Copper‐Catalysed Electrochemical CO2 Methanation via the Alloying of Single Cobalt Atoms

Abstract The electrochemical reduction of carbon dioxide (CO 2 ) to methane (CH 4 ) presents a promising solution for mitigating CO 2 emissions while producing valuable chemical feedstocks. Although single‐atom catalysts have shown potential in selectively converting CO 2 to CH 4 , their limited active sites often hinder the realization of high current densities, posing a selectivity‐activity dilemma. In this study, we developed a single‐atom cobalt (Co) doped copper catalyst (Co 1 Cu) that achieved a CH 4 Faradaic efficiency exceeding 60 % with a partial current density of −482.7 mA cm −2 . Mechanistic investigations revealed that the incorporation of single Co atoms enhances the activation and dissociation of H 2 O molecules, thereby lowering the energy barrier for the hydrogenation of *CO intermediates. In situ spectroscopic experiments and density functional theory simulations further demonstrated that the modulation of the *CO adsorption configuration, with stronger bridge‐binding, favours deep reduction to CH 4 over the C−C coupling or CO desorption pathways. Our findings underscore the potential of Co 1 Cu catalysts in overcoming the selectivity‐activity trade‐off, paving the way for efficient and scalable CO 2 ‐to‐CH 4 conversion technologies.