Selective Electrosynthesis of Methanol from CO2 Over Cu/Cu2P2O7 Via the Formate Pathway

Abstract The electrochemical CO 2 reduction reaction (CO2RR) to methanol offers an eco‐friendly approach to reducing carbon emissions while producing versatile liquid fuels and feedstocks. However, achieving high selectivity for methanol, especially at high current densities, remains challenging due to competing reactions that favor methane and hydrogen formation. Here, the tailored synthesis of Cu/Cu 2 P 2 O 7 ‐based hybrid catalysts is reported for efficient and selective methanol production through the discharge of lithium‐ion batteries. The catalyst exhibits a Faradaic efficiency exceeding 50% in both H‐cells and gas‐diffusion electrode cells, achieving one of the highest reported methanol partial current densities of over 100 mA cm −2 . Experimental and computational analyses reveal a synergistic effect between Cu nanoparticles with a predominant (111) surface and Cu 2 P 2 O 7 nanoparticles, which enhances selective methanol production via the HCOOH intermediate pathway. These findings provide insights into designing cost‐effective electrocatalysts for selective methanol production.