Potential-modulated orbital interactions determine domino CO/methanol selectivity for CO₂ electroreduction on cobalt phthalocyanine.

ABSTRACT: Heterogenized cobalt phthalocyanine (hetero-CoPc) molecular catalysts exhibit domino CO/methanol selectivity during CO₂ electroreduction. However, the origin of this selectivity is not well understood, impeding the strategic optimization for methanol generation. Here, we show potential-modulated orbital interaction mechanisms governing the selectivity in hetero-CoPc based on first-principles calculations with consideration of carbon support and electrochemical interfaces. Specifically, constant-potential orbital-resolved analyses reveal that electrons introduced by applied potentials initially occupy the semi-occupied Co-3d_z² orbital, thus suppressing CO-5σ → Co-3d_z² electron donation. This induces gradual weakeni

SUBMITTER: Zhang J 

PROVIDER: S-EPMC12652289 | biostudies-literature | 2025 Nov

REPOSITORIES: biostudies-literature