Artículos SCI

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

Access to clean water is crucial for human health, yet microbial contamination poses significant challenges. This study investigates the effectiveness of novel photocatalytic catalysts: heterostructured TiO₂/AgBr and faceted titanium dioxide, for microbial inactivation under ultraviolet and visible light. Both catalysts were synthesized and characterized. Performance was evaluated using real wastewater samples and saline solutions, targeting gram-positive and gram-negative bacteria. The experimental approach included testing the photocatalysts with and without the addition of peroxydisulfate to assess its impact on inactivation effectiveness. Results indicated that the TiO₂/AgBr catalyst outperformed the faceted titanium dioxide one due to its superior visible light absorption and enhanced charge separation, achieving complete inactivation of environmental strains of Escherichia coli and significant inactivation for Enterococcus faecalis in real wastewater. The inclusion of peroxodisulfate with TiO₂/AgBr significantly improved inactivation rates, demonstrating a synergistic effect. Regarding wastewater composition, the treatment achieves a significant COD removal while the rest of studied parameters remain stable. Both catalysts effectively prevented bacterial regrowth for up to 48 hours, underscoring its long-term efficacy. Overall, these findings highlight the potential application of TiO₂/AgBr combined with peroxodisulfate as an effective strategy for microbial inactivation, contributing to the advancement in water treatment technologies across real environmental contexts.

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

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

A joint theory-experimental study is presented of irregularly shaped nano-pores in amorphous silicon. STEM- ELLS spectra were measured for each pore. The observed helium 1 s 2- 1 s 2 p( 1 P ) excitation energies were found to be shifted from that of a free atom. The relation between the helium density in the pore and these energy shifts is explored and shown to be completely consistent with earlier studies of helium in its bulk condensed phases as well as encapsulated as bubbles in solid silicon. The density, pressure and depth of the pores, all key properties for applications, were determined. An alternative and novel method for determining the depth of the pores more accurately is presented.

Abstract

The first demonstration of plasma-flash sintering (PFS) is presented in this work. PFS is performed under a low-pressure atmosphere that consecutively generates plasma and flash events. It is shown, by using several combined characterization techniques, that PFS stabilizes metastable phases on the surface of the material, which may be partially, but not solely, attributed to the generation of oxygen vacancies, and induces the absorption of ionized species, if a reactive atmosphere is employed. Even though additional research is required to understand the fundamentals of PFS, it is evidenced its potential to be used as a material surface engineering tool, which may widen the technological capabilities of flash sintering.

Cover Photograph: Plasma-Flash Sintering (PFS) is performed under low-pressure atmosphere that consecutively generates plasma and flash events. This study shows that PFS stabilizes metastable phases on the surface of the material and enables absorption of ionized species generated in the plasma, giving this technique potential to be used as a surface engineering tool. Read more in the rapid communication in this issue,

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

Poly(vinylidene fluoride) (PVDF) is a piezoelectric and thermoplastic material with great potential for additive manufacturing (AM) applications. Using barium titanate (BaTiO₃) as filler, PVDF-based composite materials were developed, characterized, and processed by AM material extrusion (MEX). The morphological features and phase transformations occurring throughout the processing of BaTiO₃-filled PVDF, from the compounding to the printed part, were analyzed. The morphology of the powder feedstock after dispersion in a high-energy ball mill changed from spheroidal to laminar and β-phase formation was favored. Microhardness gradually increased with the BaTiO₃ content, obtaining an enhancement of ~60% for a content of 25 vol%, and supported the good dispersion of the filler. A ~48% increase of the dielectric permittivity was also achieved. After extrusion, filaments with a filler content of 15 vol% showed a more stable diameter, as well as higher crystallinity and surface roughness, compared with those with lower BaTiO₃ contents. Material extrusion of filament and direct printing of pellets based on MEX were successfully used to obtain AM parts. Composite parts showed enhanced surface roughness, hydrophilicity, and flexural modulus (up to ~33% for the 7 vol% composite compared with the PVDF), thus leading to superior mechanical characteristics and potential biomedical applications.

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

Microplastics fibers shed from washing synthetic textiles are released directly into the waters and make up 35% of primary microplastics discharged to the aquatic environment. While filtration devices and regulations are in development, safe disposal methods remain absent. Herein, we investigate catalytic hydrothermal carbonization (HTC) as a means of integrating this waste (0.28 million tons of microfibers per year) into the circular economy by catalytic upcycling to carbon nanomaterials. Herein, we show that cotton and polyester can be converted to filamentous solid carbon nanostructures using a Fe-Ni catalyst during HTC. Results revealed the conversion of microfibers into amorphous and graphitic carbon structures, including carbon nano- tubes from a cotton/polyethylene terephthalate (PET) mixture. HTC at 200 degrees C and 22 bar pressure produced graphitic carbon in all samples, demonstrating that mixed microfiber wastes can be valorized to provide potentially valuable carbon structures by modifying reaction parameters and catalyst formulation.

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

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

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

This work shows the synthesis and characterization of the Zn2-xGeO4-GeO2:(x)Mn2+ (x = 0.10, 0.25, and 0.50 at.%) films using the Ultrasonic Spray Pyrolysis (USP) technique. These films were deposited at 500 degrees C and heat treated at 800 degrees C for 13 h. X-ray diffraction (XRD) measurements showed the rhombohedral and hexagonal phases of Zn2-xGeO4 (78.8 %) and GeO2 (21.2 %), respectively. SEM micrographs exhibited the surface morphology of these films. The STEM and HAADF show Ge, Zn, and O atomic layers. In addition, XPS was carried out to observe the oxidation states of Mn2+ (75.4 %) and Mn3+ (24.6 %) for the films doped with Mn ions (0.10 at.%). Incorporating manganese ions into the Zn2-xGeO4-GeO2 host lattice generated an extremely green emission, exciting at 250 nm. The photoluminescence and persistence luminescence properties were studied in accordance with the manganese doping concentration. For photoluminescence, it was found that the optimal doping percentage was 0.25 at.%, and for persistence luminescence, it was 0.10 at.% Mn with lambda(ex) = 250 nm. Quantum efficiency measurements gave a result of 100 %. In addition, preliminary CL measurements were exhibited.

Abstract

Introducing quantum dots (QDs) as the active element of an optoelectronic device demands its incorporation in the shape of interconnected arrays that allow for some degree of electronic coupling in order to inject/extract charge carriers. In doing so, beyond reducing the degree of quantum confinement, carriers are exposed to an enhanced defect landscape as they can access adjacent QDs, which is at the origin of the strong reduction of photoluminescence observed in QD solids when compared to that of the isolated QDs. In this work we demonstrate how a proper defect passivating strategy or atmospheric treatment can greatly enhance charge diffusion in a QD film, needed for an optimal carrier injection/extraction demanded for optoelectronic applications, and also improved its stability against external radiation. From a fundamental perspective, we provide evidence showing that trap density distribution, rather than QD size distribution, is mostly responsible for the observed variations in emission decay rates present in the QD networks under analysis.
Different treatments (comprising polymeric encasement and different atmospheres) are applied to quantum dot solids in order to modify their defect landscape. The role of the latter in both, carrier recombination and stability, is unveiled.

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

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.

Abstract

Triboelectric nanogenerators (TENGs) are the most promising technology for harvesting energy from low-frequency liquid flows and impacts such as rain droplets. However, current drop energy harvester technologies suffer from low output power due to limitations in triboelectric materials, suboptimal device designs, and the inability to fully capture the kinetic energy of falling drops. This article introduces a microscale TENG capable of efficiently converting drop impact energy into electrical power in a single, rapid step. The device features a capacitive structure that enhances energy conversion through instantaneous capacitance changes when the drops contact the submillimetric top electrodes. This compact design establishes a path toward the development of dense arrays and rain panels and is adaptable to various liquids, scales, triboelectric surfaces, and thin-film configurations, including flexible and transparent materials. 

Abstract

Embracing a circular economy in the textile industry represents a crucial step toward sustainability, where fashion and textile sectors contribute significantly to CO2 emissions. However, transitioning from a linear “take-make-waste” model to circularity, poses multifaceted challenges, that highlight the staggering volume of annual textile waste surpassing industry predictions, thus emphasizing the urgent need for comprehensive strategies. Despite advancements in recycling technologies, challenges persist in collecting and sorting textile waste, where fragmentation in waste management and recycling processes hinders effective management of post-consumer waste. Addressing these challenges demands elevated efforts in collection, sorting, and pre-processing, alongside regulatory interventions to drive enhanced waste collection and circular business models. Efforts are underway to promote sustainable textile recycling, with initiatives like the EU’s Sustainable and Circular Textiles Strategy aiming to reduce reliance on virgin resources. However, achieving a circular textile market in the near future requires collaborative action and innovative solutions. Though challenges in scaling and technological limitations still remain, recent breakthroughs in textile-recycling technologies offer promise, signaling a shift toward scalable and sustainable alternatives to virgin fibers, where bio-based chemical processes, and thermochemical recycling processes present transformative opportunities. Where, bold scaling targets, collaborative efforts, and short-term funding support narrated in this perspective article are imperative to accelerate the transition to a circular textile economy, thus delving into the pivotal role of textile recycling, tracing the evolution of recycling technologies, and addressing critical challenges hindering widespread adoption.

Abstract

Dry reforming of methane (DRM) represents an alluring approach to the direct conversion of CO2 and CH4, gases with the highest global warming potential, into syngas, a value-added intermediate used in chemical industry. In this study, mixed oxide structures of cerium and zirconium doped with 10 wt% Ni were used due to the high thermal stability. This study showcased the importance of choosing suitable conditions and explored the impact of calcination temperature on Ce-Zr mixed oxides with Ni. XRD analysis confirmed the existence of different crystalline phases according to the calcination temperature. Redox characterisation showed a trade-off among calcination temperature, the dispersion of Ni clusters and its interaction with the support structure. Calcined catalysts at 900 and 1000 degrees C underwent harsh, long-term DRM conditions. Despite the low surface area of the designed catalysts, the stability experiments proved a relation between dispersion of Ni active phase and catalytic performance, showing an optimum calcination temperature of 1000 degrees C.

Abstract

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.

Abstract

Carbon is a critical material for existing and emerging energy applications and there is considerable global effort in generating sustainable carbons. A particularly promising area is iron-catalyzed graphitization, which is the conversion of organic matter to graphitic carbon nanostructures by an iron catalyst. In this paper, it is reported that iron-catalyzed graphitization occurs via a new type of mechanism that is called homogeneous solid-state catalysis. Dark field in situ transmission electron microscopy is used to demonstrate that crystalline iron nanoparticles “burrow” through amorphous carbon to generate multiwalled graphitic nanotubes. The process is remarkably fast, particularly given the solid phase of the catalyst, and in situ synchrotron X-ray diffraction is used to demonstrate that graphitization is complete within a few minutes.

Abstract

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 LaCo_0.8Cu_0.2O₃ under reducing/oxidizing atmosphere (redox) and Preferential Oxidation of CO (PrOx, with high H₂ concentration) conditions and their reversibility. LaCo_0.8Cu_0.2O₃ 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.

Abstract

Research on high-field magnetic resonance imaging (HF-MRI) has been increased in recent years, aiming to improve diagnosis accuracy by increasing the signal-to-noise ratio and hence image quality. Conventional contrast agents (CAs) have important limitations for HF-MRI, with the consequent need for the development of new CAs. Among them, the most promising alternatives are those based on Dy3+ or Ho3+ compounds. Notably, the high atomic number of lanthanide cations would bestow a high capability for X-ray attenuation to such Dy or Ho-based compounds, which would also allow them to be employed as CAs for X-ray computed tomography (CT). In this work, we have prepared uniform NaDy(WO4)(2) and NaHo(WO4)(2) nanoparticles (NPs), which were dispersible under conditions that mimic the physiological media and were nontoxic for cells, meeting the main requirements for their use in vivo. Both NPs exhibited satisfactory magnetic relaxivities at 9.4 T, thus making them a promising alternative to clinical CAs for HF-MRI. Furthermore, after their intravenous administration in tumor-bearing mice, both NPs exhibited significant accumulation inside the tumor at 24 h, attributable to passive targeting by the enhanced permeability and retention (EPR) effect. Therefore, our NPs are suitable for the detection of tumors through HF-MRI. Finally, NaDy(WO4)(2) NPs showed a superior X-ray attenuation capability than iohexol (commercial CT CA), which, along with their high r(2) value, makes them suitable as the dual-probe for both HF-MRI and CT imaging, as demonstrated by in vivo experiments conducted using healthy mice.

Abstract

Intraband carrier relaxation in quantum dots (QDs) has been a subject of extensive spectroscopic investigation for several decades, and have been used to optimize the efficiency of opto-electronic processes. In the past few years, metal halide perovskites-based QDs have been shown to exhibit slow hot-carrier cooling characteristics that are desirable for photo-energy harvesting technologies. While several mechanisms are proposed to rationalize the retardation of the cooling dynamics, including hot-phonon bottleneck and polaronic effects, the role of inter-particle connectivity in these dynamics is largely ignored. Here, an in-depth study of photo-excitation dynamics and carrier cooling on perovskite QD solids with varying degrees of inter-dot coupling is presented. It is observed that inter-particle connectivity has deterministic effects on the many-body interactions that are relevant for carrier cooling. These include carrier-carrier interactions that result in Auger-reheating of the carriers, and lattice characteristics that subsequently affect the phonon-assisted cooling dynamics. This spectroscopic study of ultrafast carrier dynamics in perovskite QD solids establishes inter-dot separation as a critical material design parameter for the optimization of photo-generated carrier temperature, which fundamentally determines the luminescence characteristics and thus the opto-electronic quality of the material.

The photo-excitation dynamics and carrier cooling in metal halide perovskite quantum dot solids are investigated here. Evidence for the deterministic role of inter-particle connectivity on the many-body interactions relevant to carrier cooling is discussed. These include carrier-carrier interactions that result in Auger-reheating of the carriers, and lattice coupling that subsequently affects the phonon-assisted cooling dynamics. image

Abstract

Water quality and usability are global concerns due to microbial and chemical pollution resulting from anthropogenic activities. Therefore, strategies for eliminating contaminants are required. In this context, the removal and decrease in antibiotic activity (AA) associated with levofloxacin (LEV), using TiO₂ and Ag/TiO₂ catalysts, with and without sunlight and peroxydisulfate, was evaluated. Additionally, the disinfection capacity of catalytic systems was assessed. The catalysts were synthesized and characterized. Moreover, the effect of Ag doping on visible light absorption was determined. Then, the photocatalytic treatment of LEV in water was performed. The materials characterization and EPR analyses revealed that LEV degradation and AA decrease were ascribed to a combined action of solar light, sulfate radical, and photocatalytic activity of the TiO₂-based materials. Also, the primary byproducts were elucidated using theoretical analyses (predictions about moieties on LEV more susceptible to being attacked by the degrading species) and experimental techniques (LC-MS), which evidenced transformations on the piperazyl ring, carboxylic acid, and cyclic ether on LEV. Moreover, the AA decrease was linked to the antibiotic transformations. In addition, the combined system (i.e., light/catalyst/peroxydisulfate) was shown to be effective for E. coli inactivation, indicating the versatility of this system for decontamination and disinfection.