Manipulating Cu Surface Carbophobicity with Pb for Efficient CO‐to‐Ethanol Electroconversion

ABSTRACT Electrochemical CO reduction to ethanol offers a sustainable route for carbon utilization, but the uncontrollable hydrogenation pathway in post C─C coupling limits its selectivity. Herein, we introduced Pb doping to modulate the carbophobicity of Cu catalyst, thereby directing hydrogenation toward the β‐C of the key * CH 2 CHO intermediate and boosting ethanol production. Density functional theory calculations revealed that Pb incorporation reduced electron transfer from Cu to * CH 2 CHO, weakening the Cu─C bond and favoring the β‐C hydrogenation over the ethylene pathway. In situ X‐ray absorption spectroscopy confirmed that Pb doping lowered the electron density at Cu sites, resulting in weakened CO adsorption, consistent with a carbophobic catalyst surface. In situ attenuated total reflectance Fourier transform infrared spectroscopy further revealed suppressed CO coverage and enhanced accumulation of ethanol‐pathway intermediates ( * OC 2 H 5 ) on the Pb‐doped Cu. As a result, the optimized PbCu catalyst achieved an ethanol Faradaic efficiency of 55.2% with a partial current density of ∼500 mA cm −2 , outperforming most reported CO reduction catalysts. This work highlights carbophobicity engineering as a powerful strategy to fine‐tune intermediate binding and selectively drive ethanol production in CO/CO 2 electroreduction.