Dynamic Restructuring of Cu₇S₄/Cu for Efficient CO₂ Electro‐reduction to Formate

Optimized catalytic properties and reactant adsorption energy played a crucial role in promoting CO 2 electrocatalysis. Herein, Cu 7 S 4 /Cu underwent in situ dynamic restructuring to generate S−Cu 2 O/Cu hybrid catalyst for effective electrochemical CO 2 reduction to formate that outperformed Cu 2 O/Cu and Cu 7 S 4 . Thermodynamic and in situ Raman spectra revealed that the optimized adsorption of the HCOO* intermediate on S−Cu 2 O/Cu was regulated and the H 2 pathway (surface H) was suppressed by S‐doping. Meanwhile, Cu 7 S 4 /Cu nanoflowers created abundant boundaries for ECR and strengthened the CO 2 adsorption by inducing Cu. These findings provide a new perspective on synthetic methods for various electrocatalytic reduction processes.