Selective Production of Methanol via Bidentate Coordination of an Intermediate on the Dual‐Atom Electro‐Catalyst

Abstract

Electrochemical CO2 reduction offers a route to produce liquid fuels such as methanol; however, strong competition from hydrogen evolution and limited control over key reaction intermediates lead to low single‐product selectivity and poor stability under operating conditions. Heteronuclear dual‐atom catalysts (DACs) have shown great promise in this regard because two neighboring catalyst atoms can cooperatively bind and polarize oxygenated intermediates. Despite these attractive features, DACs often struggle to stabilize the right early intermediate for methanol, so CO2 protonation defaults back to *COOH (and then *CO), which breaks methanol selectivity. Here, we utilize DAC systems stabilized on a carbon nitride (C3N4) framework to resolve this mechanistic bottleneck at the molecular level using density functional theory and constrained molecular dynamics simulations. A Sn–N2/Cu–N2 DAC embedded in a C3N4 framework, coupled to an explicit aqueous interface and evaluated under an applied potential, is shown to favor methanol formation through a six‐electron *OCHO pathway. The neighboring Sn and Cu sites synergistically stabilize a bidentate *OCHO intermediate through Sn─O p‐orbital interactions, while suppressing formation of *COOH. The results provide a clear design rule for methanol‐selective CO2RR: enforce cooperative bidentate binding that locks in *OCHO and redirects the first protonation step away from *COOH and toward methanol.