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Title: Reversible and Selective CO2 to HCO2- Electrocatalysis near the Thermodynamic Potential

Abstract

Reversible catalysis is an emblem 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 show reversible CO2/HCO2- 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 CO2 reduction. We demonstrate how the experimentally measured free energy of each step directly contributes to the <50mV overpotential. We also find that for CO2 reduction, H2 evolution is negligible and the Faradaic efficiency for HCO2- production is nearly quantitative. A free-energy analysis reveals H2 evolution is endergonic, providing a thermodynamic basis for highly selective CO2 reduction.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]
  1. Univ. of California, Irvine, CA (United States)
Publication Date:
Research Org.:
Univ. of California, Irvine, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Sloan Foundation
Contributing Org.:
Canadian Institute for Advanced Research (CIFAR)
OSTI Identifier:
1599223
Alternate Identifier(s):
OSTI ID: 1597124
Grant/Contract Number:  
SC0012150; 0000243266
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 59; Journal Issue: 11; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
10 SYNTHETIC FUELS; Carbon dioxide reduction; electrocatalysis; formate; reversible catalysis; thermochemistry

Citation Formats

Cunningham, Drew W., Barlow, Jeffrey M., Velazquez, Reyna S., and Yang, Jenny Y.. Reversible and Selective CO2 to HCO2- Electrocatalysis near the Thermodynamic Potential. United States: N. p., 2019. Web. https://doi.org/10.1002/anie.201913198.
Cunningham, Drew W., Barlow, Jeffrey M., Velazquez, Reyna S., & Yang, Jenny Y.. Reversible and Selective CO2 to HCO2- Electrocatalysis near the Thermodynamic Potential. United States. https://doi.org/10.1002/anie.201913198
Cunningham, Drew W., Barlow, Jeffrey M., Velazquez, Reyna S., and Yang, Jenny Y.. Tue . "Reversible and Selective CO2 to HCO2- Electrocatalysis near the Thermodynamic Potential". United States. https://doi.org/10.1002/anie.201913198. https://www.osti.gov/servlets/purl/1599223.
@article{osti_1599223,
title = {Reversible and Selective CO2 to HCO2- Electrocatalysis near the Thermodynamic Potential},
author = {Cunningham, Drew W. and Barlow, Jeffrey M. and Velazquez, Reyna S. and Yang, Jenny Y.},
abstractNote = {Reversible catalysis is an emblem 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 show reversible CO2/HCO2- 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 CO2 reduction. We demonstrate how the experimentally measured free energy of each step directly contributes to the <50mV overpotential. We also find that for CO2 reduction, H2 evolution is negligible and the Faradaic efficiency for HCO2- production is nearly quantitative. A free-energy analysis reveals H2 evolution is endergonic, providing a thermodynamic basis for highly selective CO2 reduction.},
doi = {10.1002/anie.201913198},
journal = {Angewandte Chemie (International Edition)},
number = 11,
volume = 59,
place = {United States},
year = {2019},
month = {12}
}

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