Construction of Cu-OV-Ce and Cu nanoparticle dual synergetic active sites for robust electrochemical CO2 reduction to CH4

Abstract

Cu single atom and Cu/CeO₂ interface have shown excellent electrochemical reduction of CO₂ performance, while the synergetic effect between the two active sites has not yet been clearly explained. Herein, one Cu-CeO₂-based electrocatalyst supported on carbon carrier (Cu-CeO₂@C) was synthesized. The in-situ generated carbon carrier enables the fabrication of integrated Cu-O_V-Ce linkage and Cu/CeO₂ interfacial dual-active centers. The neighboring Cu nanoparticle facilitated electron delocalization at Cu-O_V-Ce linkage sites and modulated their Fermi level, thereby efficiently enhancing its CO₂ adsorption and activation capacities. These effects enabled Cu-CeO₂@C to achieve a high CH₄ Faraday efficiency of 78.1%, a superior turnover frequency of 1.03 s⁻¹, and a substantial methane cathodic energy efficiency of 36.3%, outperforming most currently reported Cu-based catalysts. This work not only provides a new insight into the synergetic effect of Cu-O_V-Ce linkage and Cu nanoparticle on e-CO₂RR, but also sheds light on the rational design of efficient Cu-CeO₂-based electrocatalyst.