Coupling *CO Protonation on Cu Single Atoms With H 2 O Dissociation on Bi Nanoclusters for Synergistic CO 2 ‐to‐Methanol Electrosynthesis

ABSTRACT The electrochemical reduction of CO 2 to methanol (CH 3 OH) represents a promising strategy for mitigating global warming and energy shortages. However, the rational design of high‐performance electrocatalysts for selective CO 2 ‐to‐CH 3 OH conversion remains challenging. Herein, we construct a dual‐site catalyst featuring Cu single atoms (Cu SAs ) and Bi nanoclusters (Bi NCs ) co‐anchored on a hierarchical porous nitrogen‐doped carbon (NC) support (Cu SAs Bi NCs /NC). It delivers a high CH 3 OH Faradaic efficiency (FE) of 73.6% with a stability of 120 h in an H‐cell, and reaches a CH 3 OH partial current density of 106.6 mA cm −2 with 82% FE in a flow cell. The excellent performance is attributed to a synergistic mechanism: Cu SAs promote the generation and protonation of the key *CO intermediate, while Bi NCs facilitate H 2 O dissociation to supply *H to adjacent Cu sites. Their electronic interaction strengthens *CO adsorption and lowers its protonation barrier at Cu sites, while accelerating H 2 O activation at Bi sites. Furthermore, the confinement effect of the hierarchical pore structure in the NC support facilitates the enrichment of *CO intermediate and stabilizes the catalyst. This work establishes a conceptual framework for developing synergistic electrocatalysts through precise atomic‐scale component integration, offering an appealing strategy to boost CH 3 OH production by simultaneously tuning *CO adsorption/protonation and H 2 O dissociation.