Journal
NATURE COMMUNICATIONS
Volume 13, Issue 1, Pages -Publisher
NATURE PORTFOLIO
DOI: 10.1038/s41467-022-33199-8
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Funding
- Samsung Science and Technology Foundation [SSTF-BA2101-08]
- National Research Foundation of Korea (NRF) - Korea government (MSIT) [2021R1A5A1030054]
- KIST Institutional Program
- Korea Institute of Science and Technology Information (KISTI) National Supercomputing Center [KSC-2020-CHA-0006]
- MSIT
- POSTECH
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This study investigates the cation-coupled electron transfer in the CO2 reduction reaction and establishes the H+- and M+-associated electron transfer mechanisms for CH4 and CO/C2H4 formations. The theoretical scenarios are supported by Nernstian shifts of polarization curves and the first-order kinetics of CO/C2H4 formation on the electrode surface charge density.
Electrocatalysis, whose reaction venue locates at the catalyst-electrolyte interface, is controlled by the electron transfer across the electric double layer, envisaging a mechanistic link between the electron transfer rate and the electric double layer structure. A fine example is in the CO2 reduction reaction, of which rate shows a strong dependence on the alkali metal cation (M+) identity, but there is yet to be a unified molecular picture for that. Using quantum-mechanics-based atom-scale simulation, we herein scrutinize the M+-coupling capability to possible intermediates, and establish H+- and M+-associated ET mechanisms for CH4 and CO/C2H4 formations, respectively. These theoretical scenarios are successfully underpinned by Nernstian shifts of polarization curves with the H+ or M+ concentrations and the first-order kinetics of CO/C2H4 formation on the electrode surface charge density. Our finding further rationalizes the merit of using Nafion-coated electrode for enhanced C2 production in terms of enhanced surface charge density. CO2 reduction rate shows a strong dependence on alkali metal cation identity but a unified molecular picture for underlying mechanism requires further investigation. Using advanced molecular simulations and experimental kinetic studies, here the authors establish a unified mechanism for cation-coupled electron transfer.
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