Christopher J. Lee, Marcus A. Sharp, Benjamin A. Jackson, Mausumi Mahapatra, Simone Raugei, Líney Árnadóttir, Mal-Soon Lee, Bruce D. Kay, Zdenek Dohnálek
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引用次数: 0
Abstract
The stability and activity of supported single-atom catalysts (SACs) represent critical yet opposing factors limiting our ability to explore and exploit their catalytic properties. This study demonstrates the operation of a catalyst that is dynamically activated in the presence of surface intermediates and reverts to a stable but inactive form when the reaction is completed. We employ atomically defined Rh/Fe3O4(001) catalysts to demonstrate how structurally stable Rh, bound in surface octahedral Fe sites, gets destabilized to form highly active Rh adatoms and small clusters. Conversion of formic acid, leading initially to surface formate and hydroxyl species, is employed as a model reaction to probe the dynamics of such processes. We find that surface hydroxyl recombination to water through the Mars–van Krevelen mechanism reduces Rh coordination, triggering its conversion to active Rh adatoms. Upon completion of the reaction (surface-intermediate free catalyst), Rh adatoms return back to the stable octahedral Rh sites, limiting Rh sintering. Since lattice oxygen exchange is observed in many acid–base and redox chemistries, the process can be broadly applicable to controlling the activation and stability of the range of SACs.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.