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

The electrochemical CO₂ 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/Cu₂P₂O₇-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 Cu₂P₂O₇ nanoparticles, which enhances selective methanol production via the HCOOH intermediate pathway. These findings provide insights into designing cost-effective electrocatalysts for selective methanol production.