In operando XAS investigation of reduction and oxidation processes in cobalt and iron mixed spinels during the chemical loop reforming of ethanol

FeCo2O4 and CoFe2O4 nanoparticles have been studied as oxygen carriers for the Chemical Loop Reforming (CLR) of ethanol. By using in operando X-ray absorption spectroscopy we have followed in real time the chemical and structural changes that take place on the materials as a function of temperature and reactive atmosphere (i.e. ethanol/water streams). During the first step of CLR for both oxides the most active chemical species are the cations in the tetrahedral sites, irrespective of their chemical nature. Quite rapidly the spinel structure is transformed into a mix of wustite-type oxide and metal alloys, but the formation of a metal phase is easier in the case of cobalt, while iron shows a marked preference to form wustite type oxide. Despite the good reducibility of FeCo2O4 imparted by the high amount of cobalt, its performance in the production of hydrogen is quite poor due to an inefficient oxidation by water steam, which is able to oxidize only the outer shell of the nanoparticles. In contrast, CoFe2O4 due to the residual presence of a reducible wustite phase shows a higher hydrogen yield. Moreover, by combining the structural information provided by X-ray absorption spectroscopy with the analysis of the byproducts of ethanol decomposition we could infer that FeCo2O4 is more selective than CoFe2O4 for the selective dehydrogenation of ethanol to acetaldehyde because of the higher amount of Fe(III) ions in tetrahedral sites

Ag-Vanadates/GO Nanocomposites by Aerosol-Assisted Spray Pyrolysis: Preparation and Structural and Electrochemical Characterization of a Versatile Material

In this article, we describe the deposition by aerosol-assisted spray pyrolysis of different types of silver vanadate nanocomposites with and without graphene oxide (GO) on different substrates (carbon paper (CP) and fluorine-doped tin oxide (FTO)). When deposited on CP, different amounts of GO were added to the Ag and V precursor solution to study the effect of GO on the physicochemical properties of the resulting Ag-vanadate. It is shown that the addition of GO leads mainly to the formation of nanoparticles of the Ag2V4O11 phase, whereas Ag2V4O11 and Ag3VO4 are obtained without the addition of GO. The morphology and chemical properties of the composites were determined by scanning and transmission electron microscopies, X-ray diffraction, X-ray photoemission spectroscopy, and UV\u2013visible and Raman spectroscopies. In addition, the photoelectrochemical (PEC) properties of such composites were studied by CV, linear sweep voltammetry, and electrochemical impedance spectroscopy. The ideal AgxVOy and GO ratio was optimized for obtaining higher photocurrent values and a good stability. The results showed that the presence of GO improves the electrical conductivity of the catalyst layer as well as the electron injection from the oxide to the electrode surface. The deposition of pure Ag2V4O11 on FTO does not lead to samples with stable PEC performances. Samples grown on CP supports showed an efficient electrochemical detection of small amounts of ethylenediamine in water solution

Cobalt Spinel Nanocubes on N-Doped Graphene: A Synergistic Hybrid Electrocatalyst for the Highly Selective Reduction of Carbon Dioxide to Formic Acid

Carbon dioxide reduction into useful chemical products is a key technology to address urgent climate and energy challenges. In this study, a nanohybrid made by Co₃O₄ and graphene is proposed as an efficient electrocatalyst for the selective reduction of CO₂ to formate at low overpotential. A comparison between samples with different metal oxide to carbon ratios and with or without doping of the graphene moiety indicates that the most active catalyst is formed by highly dispersed and crystalline nanocubes exposing {001} oriented surfaces, whereas the nitrogen doping is critical to obtain a controlled morphology and to facilitate a topotactic transformation during electrocatalytic conditions to CoO, which results in the true active phase. The nanohybrid made up by intermediate loading of Co₃O₄ supported on nitrogen-doped graphene is the most active catalyst, being able to produce 3.14 mmol of formate in 8 h at −0.95 V vs SCE with a Faradaic efficiency of 83%

Electrocatalizadores para pilas de combustible de membrana de intercambio protónico

Electrocatalizadores para pilas de combustible de membrana de intercambio protónico. Procedimiento de obtención de un material de carbono mesoporoso (SMC) que comprende: la adición de sílice coloidal a un precursor polimérico de carbono; el curado térmico; el carbonizado del compuesto obtenido; lavado del compuesto carbonizado con ácido fluorhídrico (HF) o NaOH; y la oxidación del material lavado. Además la invención se refiere a un catalizador para pilas de combustible de electrolito polimérico basado en la utilización del nuevo soporte carbonoso mesoporoso.Peer reviewedConsejo Superior de Investigaciones Científicas (España), Universidad de La LagunaA1 Solicitud de patente con informe sobre el estado de la técnic

VO2/V2O5:Ag nanostructures on a DVD as photoelectrochemical sensors

The electrochemical deposition of a mixed oxide on the Ag nanostructured surface of a commercial digital versatile disc (DVD) is described. The VO2/V2O5 mixture shows interesting photoelectrocatalytic performances under visible-light illumination after diffusion of the Ag+ ions from the Ag-DVD substrate through the layer and formation of surface vanadates, which also allows it to be applied as an inexpensive sensing device. The samples were characterized with X-ray photoemission spectroscopy (XPS), scanning electron microscopy (SEM), electrochemical impedance spectroscopy (EIS), and Raman measurements. The sensing properties towards oxidizable organic substances, such as glucose, were tested

Carbon-supported Fe catalysts for CO2 electroreduction to high-added value products: a DEMS study: effect of the functionalization of the support

Vulcan XC-72R-supported Fe catalysts have been synthesised for the electroreduction of CO2 to high-added value products. Catalysts were obtained by the polyol method, using ethylene glycol as solvent and reducing agent. Prior to the metal deposition, Vulcan was subjected to different oxidation treatments in order to modify its surface chemistry and study its influence on the physicochemical and electrochemical properties of the catalysts, as well as on the product distribution. The oxidation treatments of the supportsmodify their textural properties, but do not affect significantly the physicochemical properties of catalysts. However, DEMS studies showed that the carbon support degradation, the distribution of products, and the catalytic activity toward the CO2 electroreduction reaction depend significantly on the surface chemistry of the carbon support.The authors gratefully acknowledge financial support given by MICINN (MAT2008-06631-C03-01 and 02) and Gobierno de Aragon and Obra Social La Caixa (GA-LC-008/2009). S. Perez-Rodrıguez acknowledges Gobierno de Aragon for the DGA grant. G. Garcıa acknowledges to the JAE program (CSIC) for financial support.Peer reviewe

Effect of the dendrimer generation used in the synthesis of Pt-Ru nanoparticles supported on carbon nanofibers on the catalytic activity towards methanol oxidation

Pt-Ru nanoparticles supported on carbon nanofibers (CNF) were synthesized by the sodium borohydride reduction method, using different generation dendrimers (zero, one, two and three generations). After the synthesis process, these materials were submitted to a heat treatment at 350 °C, in order to clean the nanoparticle surface of organic residues. TEM characterization showed that the Pt-Ru nanoparticles size ranged between 1.9 and 5.5 nm. The use of dendrimers did not totally avoid the formation of aggregates, although monodisperse sizes were observed. The heat treatment produces the desired surface cleaning, although promoted the formation of agglomerates and crystalline Ru oxides. The study of the electrochemical activity towards the methanol oxidation displayed some clues about the influence of both the dendrimer generation and the presence of Ru oxides. Moreover, the apparent activation energy Eap for this reaction was determined. The results showed a beneficial effect of the heat treatment on the methanol oxidation current densities for the materials synthesized with the biggest dendrimers, being the methanol deprotonation and COad diffusion the predominant rate determining steps (rds).We acknowledge support from the Unit of Information Resources for Research at the "Consejo Superior de Investigadciones Científicas" CSIC for the article-processing charges contribution.: This work was carried out with the support of Ministry of Economy and Competitiveness (MINECO) through the project ENE2014-52158-C2-2-R and 1-R (co-funded by FEDER). J.C.C. is indebted to the Alβan Program for the predoctoral fellowship No. E07D403742CO