Structure-activity relationship of Cu-based catalysts for the highly efficient CO₂ electrochemical reduction reaction.

ABSTRACT: Electrocatalytic carbon dioxide reduction (CO₂RR) is a relatively feasible method to reduce the atmospheric concentration of CO₂. Although a series of metal-based catalysts have gained interest for CO₂RR, understanding the structure-activity relationship for Cu-based catalysts remains a great challenge. Herein, three Cu-based catalysts with different sizes and compositions (Cu@CNTs, Cu₄@CNTs, and CuNi₃@CNTs) were designed to explore this relationship by density functional theory (DFT). The calculation results show a higher degree of CO₂ molecule activation on CuNi₃@CNTs compared to that on Cu@CNTs and Cu₄@CNTs. The methane (CH₄) molecule is produced on both Cu@CNTs and CuNi₃@CNTs, while carbon monoxide (CO) is synthesized on Cu₄@CNTs. The Cu@CNTs showed higher activity for CH₄ production with a low overpotential value of 0.36 V compared to CuNi₃@CNTs (0.60 V), with *CHO formation considered the potential-determining step (PDS). The overpotential value was only 0.02 V for *CO formation on the Cu₄@CNTs, and *COOH formation was the PDS. The limiting potential difference analysis with the hydrogen evolution reaction (HER) indicated that the Cu@CNTs exhibited the highest selectivity of CH₄ among the three catalysts. Therefore, the sizes and compositions of Cu-based catalysts greatly influence CO₂RR activity and selectivity. This study provides an innovative insight into the theoretical explanation of the origin of the size and composition effects to inform the design of highly efficient electrocatalysts.

SUBMITTER: An R 

PROVIDER: S-EPMC9947715 | biostudies-literature | 2023

REPOSITORIES: biostudies-literature