Title
CO oxidation by Pt2/Fe3O4: Metastable dimer and support configurations facilitate lattice oxygen extraction
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Abstract
Heterogeneous catalysts based on subnanometer metal clusters often exhibit strongly size-dependent properties, and the addition or removal of a single atom can make all the difference. Identifying the most active species and deciphering the reaction mechanism is extremely difficult, however, because it is often not clear how the catalyst evolves in operando. Here, we use a combination of atomically resolved scanning probe microscopies, spectroscopic techniques, and density functional theory (DFT)–based calculations to study CO oxidation by a model Pt/Fe3O4(001) “single-atom” catalyst. We demonstrate that (PtCO)2 dimers, formed dynamically through the agglomeration of mobile Pt-carbonyl species, catalyze a reaction involving the oxide support to form CO2. Pt2 dimers produce one CO2 molecule before falling apart into two adatoms, releasing the second CO. Olattice extraction only becomes facile when both the Pt-dimer and the Fe3O4 support can access metastable configurations, suggesting that substantial, concerted rearrangements of both cluster and support must be considered for reactions occurring at elevated temperature.
Keywords
Multidisciplinary
Object type
Language
English [eng]
Persistent identifier
Appeared in
Title
Science Advances
Volume
8
Issue
13
ISSN
2375-2548
Issued
2022
Publication
American Association for the Advancement of Science (AAAS)
Version type
Date issued
2022
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Rights
Rights statement
© 2022 The Authors, some rights reserved
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