Abstract Electrochemical CO 2 reduction to CH 4 is extensively investigated. As the most deeply reduced C1 product, CH 4 formation involves a kinetically sluggish eight‐electron transfer pathway, resulting in poor reaction selectivity. A carbon‐supported LaCu nanosphere catalyst with Cu vacancies (La 0.05 Cu v1 @C) is reported here for efficient CO 2 ‐to‐CH 4 conversion. Experimental results demonstrate that the La 0.05 Cu v1 @C material achieves a methane Faradaic efficiency (FE CH4 ) of 73.3% at −1.6 V versus reversible hydrogen electrode (RHE), outperforming the control samples. Atomically dispersed La induces electron transfer, forming an asymmetric adsorption site to enhance CO 2 adsorption and activation, while Cu vacancies optimize intermediate adsorption strength, suppressing C─C coupling and promoting hydrogenation pathways. La sites can also promote water dissociation to supply protons for subsequent methane formation. By synergizing defect engineering and heteroatom doping, this research establishes a new paradigm for developing selective copper‐based catalysts in methane activation systems.
Dai et al. (Thu,) studied this question.