Compressive Strain-Mediated Bond Length Tailoring in CuO Reveals the Bridge to Efficient Electrocatalytic CO2-to-Ethylene

Abstract

Modulation of the electronic microenvironment of copper (Cu) sites during electrochemical carbon dioxide reduction (ECR) is essential for controlling the strength of intermediate adsorption and improving electron transfer. However, precisely regulating the electronic microenvironment around the Cu through adjusting of Cu-O bond length remains a significant challenge. Here, we report a strategy to that achieves fine-tuned control over the electronic microenvironment around the active center through lattice compression. Experimental results show that the introduction of Cd alters the Cu-O bond length and the electronic microenvironment around Cu and significantly enhanced the adsorption of *CO and *COOH intermediates. Density functional theory calculations reveal that the optimal degree of lattice compression modulates the binding energy of *COOH intermediates, and enhances the d-band center, improving CO2 adsorption. Furthermore, we verified that the structure-activity relationship between bond length change and catalytic activity is consistent with a volcanic type. Remarkably, the O-CuCd-4 catalysts exhibited impressive CO2-to-C2H4 conversion performance (FEC2H4 ≈ 60% and EEC2H4 ≈ 30%) with a good stability that matches or exceeds most reported Cu-based oxides. This study provides a rational pathway for designing catalysts with precisely modifiable electronic microenvironments, resulting in enhanced CO2 conversion activity and long-term stability.