Theoretical Insights into the Activation and Conversion of Electrochemical CO2 Reduction on 3d Transition Metal-Doped Cu(111) Stepped Structures

Abstract

The activation of CO₂ is essential for efficient electrochemical conversion, yet its weak physisorption on pristine Cu surfaces severely hinders catalytic performance. To overcome this limitation, we designed Cu stepped structures to create highly reactive sites for enhanced CO₂ adsorption and further doped the edges with 3d transition metals (V, Cr, Mn, Fe, Co, and Ni) to improve CO₂ reduction. Density functional theory calculations reveal that these dopants significantly reduce the OCO angles and elongate the CO bonds, transforming CO₂ from its original linear configuration into a bent geometry at the interface. Notably, dual-V and dual-Fe doping on Cu stepped surfaces demonstrates a strong interaction with CO₂, leading to a high degree of activation. The computational results demonstrate that these modifications significantly enhance CO₂ activation and favor methane generation. This study provides valuable insights into the design of advanced Cu-based electrocatalysts for efficient and selective CO₂ activation, offering a pathway toward sustainable CO₂ utilization.