Operando X-ray Spectroscopy
Key activity descriptors of nickel-iron oxygen evolution electrocatalysts in the presence of alkali metal cations
Ni-Fe oxyhydroxide is among the most active oxygen evolution electrocatalysts. Electrolyte alkali metal cations modify the activity and reaction intermediates, however, the exact mechanism is at question due to unexplained deviations from the cation size trend. Our X-ray absorption spectroelectrochemical results show that the OER activity follows the variations in .electrolyte pH rather than a specific cation. Our DFT-based reactivity descriptors confirm the conclusions of an indirect pH effect.
A fundamental understanding of the active sites in technical CoMo/ Al2O3 catalysts is crucial to improve the production of clean transportation fuels by hydrodesulfurization (HDS), which removes sulfur from fossil fuels. Sulfur dioxide, resulting from fossil fuel combustion, is one of the main causes for acid rain. In situ X-ray spectroscopic experiments at the SuperXAS beamline of the SLS provided insight in the structure and number of active sites (“Co−Mo−S”) in sulfided CoMo/ Al2O3 catalysts. When the Co to Mo ratio is less than 0.1, cobalt forms isolated sites on the MoS2 phase, where the cobalt promoter atoms are in centrosymmetric octahedral coordination with six-sulfur ligands.
In this work, the complementarity of pump-probe experiments at SwissFEL (ALVRA endstation) and at synchrotrons (SuperXAS beamline of SLS and ID09 of ESRF) is used to investigate the triplet excited state of Cu OLED materials. Details about the charge transfer and structural rearrangements in the excited state of this material are revealed and obtained data can be used to verify computational methods for rational development of new OLED materials.
Elucidating the Oxygen Activation Mechanism on Ceria-Supported Copper-Oxo Species Using Time-Resolved X-ray Absorption Spectroscopy
We monitored the dynamic structure of the active sites in a catalyst containing highly dispersed copper-oxo species on ceria during low-temperature CO oxidation using time-resolved X-ray absorption spectroscopy. We quantitatively demonstrate that the CO oxidation mechanism below 90 °C involves an oxygen intermediate strongly bound to the active sites as well as the redox activity of Cu2+/Cu+ and Ce4+/Ce3+ couples.
Unlike the homogeneous Wacker process, the understanding of the mechanism of the heterogeneous system has long remained to be superficial. Here the authors investigated the mechanism of heterogeneous Wacker oxidation over Pd-Cu/zeolite Y through transient XAS coupled with kinetic studies and chemometric analysis.
Enhanced CH3OH selectivity in CO2 hydrogenation using Cu-based catalysts generated via SOMC from GaIII single-sites
Small and narrowly distributed nanoparticles of copper alloyed with gallium supported on silica containing residual GaIII sites can be obtained via surface organometallic chemistry. This material is highly active and selective for CO2 hydrogenation to CH3OH. In situ X-ray absorption spectroscopy shows that gallium is oxidized under reaction conditions while copper remains as Cu0.
Structural selectivity of supported Pd nanoparticles for catalytic NH3 oxidation resolved using combined operando spectroscopy
The link between Pd nanoparticle structure and surface reactivity for NH3 abatement was found using operando X-ray absorption fine structure spectroscopy, diffuse reflectance infrared Fourier-transformed spectroscopy and on-line mass spectrometry.
This work presents a new approach for synthesizing Fe-based oxygen reduction reaction (ORR) catalysts using sodium carbonate (Na2CO3) as an inexpensive but effective pore-inducing agent offering microporosity control.
Kinetics of Lifetime Changes in Bimetallic Nanocatalysts Revealed by Quick X‐ray Absorption Spectroscopy
The different reaction steps involved in repeated Pt13In9 segregation‐alloying are identified by XAS and kinetically characterized at the single‐cycle level.