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Hydride Rebound: A Frustrated Lewis Pair (FLP)-Type Cooperative Mechanism for H2 Activation by a Potassium Aluminyl Compound.
Chemistry
January 2025
University of Oxford, Inorganic Chemistry Laboratory, UNITED KINGDOM OF GREAT BRITAIN AND NORTHERN IRELAND.
Combining experiment and theory, the mechanisms of H2 activation by the potassium-bridged aluminyl dimer K2[Al(NON)]2 (NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tertbutyl-9,9-dimethylxanthene) and its monomeric K+-sequestered counterpart have been investigated. These systems show diverging reactivity towards the activation of dihydrogen, with the dimeric species undergoing formal oxidative addition of H2 at each Al centre under ambient conditions, and the monomer proving to be inert to dihydrogen addition. Noting that this K+ dependence is inconsistent with classical models of single-centre reactivity for carbene-like Al(I) species, we rationalize these observations instead by a cooperative frustrated Lewis pair (FLP)-type mechanism (for the dimer) in which the aluminium centre acts as the Lewis base and the K+ centres as Lewis acids.
View Article and Find Full Text PDFHydrogen Sensing via Heterolytic H2 Activation at Room Temperature by Atomic Layer Deposited Ceria.
ChemSusChem
January 2025
Brandenburgische Technische Universitat Cottbus-Senftenberg, Angewandte Physik und Halbleiterspektroskopie, Konrad-Zuse-Str. 1, 03046, Cottbus, GERMANY.
Ultrathin atomic layer deposited ceria films (< 20 nm) are capable of H2 heterolytic activation at room temperature, undergoing a significant reduction regardless of the absolute pressure, as measured under in-situ conditions by near ambient pressure X-ray photoelectron spectroscopy. ALD-ceria can gradually reduce as a function of H2 concentration under H2/O2 environments, especially for diluted mixtures below 10%. At room temperature, this reduction is limited to the surface region, where the hydroxylation of the ceria surface induces a charge transfer towards the ceria matrix, reducing Ce4+ cations to Ce3+.
View Article and Find Full Text PDFMethane to Methanol Transformation on Cu/H-ZSM-5 Zeolite. Characterization of Copper State and Mechanism of the Reaction.
Chemistry
January 2025
Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Prospekt Akademika Lavrentieva 5, Novosibirsk, 630090, Russia.
Cu-modified zeolites provide methane conversion to methanol with high selectivity under mild conditions. The activity of different Cu-sites for methane transformation is still under discussion. Herein, ZSM-5 zeolite has been loaded with Cu cations (1.
View Article and Find Full Text PDFA Zero-Gap Electrolyzer Enables Supporting Electrolyte-Free Seawater Splitting for Energy-Saving Hydrogen Production.
Angew Chem Int Ed Engl
January 2025
Qingdao Industrial Energy Storage Research Institute, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, 266101, China.
Membrane-assisted direct seawater splitting (DSS) technologies are actively studied as a promising route to produce green hydrogen (H), whereas the indispensable use of supporting electrolytes that help to extract water and provide electrochemically-accelerated reaction media results in a severe energy penalty, consuming up to 12.5 % of energy input when using a typical KOH electrolyte. We bypass this issue by designing a zero-gap electrolyzer configuration based on the integration of cation exchange membrane and bipolar membrane assemblies, which protects stable DSS operation against the precipitates and corrosion in the absence of additional supporting electrolytes.
View Article and Find Full Text PDFComputational Study on the Proton Reduction Potential of Co, Rh, and Ir Molecular Electrocatalysts for the Hydrogen Evolution Reaction.
ACS Omega
December 2024
MolMod-CS-Instituto de Química, Universidade Federal Fluminense, Campos de Valonginho s/n, Centro, Niterói, Rio de Janeiro 24020-14, Brazil.
In this study, comprehensive density functional theory calculations were conducted to investigate the molecular mechanism of electrocatalytic proton reduction using group 9 transition metal bpaqH (2-(bis(pyridin-2-ylmethyl)amino)--(quinolin-8-yl)acetamide) complexes. The goal was to explore how variations in the structural and electronic properties among the three metal centers might impact the catalytic activity. All three metal complexes were observed to share a similar mechanism, primarily characterized by three key steps: heterolytic cleavage of H (HEP), reduction protonation (RPP), and ligand-centered protonation (LCP).
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