Pd-Based Multi-Site Catalysts for Selective CO2-to-Methanol Conversion.

Developing a multi-site Pd-based electrocatalyst for CO2-to-C1 conversion with high performance and selectivity in the hydrogenation pathway for the CO2 electroreduction reaction is both desirable and challenging. Here, we develop triple-site metallene (Pd82Bi11In7), which can achieve an unprecedented Faraday efficiency of 72.6 ± 1% for methanol production. X-ray photoelectron spectroscopy analysis indicates that some electrons transfer from In and Bi to Pd inside Pd82Bi11In7, forming local electron-rich Pd-site, local primary electron-deficient center In-site, and local secondary electron-deficient center Bi-site. Meanwhile, Pd82Bi11In7 has stronger adsorption for *COOH and *CO, which avoids the generation of formic acid and CO. Moreover, Pd82Bi11In7 reduces the potential determining step energy barrier and controls the hydrogenation path for direct methanol production. The synergistic effect of the triple-sites enables efficient CO2 electroreduction to methanol.