Formate-Dominated Reaction Networks on ZrO2-Modified Cu Surfaces

Abstract

Reaction pathway selection critically determines product distribution in CO2 hydrogenation. In this study, a comprehensive reaction network consisting of 41 elementary steps was constructed using density functional theory to compare formate- and CO-mediated pathways on ZrO2-decorated Cu surfaces. Energetic span analysis shows that ZrO2 modification reduces the energetic span of the formate route from 1.05 eV on Cu to 0.69 eV at the interface, while simultaneously increasing the barrier for CO formation. Microkinetic simulations predict methanol selectivities exceeding 75% across a temperature range of 500–540 K, in contrast to CO-dominated behavior on Cu. The analysis identifies hydrogenation of bidentate formate as the primary rate-determining step under industrially relevant pressures. These results clarify how inverse catalysts fundamentally reshape the reaction network to favor methanol formation.