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Interpreting the Electrocatalytic Voltammetry of Homogeneous Catalysts by the Foot of the Wave Analysis and Its Wider Implications
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Physical Chemistry.ORCID iD: 0000-0002-1778-3377
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Synthetic Molecular Chemistry.ORCID iD: 0000-0002-6570-6392
2019 (English)In: ACS Catalysis, ISSN 2155-5435, E-ISSN 2155-5435, Vol. 9, no 8, p. 7109-7123Article in journal (Refereed) Published
Abstract [en]

Mechanistic studies of electrocatalytic reactions play a crucial role in developing efficient electrocatalysts and solar-fuel devices. The foot of the wave analysis (FOWA) for cyclic voltammetry, recently developed by Saveant and Costentin, provides a powerful means to evaluate the performance of molecular electrocatalysts. However, there is a considerable amount of confusion in the community on how to interpret FOWA in multielectron electrochemical reactions. Herein, we further expand their earlier models from the Nernstian region to all scenarios (i.e., including non-Nernstian behavior) and systematically examine individual parameters, such as formal potentials and reaction rate constants, to explore deeper insights and limitations. Detailed analysis from in silico voltammograms based on different mechanistic models reveals characteristic features of FOWA traces for different kinetic phenomena, which is useful to diagnose kinetic profiles and elucidate the limits of FOWA. The lessons learned from these analyses are further used to reconcile the discrepancy of rate constants determined by FOWA versus other methods, such as time-resolved spectroscopy, for molecular electrocatalysts that catalyze proton reduction or the reduction of CO2 to CO. Such reconciliation demonstrates that electrochemical methods along with FOWA can serve as an alternative tool to determine kinetic information and probe mechanistic insights, which otherwise may be challenging and complicated to achieve by conventional methods. In addition, general guidelines and warnings are also presented to avoid potential errors or mishandling when using FOWA.

Place, publisher, year, edition, pages
AMER CHEMICAL SOC , 2019. Vol. 9, no 8, p. 7109-7123
Keywords [en]
electrocatalysis, FOWA, mechanistic studies, hydrogen evolution reaction, CO2 reduction, homogeneous electrocatalysts
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-393746DOI: 10.1021/acscatal.9b00850ISI: 000480503700052OAI: oai:DiVA.org:uu-393746DiVA, id: diva2:1369166
Available from: 2019-11-11 Created: 2019-11-11 Last updated: 2019-11-11Bibliographically approved

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Wang, Vincent Cho-ChienJohnson, Ben A.

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