A unifying mechanism for cation effect modulating C1 and C2 productions from CO2 electroreduction

Authors
Shin, Seung-JaeChoi, HansolRinge, StefanWon, Da HyeOh, Hyung-SukKim, Dong HyunLee, TaeminNam, Dae-HyunKim, HyungjunChoi, Chang Hyuck
Issue Date
2022-09
Publisher
Nature Publishing Group
Citation
Nature Communications, v.13, no.1
Abstract
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.
Keywords
ALKALI-METAL CATIONS; ELECTROCHEMICAL REDUCTION; FREE-ENERGY; SELECTIVITY; INTERFACE; WATER; AU
ISSN
2041-1723
URI
https://pubs.kist.re.kr/handle/201004/114583
DOI
10.1038/s41467-022-33199-8
Appears in Collections:
KIST Article > 2022
Files in This Item:
There are no files associated with this item.
Export
RIS (EndNote)
XLS (Excel)
XML

qrcode

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

BROWSE