Laura Calvillo

Electronic interaction between platinum nanoparticles and nitrogen-doped reduced graphene oxide: effect on the oxygen reduction reaction

In this study, low-mass loadings (ca. 5 wt%) Pt/C catalysts were synthesized using the carbonyl chemical route allowing for the heterogeneous deposition of Pt nanoparticles on different carbon-based substrates. N-doped reduced graphene oxide, reduced graphene oxide, graphene oxide, graphite and Vulcan XC-72 were used for the heterogeneous deposition of Pt nanoparticles. The effect of the chemical nature of the carbon-based substrate on the Oxygen Reduction Reaction (ORR) kinetics at Pt nanoparticles surfaces was investigated. XPS results show that using N-doped reduced graphene oxide materials for the deposition of Pt nanoparticles leads to formation of Pt–N chemical bonds. This interaction between Pt and N allows for an electronic transfer from Pt to the carbon support. It is demonstrated that ca. 25% of the total amount of N atoms were bound to Pt ones. This chemical bond also revealed by the DFT analysis, induces changes in the oxygen adsorption energy at the platinum surface, engendering an enhancement of the catalyst activity towards ORR. In comparison with Vulcan XC-72, the mass activity at 0.9 V vs. RHE is 2.1 fold higher when N-doped reduced graphene oxide is used as substrate. In conjunction with the experimental results, DFT calculations describe the interaction between supported platinum clusters and oxygen where the support was modelled accordingly with the carbon-based materials used as substrate. It is demonstrated that the presence of N-species in the support although leading to a weaker O2 adsorption, induces elongated O–O distances suggesting facilitated dissociation. Additionally, it is revealed that the strong interaction between Pt clusters and N-containing substrates leads to very slight changes of the cluster–substrate distance even when oxygen is adsorbed at the interfacial region, thus leading to a lower resistance for electron charge transfer and enabling electrochemical reactions.

Fast One-Pot Synthesis of MoS2/Crumpled Graphene p–n Nanonjunctions for Enhanced Photoelectrochemical Hydrogen Production

Aerosol processing enables the preparation of hierarchical graphene nanocomposites with special crumpled morphology in high yield and in a short time. Using modular insertion of suitable precursors in the starting solution, it is possible to synthesize different types of graphene-based materials ranging from heteroatom-doped graphene nanoballs to hierarchical nanohybrids made up by nitrogen-doped crumpled graphene nanosacks that wrap finely dispersed MoS2 nanoparticles. These materials are carefully investigated by microscopic (SEM, standard and HR TEM), diffraction (grazing incidence X-ray diffraction (GIXRD)) and spectroscopic (high resolution photoemission, Raman and UV-visible spectroscopy) techniques, evidencing that nitrogen dopants provide anchoring sites for MoS2 nanoparticles, whereas crumpling of graphene sheets drastically limits aggregation. The activity of these materials is tested toward the photoelectrochemical production of hydrogen, obtaining that N-doped graphene/MoS2 nanohybrids are seven times more efficient with respect to single MoS2 because of the formation of local p-n MoS2/N-doped graphene nanojunctions, which allow an efficient charge carrier separation.

Yttrium oxide/gadolinium oxide-modified platinum nanoparticles as cathodes for the oxygen reduction reaction.

Rare-earth-element (Y, Gd) modified Pt nanoparticles (NPs) supported on a carbon substrate (Vulcan XC-72) are synthesized via a water-in-oil chemical route. In both cases, X-ray diffraction (XRD) measurements show the non-formation of an alloyed material. Photoemission spectroscopy (XPS) results reveal that Y and Gd are oxidized. Additionally, no evidence of an electronic modification of Pt can be brought to light. Transmission electron microscopy (TEM) studies indicate that Pt-Y(2)O(3) and Pt-Gd(2)O(3) particles are well dispersed on the substrate-and that their average particle sizes are smaller than the Pt-NP sizes. The catalytic activity of the Pt-Y(2)O(3)/C and Pt-Gd(2)O(3)/C catalysts towards the oxygen reduction reaction (ORR) is studied in a 0.5 M H(2)SO(4) electrolyte. The surface and mass specific activities of the Pt-Y(2)O(3)/C catalyst towards the ORR at 0.9 V (vs. the reversible hydrogen electrode, RHE) are (54.3±1.2) μA cm(-2)(Pt) and MA=(23.1±0.5) mA mg(-1)(Pt), respectively. These values are 1.3-, and 1.6-fold higher than the values obtained with a Pt/C catalyst. Although the as-prepared Pt-Gd(2)O(3)/C catalyst has a lower catalytic activity for the ORR compared to Pt/C, the heat-treated sample shows a surface specific activity of about (53.0±0.7) μA cm(-2) Pt , and a mass specific activity (MA) of about (18.2±0.5) mA mg(-1) Pt at 0.9 V (vs. RHE). The enhancement of the ORR kinetics on the Pt-Y(2)O(3)/C and heat-treated Pt-Gd(2)O(3)/C catalysts could be associated with the formation of platinum NPs presenting modified surface properties.

Oxygen Reduction Reaction at LaxCa1-xMnO3 Nanostructures: Interplay between A-site Segregation and B-site Valency

The mean activity of surface Mn sites at LaxCa1−xMnO3 nanostructures towards the oxygen reduction reaction (ORR) in alkaline solution is assessed as a function of the oxide composition. Highly active oxide nanoparticles were synthesised by an ionic liquid-based route, yielding phase-pure nanoparticles, across the entire range of compositions, with sizes between 20 and 35 nm. The bulk vs. surface composition and structure are investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge spectroscopy (XANES). These techniques allow quantification of not only changes in the mean oxidation state of Mn as a function of x, but also the extent of A-site surface segregation. Both trends manifest themselves in the electrochemical responses associated with surface Mn sites in 0.1 M KOH solution. The characteristic redox signatures of Mn sites are used to estimate their effective surface number density. This parameter allows comparing, for the first time, the mean electrocatalytic activity of surface Mn sites as a function of the LaxCa1−xMnO3 composition. The ensemble of experimental data provides a consistent picture in which increasing electron density at the Mn sites leads to an increase in the ORR activity. We also demonstrate that normalisation of electrochemical activity by mass or specific surface area may result in inaccurate structure–activity correlations.

Electrochemical Behavior of TiOxCy as Catalyst Support for Direct Ethanol Fuel Cells at Intermediate Temperature: From Planar Systems to Powders

To achieve complete oxidation of ethanol (EOR) to CO2, higher operating temperatures (often called intermediate-T, 150-200 °C) and appropriate catalysts are required. We examine here titanium oxycarbide (hereafter TiOxCy) as a possible alternative to standard carbon-based supports to enhance the stability of the catalyst/support assembly at intermediate-T. To test this material as electrocatalyst support, a systematic study of its behavior under electrochemical conditions was carried out. To have a clear description of the chemical changes of TiOxCy induced by electrochemical polarization of the material, a special setup that allows the combination of X-ray photoelectron spectroscopy and electrochemical measurements was used. Subsequently, an electrochemical study was carried out on TiOxCy powders, both at room temperature and at 150 °C. The present study has revealed that TiOxCy is a sufficiently conductive material whose surface is passivated by a TiO2 film under working conditions, which prevents the full oxidation of the TiOxCy and can thus be considered a stable electrode material for EOR working conditions. This result has also been confirmed through density functional theory (DFT) calculations on a simplified model system. Furthermore, it has been experimentally observed that ethanol molecules adsorb on the TiOxCy surface, inhibiting its oxidation. This result has been confirmed by using in situ Fourier transform infrared spectroscopy (FTIRS). The adsorption of ethanol is expected to favor the EOR in the presence of suitable catalyst nanoparticles supported on TiOxCy.

Thermally Induced Strains on the Catalytic Activity and Stability of Pt-M2O3/C (M=Y or Gd) Catalysts towards Oxygen Reduction Reaction

Yttrium oxide and gadolinium oxide modified platinum nanoparticles supported on carbon (Vulcan XC‐72), noted as Pt–M2O3/C (M=Y and Gd), were synthesized by water‐in‐oil nanoemulsion chemical route, followed by heat treatment at 100 and 300 °C under hydrogen/nitrogen (H2/N2) atmosphere and tested as electrocatalysts for the oxygen reduction reaction (ORR). As revealed by powder X‐ray diffraction analysis, all obtained catalysts showed solely Pt face‐centered‐cubic structure, and absence of a secondary phase before and after heat treatments, indicating that Y2O3 and Gd2O3 are highly disordered (amorphous) and dispersed clusters. The surface Pt:M ratio (M=Y and Gd), as revealed by X‐ray photoelectron spectroscopy, increased after heat treatment with respect to the value of as‐prepared samples, for which the ratio was 1:1. Microstrain data extracted from Williamson–Hall plots for Pt–M2O3/C (M=Y and Gd) catalysts surprisingly increased after heat treatment at 100 °C, remaining nearly constant after heat treatment at 300 °C, whereas the value of pure Pt nanoparticles, noted as Pt/C, decreased after heat treatments. The mean particle size derived from TEM images for Pt–M2O3/C (M=Y and Gd) was almost unchanged after heat treatments, at variance with the Pt/C case where a clear increase is observed. Surface specific activity and mass activity towards ORR obtained with as‐prepared Pt–M2O3/C (M=Y and Gd) catalysts were higher than those of as‐prepared Pt/C catalyst. After heat treatment, the ORR activity of Pt–M2O3/C (M=Y and Gd) augmented, whereas that of Pt/C diminished. Moreover, after 6000 cycles between 0.5 and 0.95 V versus reversible hydrogen electrode (vs. RHE), Pt–M2O3/C (M=Y and Gd) catalysts retained a large active surface area and a high kinetic current density at 0.9 V vs. RHE in comparison with Pt/C samples. These facts assess a positive effect of the interaction between M2O3 (M=Y and Gd) and Pt catalytic centers both on the catalytic activity of the material towards ORR and on its durability.

Insights into the durability of Co–Fe spinel oxygen evolution electrocatalysts via operando studies of the catalyst structure

Elemental reorganisation and oxidation state changes of key active sites in Co–Fe spinels are investigated by in situ X-ray photoemission spectroscopy (XPS) and operando X-ray absorption spectroscopy (XAS) under oxygen evolution operating conditions. The combination of the two techniques allows identifying both the surface and bulk modifications on the oxides and relating them to the activity loss during extended cycling. The results show that Co–Fe spinels experience a surface irreversible phase evolution under oxygen evolution reaction (OER) conditions, resulting in the formation of an amorphous layer composed of new stable Co(III) and Fe(III) species. Accelerated ageing tests show that the durability, intended as the performance loss during cycling treatments, is not directly related to the structural/chemical stability of the spinels but to the new species formed at the surface due to the electrochemical work. Thus, the material that experienced more significant changes was also the most durable one, demonstrating that the understanding of the chemical and/or structural evolution of the materials during the catalytic process can be the key for the design of highly active and stable catalysts.

Molybdenum Doping Augments Platinum-Copper Oxygen Reduction Electrocatalyst

Improving the efficiency of Pt-based oxygen reduction reaction (ORR) catalysts while also reducing costs remains an important challenge in energy research. To this end, we synthesized highly stable and active carbon-supported Mo-doped PtCu (Mo-PtCu/C) nanoparticles (NPs) from readily available precursors in a facile one-pot reaction. Mo-PtCu/C displays two-to-fourfold-higher ORR half-cell kinetics than reference PtCu/C and Pt/C materials, a trend that was confirmed in proof-of-concept experiments by using a H2 /O2 microlaminar fuel cell. This Mo-induced activity increase mirrors observations for Mo-PtNi/C NPs and possibly suggests an emerging trend. Electrochemical-accelerated stability tests revealed that dealloying was greatly reduced in Mo-PtCu/C in contrast to the binary alloys PtCu/C and PtMo/C. Supporting DFT studies suggested that the exceptional stability of Mo-PtCu could be attributed to oxidative resistance of the Mo-doped atoms. Furthermore, our calculations revealed that oxygen could induce segregation of Mo to the catalytic surface, at which it effected beneficial changes to the surface oxygen adsorption energetics in the context of the Sabatier principle.

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.

Combined Photoemission Spectroscopy and Electrochemical Study of a Mixture of (Oxy)carbides as Potential Innovative Supports and Electrocatalysts.

Active and stable non-noble metal materials, able to substitute Pt as catalyst or to reduce the Pt amount, are vitally important for the extended commercialization of energy conversion technologies, such as fuel cells and electrolyzers. Here, we report a fundamental study of nonstoichiometric tungsten carbide (WxC) and its interaction with titanium oxycarbide (TiOxCy) under electrochemical working conditions. In particular, the electrochemical activity and stability of the WxC/TiOxCy system toward the ethanol electrooxidation reaction (EOR) and hydrogen evolution reaction (HER) are investigated. The chemical changes caused by the applied potential are established by combining photoemission spectroscopy and electrochemistry. WxC is not active toward the ethanol electrooxidation reaction at room temperature but it is highly stable under these conditions thanks to the formation of a passive thin film on the surface, consisting mainly of WO2 and W2O5, which prevents the full oxidation of WxC. In addition, WxC is able to adsorb ethanol, forming ethoxy groups on the surface, which constitutes the first step for the ethanol oxidation. The interaction between WxC and TiOxCy plays an important role in the electrochemical stability of WxC since specific orientations of the substrate are able to stabilize WxC and prevent its corrosion. The beneficial interaction with the substrate and the specific surface chemistry makes tungsten carbide a good electrocatalyst support or cocatalyst for direct ethanol fuel cells. However, WxC is active toward the HER and chemically stable under hydrogen reduction conditions, since no changes in the chemical composition or dissolution of the film are observed. This makes tungsten carbide a good candidate as electrocatalyst support or cocatalyst for the electrochemical production of hydrogen.