon water immersion of plasma-treated seeds mobilized ions tend to lixiviate more efficiently than in pristine seeds. The detection of a significant concentration of NO3 - anions in the water has been attributed to a secondary reaction of nitrogen species incorporated into the seeds during plasma exposure with reactive oxygen species formed on their surface during this treatment. The implications of these findings for the improvement of the germination capacity of seeds are discussed.

Abstract

Magnetron sputtering (MS) is an emerging technique to prepare electrocatalysts for oxygen and hydrogen evolution reactions that take place in alkaline water electrolysis. It is a physical vapour deposition method that provides a strict control over the composition, chemical state, and microstructure. It permits to adjust complex stoichiometries and guarantees reproducibility. This technology allows to deposit electrocatalysts on suitable current collectors to get anode and cathode electrodes in a one-step process. Furthermore, MS is an environment friendly technology with easy scalability for industrial electrode production. Additionally, when operated in an oblique angle deposition configuration, it allows precise control of the microstructure of the deposits that can be tuned from compact to mesoporous. On this brief review we discuss recent studies on the field showing the possibility of using MS for the preparation of catalyst layers with complex compositions, bi-layer structure configurations, and bimetallic, trimetallic, and multicomponent alloys.

Abstract

In this paper, we investigate the Casimir-Lifshitz free energy mechanism that governs both ice growth and melting near metal surfaces, with a particular focus on the role of oxidation. Our study reveals that metals such as gold, iron, and aluminum induce incomplete premelting, resulting in micron-sized liquid water layers when in contact with ice. These layers could have significant implications for the defrosting of metallic surfaces. When exposed to water vapor at the triple point, aluminum and other metals can induce the formation of notably thick layers of either liquid water or ice, which can theoretically become infinitely thick if other interactions are disregarded. However, when aluminum undergoes oxidation to form alumina, its behavior changes dramatically. Alumina surfaces cause complete melting when in direct contact with bulk ice and result in only micron-sized layers of water or ice in vapor conditions. In contrast, magnetite, the oxidized form of iron, retains metalliclike behavior due to its high dielectric constant, similar to other metals, and continues to support thick layers of water or ice. This distinction highlights the significant influence of oxidation on the dynamics of ice growth and melting near different metal surfaces.

Abstract

Metal-Organic frameworks (MOFs) are promising candidates for advanced photocatalytically active materials. These porous crystalline compounds have large active surface areas and structural tunability and are thus highly competitive with oxides, the well-established material class for photocatalysis. However, due to their complex organic and coordination chemistry composition, photophysical mechanisms involved in the photocatalytic processes in MOFs are still not well understood. Employing electron paramagnetic resonance (EPR) spectroscopy and time-resolved photoluminescence spectroscopy (trPL), the fundamental processes of electron and hole generation are investigated, as well as capture events that lead to the formation of various radical species in UiO-66, an archetypical MOF photocatalyst. A manifold of photoinduced electron spin centers is detected, which is subsequently analyzed and identified with the help of density-functional theory (DFT) calculations. Under UV illumination, the symmetry, g-tensors, and lifetimes of three distinct contributions are revealed: a surface O2-radical, a light-induced electron-hole pair, and a triplet exciton. Notably, the latter is found to emit (delayed) fluorescence. The findings provide new insights into the photoinduced charge transfer processes, which are the basis of photocatalytic activity in UiO-66. This sets the stage for further studies on photogenerated spin centers in this and similar MOF materials.

Abstract

One of the biggest players in the world economy is the naval industry, which mainly controls the merchandise transportation sector. Any issue with ships could represent millions of USD of loss and increases in the cost of goods for the population worldwide. Two main problems which this industry has fought are corrosion and biofouling. Lastly, the pollution of the sea has gained importance, and more strict policies have been applied regarding the use of certain products by this industry. One of these is paintings, which represented this industry's definitive solution to avoid the mentioned problems for a long time. This situation allowed to explore other solutions like PVD coatings through multifunctional coatings. Zirconium nitride has been demonstrated to be useful in resisting corrosion with reliable mechanical properties. However, this material does not possess antimicrobial action. The present study presents a nanostructured coating combining ZrN with Cu, which works as a biocide, contributing to the desired multifunctionality. The developed coating was obtained using a hybrid magnetron co-sputtering employing High-power impulse (HiPIMS) and direct current (DCMS) power sources under a reactive atmosphere. SEM, EDX, XRD and Raman spectroscopy were used to assess the physico-chemical properties of the coatings. Besides, depth-sensing nano-indentation explored the mechanical properties. The tribological performance was tested by a reciprocating tribometer under dry and wet (with 3.5 % w/w NaCl solution) contact conditions and employing a soda lime glass ball as a counterbody. The results showed that adding Cu to ZrN through this technology resulted in a limited hardness reduction from 19 (pure ZrN) to 14 GPa. Also, the chemical activation with NaOCl solution softens the obtained coating and, together with the saline solution, influences the wear resistance. However, the nanostructured coating has been demonstrated to be suitable for use under real conditions, without loss of its protection over the used substrate. It opens a new possibility of a solution for the naval industry.

Abstract

This study presents the photocatalytic degradation of the aminophosphonate ethylenediaminetetra(methylenephosphonic acid) (EDTMP) with a range of different doped nanoparticles (NP). The photocatalysts were based on TiO2 benchmark P25 and gold (Au) doped either with sodium (Na), potassium (K) or yttrium (Y). The synthesized photocatalysts were characterized via TEM, XRF, XRD, UV-DRS (band gap estimation) and N2-phys- isorption. Photocatalytic pre-screening at pH values of 3, 7 and 10 indicated highest o-PO4 release of EDTMP at pH 7 and 10 for NP either doped with K or Y. The results of LC/MS analysis showed that the NPs doped with 5 % Y (Au2/Y5/P25) resulted in the fastest degradation of EDTMP. The target compound was completely degraded within 60 min, 4 times faster than photochemical treatment of unadulterated EDTMP. Importantly, also the transformation products were accelerated by the photocatalytic treatment with Au2/P25 either doped with 5 % Y or 10 % K. The results of scavenger experiments indicated that the enhanced photocatalytic degradation of EDTMP is primarily attributable to the presence of hydroxyl radicals in the bulk and to a lesser extent to center dot O2- and electron-holes (h+) at the surface of the catalysts. The study demonstrates that the catalytic efficiency of TiO2 nanocomposites is significantly influenced by the choice of dopants, which affect particle size, band gap, and photocatalytic activity. Yttrium at low concentrations (i.e., 5 wt% Y) doping emerged as particularly effective, enhancing both the visible light absorption and h+ separation, leading to superior photocatalytic performance in the degradation of EDTMP. The Au content also plays a crucial role in enhancing the photocatalytic efficiency. However, the combination of Au and Na doping was found to be less effective for this photocatalysis in aqueous media, potentially due to larger particle sizes and insufficient dopant contents. In conclusion, the findings emphasise the necessity of optimising both the selection of dopants and the design of catalysts in order to enhance photocatalytic applications.

Abstract

In contemporary catalytic interface exploration, experimental studies often take a backseat to theoretical simulations, hindering the development of pristine catalytic interfaces. This research leverages monolayer dispersion theory to design an efficient CO oxidation catalyst through precise manipulation of non-precious metal NiO-CeO2 interfaces. Employing the pioneering XRD extrapolation method, we fabricated monolayer dispersed Ni-O-Ce and Ce-O-Ni interfaces, unlocking insights into their impact on the CO oxidation mechanism. The method accurately quantified monolayer dispersion capacities: 0.526 mmol NiO/(100 m2 CeO2) for NiO/CeO2 and 0.0638 mmol CeO2/(100 m2 NiO) for CeO2/NiO, revealing intricate interactions between active components and supports. Utilizing numerical values derived from monolayer dispersion theory, we constructed CeO2-sup- ported NiO (Ni-O-Ce) and NiO-supported CeO2 (Ce-O-Ni) catalysts in a monolayer dispersed state. The Ni-O-Ce interface, generating abundant oxygen vacancies, significantly enhanced CO adsorption and facilitated surface reactive oxygen species production, leading to a remarkable 14-fold increase in intrinsic CO oxidation activity and a notable 4.2-fold improvement in water resistance. Integrating XRD extrapolation, H2-TPR, O2-TPD, COTPD, XPS, Raman, and in situ IR techniques, our study demonstrates the feasibility of crafting efficient catalysts with monolayer dispersed atomic-scale catalytic interfaces to elucidate the mechanisms underlying catalytic interface effects on CO oxidation.

Abstract

The direct conversion of carbon dioxide into hydrocarbons is a very desirable but difficult approach for achieving lower value-added olefins with minimal CO selectivity. In this effort, we report the direct conversion of CO2 into light olefins on a Cu/CeO2 hybrid catalyst mixed with SAPO-34 zeolite. The samples are characterized by N-2 sorption, XRD, TEM, SEM, NH3-TPD and H-2 -TPR. The results showed that the acidity of modified zeolite had decreased. The response surface methodology has been used to optimize the operating parameters (temperature and space velocity (SV)) of process. A high olefin selectivity of 70.4% has been obtained on CuCe/SAPO-34 at H-2/CO2 =3, 10 h, 382.46 degrees C, 17.33 L/g.h and 20 bar. The optimum operating conditions for multiple responses have also been achieved. The optimal values are T = 396.26 degrees C and SV = 5.80 L/g.h. Under these conditions, the predicted olefin and CO selectivity and CO2 conversion are 61.83%, 57.11% and 13.15%, respectively. Multiple optimization outputs are outstanding for obtaining the suitable operating conditions.

Abstract

Acoustic waves (AW) have recently emerged as an energy-efficient ice-removal procedure compatible with functional and industrial-relevant substrates. However, critical aspects at fundamental and experimental levels have yet to be disclosed to optimize their operational conditions. Identifying the processes and mechanisms by which different types of AWs induce de-icing are some of these issues. Herein, using model LiNbO3 systems and two types of interdigitated transducers, the e-icing and anti-icing efficiencies and mechanisms driven by Rayleigh surface acoustic waves (R-SAW) and Lamb waves with 120 and 510 mu m wavelengths, respectively, are analyzed. Through the experimental analysis of de-icing and active anti-icing processes and the finite element simulation of the AW generation, propagation, and interaction with small ice aggregates, it is disclosed that Lamb waves are more favorable than R-SAWs to induce de-icing and/or prevent the freezing of small ice droplets. Prospects for applications of this study are supported by proof of concept experiments, including de-icing in an icing wind tunnel, demonstrating that Lamb waves can efficiently remove ice layers covering large LN substrates. Results indicate that the de-icing mechanism may differ for Lamb waves or R-SAWs and that the wavelength must be considered as an important parameter for controlling the efficiency.

Abstract

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.

Abstract

Dredged material is a common environmental and economic issue worldwide. Tons of highly contaminated material, derived from cleaning the bottoms of bays and harbours, are stored until depuration. These volumes occupy huge extensions and require costly treatments. The Ria of Huelva (southwest Spain) receives additionally high metal contamination inputs from the Odiel and Tinto Rivers which are strongly affected by acid mine drainage (acid lixiviates with high metal content and sulphates). These two circumstances convert the port of Huelva into an acceptor/accumulator of contamination. The current study proposes an alternative active treatment of dredged material and mining residues using ASEC (Adiabatic Sonic Evaporation and Crystallization) technology to obtain distilled water and valuable solid conglomerates. Different samples were depurated and the efficiency of the technology was tested. The results show a complete recovery of the treated volumes with high-quality water (pH similar to 7, EC < 56 mu S/cm, complete removal of dissolved elements). Also, the characterization of the dried solids enable the calculation of approximate revenues from the valorization of some potentially exploitable elements (Rio Tinto: 4 M, Tharsis: 3.7 M, dredged material: 2.5 M USD/yr). The avoidance of residue discharge plus the aggregated value would promote a circular economy in sectors such as mining and dredging activities.

Abstract

Smart textiles represent a revolutionary approach to wearable technology with applications ranging from healthcare to energy harvesting. This review paper explores the importance of textile technologies and highlights their potential to revolutionize consumer electronics. Conventional technologies are sometimes heavy, and lack comfort and flexibility, but smart textiles seamlessly integrate into everyday clothing, improving wearability and user experience. The article emphasizes the need for sustainable sourcing and environmentally friendly production methods, as well as responsible manufacturing and disposal practices. Manufacturing techniques such as wet spinning, melt spinning, electrostatic spinning, weaving, knitting, and printing are detailed and shed light on their role in incorporating electronics into textiles. Several applications of textile-based devices are being explored, including biochemical sensing, temperature monitoring, energy harvesting, energy storage, and smart displays. Each application demonstrates the versatility and potential of smart textiles in different areas. Despite optimistic progress, challenges remain, from improving energy efficiency to protecting user privacy and data security. The review analyzes these problems and suggests future improvements, including interdisciplinary collaboration to find new solutions. Finally, an overview of the current state of smart textiles provides the future of this technology. It serves as an in-depth reference for academics and readers interested in understanding recent advances and discoveries in textile technologies, highlighting the importance of this rapidly growing industry.

Abstract

The instability and limited scalability of halide perovskites hinder their long-term viability in applications as X-ray detectors. Here, we introduce a sol-gel ship-in-bottle approach to produce a monolithic perovskite@metal-organic framework (MOF) composite, combining the properties of the individual building blocks and enhancing density, robustness, and stability. By tuning seed particles below 100 nm, we achieve highly crystalline, dense composites with up to 40% perovskite loading. Structural and optical characterization unveils perovskite nanocrystals forming within MOF mesopores, maximizing stability and preventing degradation, maintaining over 90% photoluminescence and structural integrity after weeks of exposure to humidity, heat, and solvents. Proposed as an innovative class of scintillator, these monolithic perovskite@MOFs attenuate X-rays efficiently and exhibit outstanding stability under high radiation doses equivalent to 110,000 typical chest X-rays, with a radioluminescence lifetime of 10 ns, outperforming commercial scintillators. This approach offers vast potential for developing high-performance, cost-effective, and stable devices for radiation detection and other optoelectronic applications.

Abstract

Ethylene, as an important chemical raw material, could be produced through the coal-based acetylene hydrogenation route. Nickel-based catalysts demonstrate significant activity in the semihydrogenation reaction of acetylene, but they encounter challenges related to catalyst deactivation and overhydrogenation. Herein, the effect of Sn promoter on Ni/CeO2 catalysts has been comprehensively explored for acetylene semihydrogenation. The optimized Ni/8%Sn-CeO2 catalytic performance was significantly improved, with 100% acetylene conversion and 82.5% ethylene selectivity at 250 degrees C, and the catalyst maintained high catalyst performance within a 1000 min stability test. A series of characterization tests show that CeO2 modified by moderate Sn4+ doping is more conducive to modulating the charge structure and geometry of the Ni active center. Additionally, the in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy and density functional theory results indicated that catalysts doped with Sn4+ facilitated more efficient desorption of ethylene from the catalyst surface compared to Ni/CeO2 catalysts, thus improving ethylene selectivity and yield. This study highlights an effective strategy for improving the catalytic performance of rare-earth-based catalysts through the incorporation of effective metal promoters.

Abstract

Plant biomass is an attractive precursor to prepare activated carbons with high surface area for CO2 adsorption due to its low-cost and easy regeneration. Despite this interest, there are still remaining questions regarding the optimal processing conditions and the choice of activating agent. Moreover, since plant biomass shows a highly variable proportion of different biopolymers (cellulose, hemicellulose, lignin), it is important to understand the activation effect on each constituent. In this work, carbons obtained from pyrolysis of cellulose were activated using two potassium salts, using two different activation temperatures. The samples were characterized to elucidate the influence of the activation conditions on their CO2 adsorption capacity. In general, all the carbons activated at higher temperature showed higher adsorption capacity. These results are comparable with other carbons derived from biomass described in the bibliography. Among the activated carbons studied, the carbon activated only with KOH exhibits the highest CO2 adsorption capacity at 1 bar meanwhile the highest adsorption capacity at saturation pressure belongs to the carbon activated with larger ratio of KNO3.

Abstract

Lead halide perovskite nanocrystals are attractive for light emitting devices both as electroluminescent and color-converting materials since they combine intense and narrow emissions with good charge injection and transport properties. However, while most perovskite nanocrystals shine at green and red wavelengths, the observation of intense and stable blue emission still remains a challenging target. In this work, a method is reported to attain intense and enduring blue emission (470–480 nm), with a photoluminescence quantum yield (PLQY) of 40%, originating from very small CsPbBr₃ nanocrystals (diameter < 3 nm) formed by controllably exposing Cs₄PbBr₆ to humidity. This process is mediated by the void network of a mesoporous transparent scaffold in which the zero-dimensional Cs₄PbBr₆ lattice is embedded, which allows the fine control over water adsorption and condensation that determines the optimization of the synthetic procedure and, eventually, the nanocrystal size. The approach provides a means to attain highly efficient transparent and stable blue light-emitting films that complete the palette offered by perovskite nanocrystals for lighting and display

Abstract

Herein, it is reported the concomitant synthesis and sintering in a single step of (Mn0.2Co0.2Ni0.2Cu0.2X0.2)Fe2O4 (X=Fe, Mg), a spinel-structured high-entropy oxides, by the reactive flash sintering technique. A single phase, identified with a spinel crystal structure Fd3m, was obtained in just 30 min at a furnace temperature of 1173 K. The structural and magnetic properties of the prepared compounds were assessed by the combined use of various techniques, aiming to understand the correlations between functional properties and crystal structure. Characteristic features of the Mossbauer spectra prove the existence of different nonequivalent Fe environments . Both compositions display soft magnetic behavior, characterized by low coercive fields and saturation magnetization reached at low fields. Thus, the substitution of nonmagnetic Mg2+ for magnetic Fe2+ results in a decrease in magnetic parameters due to the weakening of the super-exchange interaction among the magnetic moments.

Abstract

VOx/TiO₂ catalysts with various theorical monolayer values have been prepared and used to study, for the first time, the effect of vanadium loading in the selective oxidation of glucose to formic acid. Monomeric or isolated vanadia species dominate at low loadings, evolving into polymeric chains at higher concentrations, while crystalline V₂O₅ is observed at loadings over the theoretical monolayer value. Their characterization by XRD, BET, ICP, DRIFTS, Raman, UV–vis, H₂-TPR and NH₃-TPD reveal distinct physicochemical characteristics influenced by the formed vanadia species, impacting sample acidity, reducibility, and catalytic activity. All catalysts exhibit significant activity, forming formic acid as the main product in the liquid phase and reaching a peak formic acid yield of 42 %. Post-reaction analysis reveals that the leaching-prone crystalline V₂O₅ compromises catalyst stability while isolated vanadia species demonstrate superior catalytic activity and leaching resistance. The findings of this study provide a strong basis for the development of a heterogeneous vanadia catalyst with improved interaction with the support.

Abstract

Two series of open metal site MOFs, HKUST-1 and MIL-100(Fe), have been successfully prepared using different methods of synthesis. Their features depend on the synthetic route as well as their role play in different environmental applications. The stability and performance of these BTC-based MOFs have been tested bearing in mind Congo Red (CR) removal, humidity adsorption and iodine capture and release. HKUST-1 and MIL-100(Fe) samples could offer a remarkable role in the adsorption of CR from aqueous solutions. However, the lability of HKUST-1 in water is revealed as a drawback for its reutilization in both static and agitation conditions. The former contrasts to the stability under ambient moisture. MIL-100(Fe) shows promising properties in both CR adsorption in aqueous solutions and humidity adsorption. Nonetheless, the performance largely depends on the synthesis conditions. Although CR removal is based on surface interaction, there is a relation between the adsorpted quantity and the specific surface area. The size and nature of iodine allows the diffusion in the pores of both HKUST-1 and MIL-100(Fe) MOFs. This way, the uptake of iodine is driving by the porosity and surface area of samples rather than their inherent nature. As a rule, the results of this work indicate that not only is it important the specific nature of the MOF chosen for a given application but also the way in which it has been synthesized and the conditions in which they are used. MIL-100(Fe)-R is revealed as the best suitable candidate to be used as a sorbent for CR in aqueous solutions, moisture and I2 gas.

Abstract

Surface engineering through the deposition of advanced coatings, particularly multilayer coatings has gained significant interest for enhancing the performance of coated parts. The incorporation of Si into TiN coatings has shown promise for improving hardness, oxidation resistance, and thermal stability, while high-power impulse magnetron sputtering (HiPIMS) has emerged as a technique to deposit coatings with exceptional properties. However, TiN/CrN and TiSiN/CrN coatings deposited by HiPIMS remain relatively unexplored. In this study, different TiN/CrN and TiSiN/CrN multilayer coatings with different bilayer periods from 5 to 85 nm were deposited using an industrial-scale HiPIMS reactor, and their microstructure and mechanical properties were investigated using advanced characterization techniques. Results revealed successful deposition of smooth and compact coatings with controlled bilayer periods. X-ray diffraction analysis showed separate crystalline phases for coatings with high bilayer periods, while those with smaller bilayer periods exhibited peak-overlapping and superlattice overtones, especially for the TiN/CrN coatings. Epitaxial grain growth was confirmed by highresolution transmission electron microscopy (HRTEM). HRTEM and electron energy-loss spectroscopy measurements confirmed Si incorporation into the TiN crystal lattice of TiSiN/CrN coatings reducing the crystallinity, especially for coatings with smaller bilayer periods. Nanoindentation tests revealed that coatings with a bilayer period of 15-20 nm displayed the highest hardness values regardless of the composition. The mechanical properties of the TiSiN/CrN coatings showed no improvement over those of the TiN/CrN coatings, attributed to the Si induced amorphization of the Ti(Si)N phase and the absence of SiNx phase segregation within the TiN nanocrystals in these coatings. These findings provide valuable insights into the microstructure and mechanical properties of TiN/CrN and TiSiN/CrN multilayer coatings deposited by HiPIMS in an industrial scale reactor, paving the way for their application in various industrial sectors.

Abstract

Combining Carbon Capture and Storage (CCS) with producing competitive secondary raw materials is key to decarbonizing industry and reducing resource extraction. Biogas upgrading to biomethane stand out as an alternative, but a significant gap remains in integrating this process within a circular economy framework. This issue has been recently addressed by a process that integrates biogas upgrading via caustic absorption with the production of Precipitated Calcium Carbonate (PCC) and the recovery of sodium hydroxide from waste brine solution using membrane technologies. The profitability of this approach depends on the quality of the PCC, a critical factor that this work addresses. By characterizing PCC is determined whether trace compounds in biogas contaminate the PCC and potentially affect its commercial value. It also examines the CO2 absorption process and analyzes the aqueous samples from the filtration phase of the PCC slurry. Results confirm the high purity of PCC obtained from biogas treatment using Raman spectroscopy, X-Ray Diffraction (XRD), and Scanning Electron Microscopy (SEM). The analyses show that the PCC is pure calcium carbonate, mainly in the stable calcite form, with a typical tetrahedral morphology and no detectable impurities. Characterization of aqueous solutions revealed organic trace compounds from biogas, with TOC concentrations of 9.7 (+/- 6.4) and 16.0 (+/- 8) mg C/l. Silicon measurements showed similar concentrations in the absorbent solution and filtrated PCC slurry. Additionally, ammonia escapes as gas, and hydrogen sulfide in the biogas likely contributed to sulfate salt formation. Analysis of the COQ absorption shows a first-order reaction with OH-, where the amount of COQ absorbed (46.3-50.0 g) closely matches the theoretical value of 48 g. The study reveals that most of the biogas impurities dissolve into the aqueous solution, being crucial for future studies and downstream membrane treatments, and the PCC is unaffected by these impurities with a purity suitable for commercial applications.

Abstract

The effects of a remote oxygen plasma (ROP) treatment on the surface of commercial graphite felts were investigated and compared against a conventional thermal treatment. In contrast to methodologies where the sample is directly exposed to the plasma, ROP allows for a high control of sample-plasma interaction, thereby avoiding extensive etching processes on the fibre surface. To assess the impact of ROP treatment time, the electrodes were subjected to three different periods (10, 60, and 600 seconds). X-ray photoelectron spectroscopy showed that the ROP treatment introduced nearly three times more surface oxygen functionalities than the thermal treatment. Raman spectroscopy measurements revealed a significant increase in amorphous carbon domains for the ROP samples. The thermal treatment favoured increases in graphitic defects and resulted in an order of magnitude larger ECSA compared to the ROP treated materials despite having lower content in oxygen functionalities. The electrochemical analysis showed enhanced charge-transfer overpotentials for GF400. The ROP samples exhibited a lower mass-transport overpotential than the thermally treated material and had similar permeabilities, which overall translated to the thermal treatment offering better performance at fast flow rates. However, at slow flow rates (similar to 10 mL min-1), the ROP treatment for the shortest period offered comparable performance to conventional thermal treatment.

Remote oxygen plasma is compared to conventional thermal activation of electrodes for flow batteries and their impact on the mass transport and charge transfer properties of the resulting carbons.