Dipole-field interaction: a missing link to bridge the gap between theoretical and experimental catalysis in single-atom electrocatalysts for CO2 reduction

Abstract

The CO₂-to-CO reduction behaviour on Fe/Co/Ni-based single-atom catalysts was systematically investigated. *CO is preferentially stabilized relative to *COOH under increasingly negative interfacial electric fields. A pH-dependent volcano relationship is revealed, exhibiting a rightward shift with increasing pH due to the distinct dipole moments of *CO and *COOH. Benchmarking against experimental data validates the microkinetic volcano model and identifies promising catalyst candidates. Importantly, dipole–field interactions emerge as a general descriptor, bridging theoretical predictions and experimental observations in CO₂RR and beyond.