H-assisted CO2 dissociation on PdnPt(4−n)/In2O3 catalysts: a density functional theory study

CO2 hydrogenation into valuable chemical compounds can effectively address the issues of greenhouse gas emissions and energy scarcity. The activation and dissociation processes of CO2 are crucial for its reduction reactions, but the effects of *H adatoms on the C-O cleavage are still confusing. This study investigates the H-assisted CO2 dissociation pathways on the PdnPt(4−n)/In2O3 (n = 0-4) catalysts via DFT calculation. Initially, the adsorption properties of *H2, *COOH, and *HCOO species are calculated. Then, two H-assisted CO2 dissociation channels, i.e., *CO2 + *H → *COOH → *CO + *OH and *CO2 + *H → *HCOO → *CHO + *O, are studied. Results show that Pt and Pd promote the CO2 hydrogenation and C-O bond cleavage reactions, respectively. In comparison to CO2 direct dissociation, the COOH-mediated and HCOO-mediated channels facilitate and impede the C-O bond cleavage, respectively. Overall, the Pd3Pt/In2O3 constituent is suggested for the H-assisted CO2 dissociation reaction. The electronic effects of the PdnPt(4−n) bimetals adjust the stabilities of the intermediates and barriers of the elementary steps, and the interactions between PdnPt(4−n) and In2O3 provide extra sites for the adsorbates and reaction steps. This study reveals the effects of *H on the C-O bond dissociation processes and provides useful insight into designing PdPt/In2O3 catalysts for CO2 hydrogenation reactions.