Mechanistic Insights on the Low-Temperature Oxidation of CO Catalyzed by Isolated Co Ions in N-Doped Carbon

Whitcomb, Colby A.; Sviripa, Anna; Schapowal, Michael I.; Mamedov, Konstantin; Unocic, Raymond R.; Paolucci, Christopher; Davis, Robert J.

doi:10.1021/acscatal.2c04380

Title: Mechanistic Insights on the Low-Temperature Oxidation of CO Catalyzed by Isolated Co Ions in N-Doped Carbon

Journal Article · Mon Dec 05 00:00:00 EST 2022 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.2c04380· OSTI ID:1903139

Whitcomb, Colby A. ^[1]; Sviripa, Anna ^[1]; Schapowal, Michael I. ^[1]; Mamedov, Konstantin ^[1];

^[2];

^[1];

^[1]

Univ. of Virginia, Charlottesville, VA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

Isolated cobalt ions on nitrogen-doped carbon (Co-N-C) catalyze CO oxidation at temperatures as low as 196 K, but the active site and mechanism for this reaction remain elusive. In this work, steady-state CO oxidation around 273 K over Co-N-C revealed nearly first order behavior in both CO and O₂ as well as a negative apparent activation energy. Isotopic transient analysis of the reaction confirmed a rapid turnover frequency and low surface coverage of adsorbed intermediates leading to CO₂ (< 10% of the Co). Results from kinetics experiments combined with quantum chemical calculations and molecular dynamics simulations are consistent with a reaction path involving weak adsorption of CO onto Co ions followed by a low barrier for the CO-assisted activation of weakly adsorbed O₂. Furthermore, this proposed mechanism for dioxygen activation does not involve a redox cycle with the transition metal ion and may be important in other low temperature catalytic reactions involving O₂.

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Research Organization:: Univ. of Virginia, Charlottesville, VA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0012704

OSTI ID:: 1903139

Journal Information:: ACS Catalysis, Vol. 12, Issue 24; 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
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density functional theory
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catalysts
oxidation
oxidation reactions

Title: Mechanistic Insights on the Low-Temperature Oxidation of CO Catalyzed by Isolated Co Ions in N-Doped Carbon

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