Hydrogen Spillover and Interfacial Oxygen Vacancy Pairing in Cu–ZrOx Catalysts for Selective CO₂ Conversion to Methanol

Cu–ZrOx catalysts have attracted increasing attention for CO2 hydrogenation to methanol because the oxide–metal perimeter can simultaneously activate CO2-derived intermediates and dissociate hydrogen. In this work, density functional theory calculations combined with microkinetic modeling were used to clarify how hydrogen spillover and oxygen-vacancy pairing regulate methanol formation at Cu–ZrOx interfacial sites. A total of 72 Cu–ZrOx interface models were constructed by varying ZrOx nuclearity, oxygen-vacancy density, and Cu coordination environment, and 186 elementary reaction barriers were calculated for formate, dioxymethylene, methoxy, and reverse water–gas shift pathways. The results show that isolated Zrδ+ centers stabilize HCOO* by 0.34–0.51 eV relative to Cu-only sites, whereas paired oxygen vacancies reduce the HCOO* → H2COO* hydrogenation barrier from 1.12 eV to 0.76 eV. Microkinetic simulations at 523 K and 30 bar indicate that interfaces with moderate vacancy concentration achieve a methanol selectivity of 82.6%, compared with 41.8% on vacancy-poor surfaces. Degree-of-rate-control analysis identifies HCOO* hydrogenation and CH3O* protonation as the two most influential steps, contributing 46% and 31% to the overall rate sensitivity, respectively. Electronic-structure analysis further reveals that hydrogen spillover from Cu to adjacent ZrOx sites increases the Bader charge of interfacial hydrogen by 0.18–0.24 e, strengthening its reactivity toward oxygenated C1 intermediates. These findings provide an atomistic explanation for the activity of inverse Cu–ZrOx catalysts and suggest that controlling vacancy pairing, rather than simply increasing oxide loading, is critical for improving methanol productivity.

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