Why Is Methanol Formation Suppressed in CO 2 Reduction Over Copper Electrocatalysts?

ABSTRACT Electrocatalytic CO 2 reduction (CO 2 RR) to produce methanol (CH 3 OH) provides a sustainable alternative to its energy‐intensive industrial synthesis. However, C 2+ species and CH 4 are typically the dominant products on prototypical Cu catalysts, with no CH 3 OH formation. Herein, employing constant‐potential explicit solvent methods, we systematically compared the thermodynamics and kinetics of C 2+ products (covering 21 possible C–C coupling paths), CH 4 , and CH 3 OH formation to uncover the origin of intrinsic suppression of CH 3 OH. Nine C–C coupling pathways exhibit significantly lower barriers than C 1 products, underscoring the facile formation of C 2+ products via multiple accessible routes beyond conventional CO–CO coupling. For C 1 products, the selectivity‐determining intermediate *CH 2 OH favors C–O bond cleavage toward CH 4 rather than hydrogenation to CH 3 OH, placing CH 3 OH formation at a kinetic disadvantage. This mechanism remains valid irrespective of Cu surface structures or applied potentials, and simulated Faradaic efficiencies (FE) align well with experimental trends, further validating our theoretical insight. Building on this, we propose a strategy that involves redirecting the pathway from *COOH to *HCOO and selectively stabilizing *CH 2 OH to steer its hydrogenation toward CH 3 OH. These findings establish a foundation for selective CH 3 OH production and highlight its synthesis as a key direction in electrocatalytic CO 2 conversion.