Abstract

AbstractEnergy cost is a long‐neglected but crucial issue for electrocatalytic carbon dioxide reduction reactions (CO2RRs). So far, achieving efficient CO2RR at a low energy cost is a major unresolved challenge. Herein, energy‐efficient CO2‐to‐CH3OH conversion by synergistically increasing the amount of favorable intermediates and depressing H2 generation is reported. The designed precursor electrocatalyst undergoes in situ reduction, forming Cu−C60 and ZnO−Cu dual interfaces. Cu−C60 induces an *H‐rich surface, decreasing the hydrogenation barrier and lowering the required voltage. *H‐modified ZnO‐Cu alters the mechanism of electron transfer and improves the conversion selectivity. As a result, at an applied potential as low as −0.63 V versus a reversible hydrogen electrode, a cathodic energy efficiency of 50.5% and a faradaic efficiency of 78.3% for CH3OH is obtained. This work unlocks an unconventional route for improving the catalytic performance and energy efficiency of electrocatalysts, addressing the concern of energy costs for electrocatalyzed CO2RR.

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