Cation-induced changes in the inner- and outer-sphere mechanisms of electrocatalytic CO2 reduction

Xueping Qin (), Heine A. Hansen, Karoliina Honkala and Marko M. Melander ()
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Xueping Qin: Technical University of Denmark
Heine A. Hansen: Technical University of Denmark
Karoliina Honkala: University of Jyväskylä
Marko M. Melander: University of Jyväskylä

Nature Communications, 2023, vol. 14, issue 1, 1-11

Abstract: Abstract The underlying mechanism of cation effects on CO2RR remains debated. Herein, we study cation effects by simulating both outer-sphere electron transfer (OS-ET) and inner-sphere electron transfer (IS-ET) pathways during CO2RR via constrained density functional theory molecular dynamics (cDFT-MD) and slow-growth DFT-MD (SG-DFT-MD), respectively. Our results show without any cations, only OS-ET is feasible with a barrier of 1.21 eV. In the presence of K+ (Li+), OS-ET shows a very high barrier of 2.93 eV (4.15 eV) thus being prohibited. However, cations promote CO2 activation through IS-ET with the barrier of only 0.61 eV (K+) and 0.91 eV (Li+), generating the key intermediate (adsorbed CO $${}_{2}^{\delta -}$$ 2 δ − ). Without cations, CO2-to-CO $${}_{2}^{\delta -}$$ 2 δ − (ads) conversion cannot proceed. Our findings reveal cation effects arise from short-range Coulomb interactions with reaction intermediates. These results disclose that cations modulate the inner- and outer-sphere pathways of CO2RR, offering substantial insights on the cation specificity in the initial CO2RR steps.

Date: 2023
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DOI: 10.1038/s41467-023-43300-4

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