Highly efficient cooperative CO2 electroreduction to CH4 on a copper cluster/C60 hetero-structured catalyst

Abstract

Electrochemical CO₂ reduction to CH₄ using H₂O as the reaction medium represents a green and sustainable approach for CO₂ conversion and utilization. Copper-based catalysts have emerged as promising candidates for CO₂ deep-reduction, but they still suffer from limited activity and selectivity in CO₂-to-CH₄ conversion. Herein, we report a copper cluster/C₆₀ hetero-structured catalyst that realizes highly efficient cooperative CO₂ electroreduction to CH₄. The catalyst achieves a remarkable CH₄ faradaic efficiency of 68% and a CH₄ partial current density of 255 mA cm⁻² in a gas-diffusion flow cell with an alkaline electrolyte. In situ spectroscopic experiments and theoretical calculation results unveil that the copper cluster modified with 1,10-phenanthroline facilitates CO₂ activation, while the incorporation of C₆₀ promotes H₂O dissociation, supplying sufficient activated hydrogen for the hydrogenation process. The synergy between the copper cluster and C₆₀ in the hetero-structured catalyst cooperatively promotes the formation of the key *CHO intermediate, thereby facilitating CO₂-to-CH₄ conversion. Our findings highlight the effectiveness of engineering hetero-structured catalysts for CO₂ deep-reduction into hydrocarbons.