Pd-Based Multi-Site\nCatalysts for Selective CO<sub>2</sub>‑to-Methanol Conversion

Developing a multi-site Pd-based electrocatalyst for\nCO<sub>2</sub>-to-C1 conversion with high performance and selectivity\nin the hydrogenation\npathway for the CO<sub>2</sub> electroreduction reaction is both desirable\nand challenging. Here, we develop triple-site metallene (Pd<sub>82</sub>Bi<sub>11</sub>In<sub>7</sub>), which can achieve an unprecedented\nFaraday efficiency of 72.6 ± 1% for methanol production. X-ray\nphotoelectron spectroscopy analysis indicates that some electrons\ntransfer from In and Bi to Pd inside Pd<sub>82</sub>Bi<sub>11</sub>In<sub>7</sub>, forming local electron-rich Pd-site, local primary\nelectron-deficient center In-site, and local secondary electron-deficient\ncenter Bi-site. Meanwhile, Pd<sub>82</sub>Bi<sub>11</sub>In<sub>7</sub> has stronger adsorption for *COOH and *CO, which avoids the generation\nof formic acid and CO. Moreover, Pd<sub>82</sub>Bi<sub>11</sub>In<sub>7</sub> reduces the potential determining step energy barrier and\ncontrols the hydrogenation path for direct methanol production. The\nsynergistic effect of the triple-sites enables efficient CO<sub>2</sub> electroreduction to methanol.