Molecular Modulation of Sequestered Copper Sites for Efficient Electroreduction of Carbon Dioxide to Methane

Abstract The sustainable production of methane (CH₄) via the electrochemical conversion of carbon dioxide (CO₂) is an appealing approach to simultaneously mitigating carbon emissions and achieving energy storage in chemical bonds. Copper (Cu) is a unique material to produce hydrocarbons and oxygenates. However, selective methane generation on Cu remains a great challenge due to the preferential *CO dimerization pathway toward multi‐carbon (C₂₊) products at neighboring catalytic sites. Herein, a conjugated copper phthalocyanine polymer (CuPPc) is designed by a facile solid‐state method for highly selective CO₂‐to‐CH₄ conversion. The spatially isolated CuN₄ sites in CuPPc favor the *CO protonation to generate the key *CHO intermediate, thus significantly promoting the formation of CH₄. As a result, the CuPPc catalyst exhibits a high CH₄ Faradaic efficiency of 55% and a partial current density of 18 mA cm⁻² at −1.25 V versus the reversible hydrogen electrode. It also stably operates for 12 h. This study may offer a new solution to regulating the chemical environment of the active sites for the development of highly efficient copper‐based catalysts for electrochemical CO₂ reduction.