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Mechanism of the solid-liquid interfacial reaction between dissolved Cd species and the CaCO surface.
Chemosphere
March 2025
Department of Chemistry, Faculty of Science, Okayama University of Science, 1-1 Ridaicho, Kita-ku, Okayama-shi, Okayama, 700-0005, Japan. Electronic address:
The solid-liquid interfacial reactions between heavy metal ions and CaCO play important roles in geochemical and environmental processes. In particular, the sorption of dissolved Cd species is characterized by two reaction steps. Initially, Cd is adsorbed onto the CaCO surface.
View Article and Find Full Text PDFSpeciation of Tc-Gluconate Complexes in Aqueous Systems.
Inorg Chem
March 2025
Institut für Nukleare Entsorgung (INE), Karlsruher Institut für Technologie (KIT), Campus Nord, Hermann von Helmholtzplatz 1, 76344 Eggenstein-Leopoldshafen, Germany.
Tc-gluconate complexes in aqueous systems were recently reported and characterized by Tc L-edge X-ray absorption near-edge structure (XANES) measurements [Dardenne, K.; 2021, 60, 12285-12298]. The puzzling result was reported that the Tc L-edge XANES of the sample containing Tc(IV)-gluconate species differs substantially from that of the Tc(IV)O(am,hyd) hydrous oxide reference sample, whereas the Tc K-edge XANES spectra did not differ significantly.
View Article and Find Full Text PDFSize-Dependent Ultrafast UV Photochemistry of Aliphatic Disulfides in Solution.
Chemistry
March 2025
Universitat Hamburg, Department of Physics, Institute for Nanostructure and Solid State Physics, Building 600 (CHyN), Luruper Chaussee 149, 22761, Hamburg, GERMANY.
We have investigated the photochemistry of dimethyl disulfide (DMDS) and glutathione disulfide (GSSG) in solution upon ultraviolet (UV) excitation in comparison to L-cystine by femtosecond X-ray absorption spectroscopy at the sulfur K-edge. For these aliphatic disulfides, the very similar differential absorption spectra reveal unequivocally a pair of geminate thiyl radicals as the single primary reaction product with a formation time constant of about 100 fs. We find size-dependent majority yields for disulfide recombination with DMDS reforming ten-fold slower and at lower quantum yield than L-cystine while GSSG recombines even faster than L-cystine at a yield of nearly 80 % within 2 ps after excitation.
View Article and Find Full Text PDFAlloyed molybdenum enables efficient alcohol hydrodeoxygenation with supported bimetallic catalysts.
Chem Sci
March 2025
D-CHAB, ETH Zürich Vladimir-Prelog-Weg 2 8093 Zürich Switzerland
Bimetallic heterogeneous catalysts combining group 9 metals (Rh, Ir) or group 10 metals (Ni, Pd, Pt) with Mo on a silica-based support have been synthesized surface organometallic chemistry and assessed in their catalytic activity for the hydrodeoxygenation (HDO) of alcohols with particular emphasis on the structural evolution of the catalysts and the role of Mo. The investigation was conducted with an air-free approach to isolate any sample alterations exclusively to those caused by the reaction. Structural analysis was performed using a combination of (S)TEM, IR, and XAS.
View Article and Find Full Text PDFDeconvolving lithium-ion redox in vanadium-iron oxide aerogels using X-ray absorption spectroscopy and density functional theory.
Phys Chem Chem Phys
March 2025
Code 6170, Surface Chemistry Branch, U.S. Naval Research Laboratory, Washington, DC, USA.
Substitution of vanadium into earth-abundant maghemite iron oxide introduces cation vacancies that increase Li storage capacity concomitant with a positive shift in its electrochemical potential. Expressing vanadium ferrite (VFeO) as an aerogel offers an opportunity to probe Li storage in this inherently defective spinel from highly disordered (X-ray amorphous) to nanocrystalline. To understand the redox sequence of the host cations, we use X-ray absorption near-edge spectroscopy (XANES) obtained using an in-lab X-ray absorption spectrometer in concert with density functional theory calculations to uncover the quantum mechanical-level effects that underpin relevant energy-storage behaviors.
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