Synergistic strategy of bimetallic-molecular interfaces enhances electrocatalytic CO₂ reduction to methanol

The design of highly selective catalysts for direct methanol production via CO₂ electrolysis remains challenging due to its complex pathways and intense hydrogen evolution competition. This study employed a “bimetallic-molecular” interface synergy strategy to construct Cu_xAg_1-x-SPy_z catalysts by in situ anchoring mercaptopyridine on the CuAg bimetallic surface. Experimental results indicate that the Cu_0.3Ag_0.7-Spy_0.05 catalyst in an H-cell exhibits a maximum Faradaic efficiency (FE) of 45.3% for methanol at −1.13 V (vs. RHE), while the FE for methanol in a flow cell reached 46.8% with a partial current density of 117 mA cm⁻², outperforming unmodified Cu-Ag and existing mainstream catalysts. In situ ATR-FTIR spectroscopy simultaneously captured *COOH, *CO, *CHO, *OCH₂, and *OCH₃ intermediates. Combined with DFT calculations, it was confirmed that Cu-Ag synergistically optimized *CO adsorption energy, while the modified pyridine acted as a proton relay, lowering the *CO → *CHO energy barrier by 0.27 eV to achieve directional regulation of the methanol pathway. This study establishes a scalable molecular interface engineering paradigm for highly selective CO₂ methanolation and expands novel approaches to “metal-ligand” synergistic design in complex multi-electron reactions.