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

Graphical Cu 7 S 4 /Cu nanoflowers with strong CO 2 adsorption and abundant boundaries were developed by a facile thermal reduction, which underwent in situ dynamic restructuring during ECR to generate highly active S-doped Cu 2 O/Cu hybrid catalyst. Thermodynamic and experimental analysis revealed that the optimized adsorption of the HCOO * intermediate on S−Cu 2 O/Cu was regulated and surface H was suppressed by S-doping. The high activity for CO 2 -to-HCOOH attributed to the strengthen CO 2 adsorption, abundant boundaries at Cu 2 O/Cu interfaces, and the regulation of adsorption energy by S-doping 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.