High Pressure X-ray Diffraction Study of MgMn2O4 Tetragonal Spinel

The phase stability of the MgMn2O4 spinel has been studied by means of high-pressure X-ray diffraction for pressures up to 30 GPa. Two samples with different inversion degrees have been considered. Both spinels undergo a phase transition towards an orthorhombic structure (CaMn2O4-type). For the more inverted sample the transition pressure is at least 1 GPa lower with respect to that of the less inverted spinel. Also the volume contraction, relative compressibility and density trends are different for the two samples. These variations have been explained according to differences in the cation distribution. and electronic properties of the samples.Comment: 12 pages; 4 Figures presented at the SRMS-

Combined spatially resolved operando spectroscopy: new insights into kinetic oscillations of CO oxidation on Pd/γ-Al2O3

Spatially resolved, combined energy dispersive EXAFS (EDE) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements have been performed over a fixed catalyst bed of Pd/γ-Al2O3 during kinetic oscillations of CO oxidation. The kinetic oscillations of CO oxidation over Pd (or for that matter Pt or Rh) catalysts are a complicated phenomenon that require characterisation techniques with high time resolution and spatial resolution in order to make links between catalyst structure and surface reactivity. By measuring the extent of Pd oxidation at the nanoparticle surface, from Pd K-edge EDE, and matching this with the CO coverage, from DRIFTS spectra, at multiple positions of the fixed bed reactor it is found that the majority of the catalyst undergoes a sharp transition from the CO poisoned catalyst to the highly active, oxidised Pd surface. This transition occurs initially at the end of the catalyst bed, nearest the outlet, and propagates upstream with increasing temperature of the reactor. The oscillations in Pd surface oxide formation and CO coverage are observed only in the first ∼1 mm of the bed, which gives rise to oscillations in CO2 and O2 concentrations observed by end-pipe mass spectrometry after the light-off temperature. The catalyst initially exists as less active, CO poisoned metallic Pd nanoparticles before light-off which transition to a highly active state after light-off when the Pd nanoparticle surface becomes dominated by chemisorbed oxygen. Kinetic oscillations only occur at the front of the catalyst bed where there is sufficient concentration of CO in the gas phase to compete with O2 for adsorption sites at the catalyst surface. We demonstrate the complex nature of the evolving catalyst structure and surface reactivity during catalytic operation and the need for spatially resolved operando methods for understanding and optimising catalyst technologies

Effect of salinity, pressure and temperature on the solubility of smithsonite (ZnCO₃) and Zn complexation in crustal and upper mantle hydrothermal fluids

Modelling the reservoirs and fluxes of Zn in Earth's crust and mantle requires data on the solubility of its mineral hosts and ores in coexisting fluids, as well as on the complexation of Zn in these fluids as a function of fluid composition, pressure, and temperature. However, due to experimental challenges, the availability of such data is limited to pressures below 1 GPa, which are only representative of upper crust conditions. Here, we report the effects of salinity (0–4.5 m total Cl), pressure (0.5–6 GPa) and temperature (25–400 °C) on the solubility of smithsonite (ZnCO3) and speciation of Zn in aqueous fluids. Solubilities at mineral-fluid equilibria and Zn speciation in the coexisting aqueous fluids were determined in situ at high pressure-temperature (P-T) conditions by synchrotron X-ray fluorescence (XRF) and X-ray absorption spectroscopy (XAS) using resistively heated diamond anvil cells (RH-DAC). The solubility of smithsonite increases with salinity, pressure, and temperature. In agreement with previous studies, conducted at lower pressures (below 1 GPa), we observed a gradual transition from octahedral hydrated [Zn(H2O)6]2+ to tetrahedral hydrated and chlorinated [Zn(H2O)4-nCln]2-n (n = 1–4) complexes with increasing salinity and temperature. Our results suggest that these tetrahedral complexes remain stable under the conditions relevant to cold slab dehydration. This change of coordination further enhances the solubility of smithsonite in Cl-rich fluids and provides a likely mechanism for the efficient uptake of Zn by slab-derived fluids.This work was supported by the Natural Environment Research Council (grant number NE/L002507/1)

A novel fuel cell design for operando energy-dispersive X-ray absorption measurements

A polymer electrolyte fuel cell has been designed to allow operando x-ray absorption spectroscopy (XAS) measurements of catalysts. The cell has been developed to operate under standard fuel cell conditions, with elevated temperatures and humidification of the gas-phase reactants, both of which greatly impact the catalyst utilisation. X-ray windows in the endplates of the cell facilitate collection of XAS spectra during fuel cell operation while maintaining good compression in the area of measurement. Results of polarisation curves and cyclic voltammograms showed that the operando cell performs well as a fuel cell, while also providing XAS data of suitable quality for robust XANES analysis. The cell has produced comparable XAS results when performing a cyclic voltammogram to an established in situ cell when measuring the Pt LIII edge. Similar trends of Pt oxidation, and reduction of the formed Pt oxide, have been presented with a time resolution of 5 s for each spectrum, paving the way for time-resolved spectral measurements of fuel cell catalysts in a fully-operating fuel cell.</p

Dataset for Combined spatially resolved operando spectroscopy: New insights into kinetic oscillations of CO oxidation on Pd/&gamma;-Al2O3

Data for: Combined spatially resolved operando spectroscopy: New insights into kinetic oscillations of CO oxidation on Pd/&gamma;-Al2O3 published in Journal of Catalysis.</span

Dataset for &#39;The electronic structure, surface properties, and in situ N2O decomposition of mechanochemically synthesised LaMnO3&#39;

This dataset supports the publication: Rachel H. Blackmore, Maria Elena Rivas, George Tierney, Khaled M. H. Mohammed, Donato Decarolis, Shusaku Hayama, Federica Venturini, Georg Held, Rosa Arrigo, Monica Amboage, Pip Hellier, Evan Lynch, Mahrez Amri, Marianna Casavola, Tugce Eralp Erden, Paul Collier and Peter P. Wells. The electronic structure, surface properties, and in situ N2O decomposition of mechanochemically synthesised LaMnO3. Physical Chemistry Chemical Physics Journal (PCCP)</span

Dataset for &#39;Understanding the Mechanochemical Synthesis of Manganite Perovskites and their Catalytic Behaviour&#39;

This dataset supports University of Southampton PhD thesis &#39;Understanding the Mechanochemical Synthesis of Manganite Perovskites and their Catalytic Behaviour&#39;</span