Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 59, Issue 26, Pages 10514-10518Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202000385
Keywords
density functional theory; dioxygen activation; MOFs; reaction mechanism; single-atom sites
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Funding
- German Research Foundation (DFG) through the Cluster 3DMM2O
- German Research Foundation (DFG) [WO 464/41-1]
- Helmholtz Association
- China Postdoctoral Council (OCPC)
- state of Baden-Wurttemberg through bwHPC (bwunicluster)
- state of Baden-Wurttemberg through bwHPC (JUSTUS) [RV bw17D011]
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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+/Cu2+ dimer defects, created in a controlled fashion by reducing the pristine Cu2+/Cu2+ 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+/Cu2+. 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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