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

“Bimetallic-molecular” interface strategy constructs CuxAg1-x-SPyz catalysts for efficient CO 2 -to-methanol. • Cu 0.3 Ag 0.7 -Spy 0.05 achieves 46.8% methanol FE and 117 mA cm −2 partial current in a flow cell. • DFT calculations confirm Cu-Ag optimizes *CO adsorption, while pyridine modification lowers the *CO → *CHO barrier by 0.27 eV. The design of highly selective catalysts for direct methanol production via CO 2 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 x Ag 1-x -SPy z catalysts by in situ anchoring mercaptopyridine on the CuAg bimetallic surface. Experimental results indicate that the Cu 0.3 Ag 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, *OCH 2 , and *OCH 3 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 CO 2 methanolation and expands novel approaches to “metal-ligand” synergistic design in complex multi-electron reactions. Anchored by metal‑sulfur bonds, a mercaptopyridine modified copper‑silver bimetallic composite material Cu 0.3 Ag 0.7 -SPy 0.05 is prepared. The synergistic interaction between silver and copper bimetallic sites enhances the generation and adsorption of *CO, while the pyridine groups accelerate the effective protonation of *CO to methanol. It delivers a Faradaic efficiency of 46.8% with a partial current density of 117 mA cm −2 for methanol. Download: Download high-res image (179KB) Download: Download full-size image