Single-site decorated copper enables energy- and carbon-efficient CO₂ methanation in acidic conditions

Renewable CH₄ produced from electrocatalytic CO₂ reduction is viewed as a sustainable and versatile energy carrier, compatible with existing infrastructure. However, conventional alkaline and neutral CO₂-to-CH₄ systems suffer CO₂ loss to carbonates, and recovering the lost CO₂ requires input energy exceeding the heating value of the produced CH₄. Here we pursue CH₄-selective electrocatalysis in acidic conditions via a coordination method, stabilizing free Cu ions by bonding Cu with multidentate donor sites. We find that hexadentate donor sites in ethylenediaminetetraacetic acid enable the chelation of Cu ions, regulating Cu cluster size and forming Cu-N/O single sites that achieve high CH₄ selectivity in acidic conditions. We report a CH₄ Faradaic efficiency of 71% (at 100 mA cm⁻²) with <3% loss in total input CO₂ that results in an overall energy intensity (254 GJ/tonne CH₄), half that of existing electroproduction routes.