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

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[Formula: see text]). Without

SUBMITTER: Qin X 

PROVIDER: S-EPMC10665450 | biostudies-literature | 2023 Nov

REPOSITORIES: biostudies-literature