Decoupling CO2 reduction and hydrogen evolution reactions on CuZn alloys by constructing asymmetric active microenvironments

Abstract

CuZn binary alloys have emerged as promising electrocatalysts, yet the precise regulatory mechanisms governing their catalytic performance remain elusive. In this study, we constructed CuZnX model catalysts featuring symmetry-breaking active centers by introducing heteroatoms (X = Si, P, S and Cl) at the step edges of CuZn. Theoretical calculations reveal that heteroatom X modulates the adsorption strength of the key *H intermediate through synergistic geometric effects (selective occupation of high-activity sites) and electronic effects (reconstruction of charge distribution on edge Cu atoms), thereby decoupling and optimizing the catalytic activities toward the carbon dioxide reduction reaction (CO₂RR) and the hydrogen evolution reaction (HER). This work provides new design principles for the rational design of high-performance alloy catalysts through local microenvironment engineering.