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Interplay of Electronic and Steric Effects to Yield Low‐Temperature CO Oxidation at Metal Single Sites in Defect‐Engineered HKUST‐1

Wang, Weijia; Sharapa, Dmitry I.; Chandresh, Abhinav; Nefedov, Alexei; Heißler, Stefan; Heinke, Lars; Studt, Felix; Wang, Yuemin; Wöll, Christof

In contrast to catalytically active metal single atoms deposited on oxide nanoparticles, the crystalline nature of metal‐organic frameworks (MOFs) allows for a thorough characterization of reaction mechanisms. Using defect‐free HKUST‐1 MOF thin films, we demonstrate that Cu$^{+}$/Cu$^{2+}$ dimer defects, created in a controlled fashion by reducing the pristine Cu2$^{+}$/Cu$^{2+}$ pairs of the intact framework, account for the high catalytic activity in low‐temperature CO oxidation. Combining advanced IR spectroscopy and density functional theory we propose a new reaction mechanism where the key intermediate is an uncharged O$_{2}$ species, weakly bound to Cu$^{+}$/Cu$^{2+}$. Our results reveal a complex interplay between electronic and steric effects at defect sites in MOFs and provide important guidelines for tailoring and exploiting the catalytic activity of single metal atom sites.

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Verlagsausgabe §
DOI: 10.5445/IR/1000118931
Veröffentlicht am 05.05.2020
DOI: 10.1002/anie.202000385
Zitationen: 8
Web of Science
Zitationen: 7
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Funktionelle Grenzflächen (IFG)
Institut für Katalyseforschung und -technologie (IKFT)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2020
Sprache Englisch
Identifikator ISSN: 1433-7851, 1521-3773
KITopen-ID: 1000118931
HGF-Programm 43.22.02 (POF III, LK 01) Nanocatalysis
Erschienen in Angewandte Chemie / International edition
Verlag Wiley
Band 59
Heft 26
Seiten 10514-10518
Vorab online veröffentlicht am 17.04.2020
Nachgewiesen in Web of Science
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