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

The electrochemical reduction of carbon dioxide (CO2) to methane (CH4) presents a promising solution for mitigating CO2 emissions while producing valuable chemical feedstocks. Although single-atom catalysts have shown potential in selectively converting CO2 to CH4, 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 (Co1Cu) that achieved a CH4 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 H2O 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 CH4 over the C-C coupling or CO desorption pathways. Our findings underscore the potential of Co1Cu catalysts in overcoming the selectivity-activity trade-off, paving the way for efficient and scalable CO2-to-CH4 conversion technologies.