Reversible and Selective CO 2 to HCO 2 − Electrocatalysis near the Thermodynamic Potential

Cunningham, Drew W.; Barlow, Jeffrey M.; Velazquez, Reyna S.; Yang, Jenny Y.

doi:10.1002/ange.201913198

Title: Reversible and Selective CO ₂ to HCO ₂ ⁻ Electrocatalysis near the Thermodynamic Potential

Journal Article · 03 February 2020 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.201913198 · OSTI ID:1597157

Cunningham, Drew W. ^[1]; Barlow, Jeffrey M. ^[1]; Velazquez, Reyna S. ^[1];

^[1]

Department of Chemistry University of California, Irvine Natural Sciences II Irvine CA 92697 USA

Abstract Reversible catalysis is a hallmark of energy‐efficient chemical transformations, but can only be achieved if the changes in free energy of intermediate steps are minimized and the catalytic cycle is devoid of high transition‐state barriers. Using these criteria, we demonstrate reversible CO ₂ /HCO ₂ ⁻ conversion catalyzed by [Pt(depe) ₂ ] ²⁺ (depe=1,2‐ bis (diethylphosphino)ethane). Direct measurement of the free energies associated with each catalytic step correctly predicts a slight bias towards CO ₂ reduction. We demonstrate how the experimentally measured free energy of each step directly contributes to the <50 mV overpotential. We also find that for CO ₂ reduction, H ₂ evolution is negligible and the Faradaic efficiency for HCO ₂ ⁻ production is nearly quantitative. A free‐energy analysis reveals H ₂ evolution is endergonic, providing a thermodynamic basis for highly selective CO ₂ reduction.

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Sponsoring Organization:: USDOE

OSTI ID:: 1597157

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 11 Vol. 132; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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