Anionic Single-Atom Catalysts for CO Oxidation: Support-Independent Activity at Low Temperatures

Kropp, Thomas; Lu, Zhuole; Li, Zhao; Chin, Ya-Huei Cathy; Mavrikakis, Manos

doi:10.1021/acscatal.8b03298

Anionic Single-Atom Catalysts for CO Oxidation: Support-Independent Activity at Low Temperatures

Journal Article · Fri Jan 25 00:00:00 EST 2019 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.8b03298· OSTI ID:1494746

^[1]; Lu, Zhuole ^[2]; Li, Zhao ^[2]; ^[2]; ^[3]

Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering; University of Wisconsin-Madison Department of Chemical and Biological Engineering
Univ. of Toronto, ON (Canada). Dept. of Chemical Engineering and Applied Chemistry
Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering

We study here 14 atomically dispersed transition metals on halite-type oxides (MeO, Me = Fe, Mg, Mn, and Ni) using periodic density functional theory calculations and probe structure and activity toward CO oxidation for a subset of these systems experimentally. Pd and Pt can form stable negatively charged species upon binding to oxygen vacancies; the magnitude of the metal atom binding energy depends on the O vacancy formation energies of the supporting metal oxide and the lattice match between transition metal and support. The resulting oxide-supported single-atom systems catalyze CO oxidation by molecularly adsorbed O₂ with intrinsic barriers as low as 36 kJ/mol for Pt/MnO_x(001). This high activity stems from the single sites’ ability to stabilize surface superoxide species. Furthermore, intrinsic barriers were found to depend primarily on the identity of the transition metal and to be nearly independent of the support identity. However, O₂ may heal the oxygen vacancy, which leads to catalyst deactivation. Catalyst deactivation by oxygen can be suppressed by using a more reducible support such as FeO(001) or MnO(001).

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Toronto, ON (Canada); Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: Natural Sciences and Engineering Research Council of Canada (NSERC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357; FG02-05ER15731

OSTI ID:: 1494746

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 2 Vol. 9; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO oxidation
atomic dispersion
density functional theory
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Anionic Single-Atom Catalysts for CO Oxidation: Support-Independent Activity at Low Temperatures

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