Coverage-Induced Cation Dehydration and Migration for Enhanced CO-CO Coupling on Cu Electrocatalysts

Yan, Hui-Min1,2; Zhang, Zisheng3; Wang, Yang-Gang1,2

2024-02-20

10.1021/acscatal.3c05812

ACS CATALYSIS   影响因子和分区

2155-5435

Copper is a promising catalyst for the electroreduction of CO2/CO (CO2RR/CORR) to valuable multicarbon products, but the origin of its CO-CO coupling activity remains unresolved. This greatly limits the rational design and practical application of copper-based catalysts. Herein, we have performed extensive ab initio molecular dynamics simulations with explicit solvation to investigate the free energy profile of CO-CO coupling at the complex electrochemical interface and discovered the critical role of the interplay between the alkali metal cation and CO intermediates. We have found that due to the hydrophobicity of CO, the solvated alkali metal cation (Li+, Na+, K+, or Cs+) in the electric double layer (EDL) could dynamically dehydrate and migrate toward the copper surface as the CO coverage increases. The closer-to-surface dehydrated alkali metal cation can significantly promote CO-CO coupling by stabilizing the largely polarized transition state. Notably, once CO-CO coupling is completed, the cation can be released from the product state to participate in the next catalytic cycle. The adaptive coordination environment of the alkali metal cation to the reaction coordinate makes a dynamic local environment which promotes CO-CO coupling both kinetically and thermodynamically. Our obtained insight into the dynamic process unravels the significant role of alkali metal cations and provides a perspective to understand how C-2 products are generated at the complex electrochemical interface during the CO2RR/CORR.

CO2 reduction reaction CO-CO coupling cation effect coverage effect explicit solvation

SCI ; EI

英语

第一 ; 通讯

Science, Technology and Innovation Commission of Shenzhen Municipality[22373045] ; NSFC[2019QN01L353] ; Guangdong "Pearl River" Talent Plan["KCXST20221021111207017","JCYJ20220818100410023"] ; Science, Technology and Innovation Commission of Shenzhen Municipality[2020B121201002]

Chemistry

Chemistry, Physical

WOS:001173731700001

AMER CHEMICAL SOC

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China
2.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Guangdong, Peoples R China
3.Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

Yan, Hui-Min,Zhang, Zisheng,Wang, Yang-Gang. Coverage-Induced Cation Dehydration and Migration for Enhanced CO-CO Coupling on Cu Electrocatalysts[J]. ACS CATALYSIS,2024,14(5).

Yan, Hui-Min,Zhang, Zisheng,&Wang, Yang-Gang.(2024).Coverage-Induced Cation Dehydration and Migration for Enhanced CO-CO Coupling on Cu Electrocatalysts.ACS CATALYSIS,14(5).

Yan, Hui-Min,et al."Coverage-Induced Cation Dehydration and Migration for Enhanced CO-CO Coupling on Cu Electrocatalysts".ACS CATALYSIS 14.5(2024).