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Title: Multielectron, multisubstrate molecular catalysis of electrochemical reactions: Formal kinetic analysis in the total catalysis regime

Abstract

Cyclic voltammetry responses are derived for two-electron, two-step homogeneous electrocatalytic reactions in the total catalysis regime. The models developed provide a framework for extracting kinetic information from cyclic voltammograms (CVs) obtained in conditions under which the substrate or cosubstrate is consumed in a multielectron redox process, as is particularly prevalent for very active catalysts that promote energy conversion reactions. Such determination of rate constants in the total catalysis regime is a prerequisite for the rational benchmarking of molecular electrocatalysts that promote multielectron conversions of small-molecule reactants. The present analysis is illustrated with experimental systems encompassing various limiting behaviors.

Authors:
ORCiD logo; ORCiD logo;
Publication Date:
Research Org.:
Harvard Univ., Cambridge, MA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1540266
Grant/Contract Number:  
SC0017619
Resource Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 114; Journal Issue: 43; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
Science & Technology - Other Topics

Citation Formats

Costentin, Cyrille, Nocera, Daniel G., and Brodsky, Casey N. Multielectron, multisubstrate molecular catalysis of electrochemical reactions: Formal kinetic analysis in the total catalysis regime. United States: N. p., 2017. Web. doi:10.1073/pnas.1711129114.
Costentin, Cyrille, Nocera, Daniel G., & Brodsky, Casey N. Multielectron, multisubstrate molecular catalysis of electrochemical reactions: Formal kinetic analysis in the total catalysis regime. United States. doi:10.1073/pnas.1711129114.
Costentin, Cyrille, Nocera, Daniel G., and Brodsky, Casey N. Mon . "Multielectron, multisubstrate molecular catalysis of electrochemical reactions: Formal kinetic analysis in the total catalysis regime". United States. doi:10.1073/pnas.1711129114. https://www.osti.gov/servlets/purl/1540266.
@article{osti_1540266,
title = {Multielectron, multisubstrate molecular catalysis of electrochemical reactions: Formal kinetic analysis in the total catalysis regime},
author = {Costentin, Cyrille and Nocera, Daniel G. and Brodsky, Casey N.},
abstractNote = {Cyclic voltammetry responses are derived for two-electron, two-step homogeneous electrocatalytic reactions in the total catalysis regime. The models developed provide a framework for extracting kinetic information from cyclic voltammograms (CVs) obtained in conditions under which the substrate or cosubstrate is consumed in a multielectron redox process, as is particularly prevalent for very active catalysts that promote energy conversion reactions. Such determination of rate constants in the total catalysis regime is a prerequisite for the rational benchmarking of molecular electrocatalysts that promote multielectron conversions of small-molecule reactants. The present analysis is illustrated with experimental systems encompassing various limiting behaviors.},
doi = {10.1073/pnas.1711129114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 43,
volume = 114,
place = {United States},
year = {2017},
month = {10}
}

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Cited by: 11 works
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Works referenced in this record:

Reversible Electrocatalytic Production and Oxidation of Hydrogen at Low Overpotentials by a Functional Hydrogenase Mimic
journal, February 2012

  • Smith, Stuart E.; Yang, Jenny Y.; DuBois, Daniel L.
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Turnover Numbers, Turnover Frequencies, and Overpotential in Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry and Preparative-Scale Electrolysis
journal, June 2012

  • Costentin, Cyrille; Drouet, Samuel; Robert, Marc
  • Journal of the American Chemical Society, Vol. 134, Issue 27, p. 11235-11242
  • DOI: 10.1021/ja303560c