(646e) Computational Investigation into Supported and Inverted Cu-ZrO2 Catalysts for Selective Conversion of CO2 to Methanol

Greenhouse gases like CO₂, mainly produced from fossil fuel combustion, are one of the primary reasons for global warming and climate change. The carbon-neutral conversion of CO₂ to methanol, using renewable hydrogen, provides a sustainable and lucrative technology for combating CO₂ emissions. Metal/metal-oxide systems are among the popular catalysts to facilitate selective CO₂ conversion to methanol, owing to their tunability and diverse catalytic functionality¹. Among these, Cu nanoparticles supported on ZrO₂ are one of the widely studied catalysts, attributed to their high catalytic activity and versatile properties². More recently, the inverse structured ZrO₂/Cu catalysts have shown improved performance for CO₂ hydrogenation compared to supported ones³. However, the nature of active sites and the synergistic effect between the Cu and ZrO₂ components remains elusive.

In this work, we utilize Density Functional Theory (DFT) calculations to study atomistic models representing supported and inverted Cu-ZrO₂ systems. We elucidate electronic changes induced in the metal and oxide components for both systems. We compute the adsorption energies of reaction intermediates relevant to CO₂ hydrogenation at interfacial and proximal sites for both and interface them to CO₂ hydrogenation rates through descriptor-based microkinetic modelling. We observe higher predicted activity of the inverted catalysts over supported one, consistent with experimental results, which can be attributed to more favorable electronic interactions and charge transfer characteristics in the former system.

1. Kattel, S., Liu, P. & Chen, J. G. Tuning Selectivity of CO2 Hydrogenation Reactions at the Metal/Oxide Interface. JACS 139, 9739–9754.

2. Li, K. & Chen, J. G. CO2 Hydrogenation to Methanol over ZrO2-Containing Catalysts: Insights into ZrO2 Induced Synergy. ACS Catal 9, 7840–7861 (2019).

3. Wu, C. et al. Inverse ZrO2/Cu as a highly efficient methanol synthesis catalyst from CO2 hydrogenation. Nat Commun 11, (2020).