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Metal–Ligand Exchange Coupling Promotes Iron-Catalyzed Electrochemical CO2 Reduction at Low Overpotentials

preprint
submitted on 02.03.2020 and posted on 02.03.2020 by Jeffrey Derrick, Matthias Loipersberger, Diana Iovan, Peter T. Smith, Khetpakorn Chakarawet, Jeffrey R. Long, Martin Head-Gordon, Christopher Chang
Biological and heterogenous catalysts for electrochemical CO2 reduction often exhibit a high degree of electronic delocalization that serves to minimize overpotential and maximize selectivity over hydrogen evolution. Here, we report a molecular iron(II) complex that achieves a similar feat as a result of strong metal–ligand exchange coupling. This interaction promotes an open-shell singlet electronic structure that drives the electrochemical reduction of CO2 to CO with over 90% selectivity and turnover frequencies of 100,000 s−1 at low overpotentials, with no degradation over 20 hours. The decrease in the thermodynamic barrier engendered by this strong metal–ligand exchange coupling enables homogeneous CO2 reduction catalysis in water without compromising reaction selectivity.

Funding

U. S. Department of Energy (Grand No. DE-AC02-05CH11231)

National Science Foundation (Grant No. CHE-1800252)

History

Email Address of Submitting Author

jderrick@berkeley.edu

Institution

University of California, Berkeley

Country

United States

ORCID For Submitting Author

0000-0002-3879-2897

Declaration of Conflict of Interest

The authors have submitted a provisional patent based on this technology.

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