Comparative study of methanol adsorption and decomposition on Pt and Ni decorated TiO2(110) surfaces using first principles

[Display omitted] •Methanol adsorption and decomposition on Pt10/TiO2(110) and Ni10/TiO2(110) surfaces were examined using DFT calculations.•The Pt10/TiO2(110) and Ni10/TiO2(110) surfaces exhibit varying catalytic activities in the adsorption and decomposition of CH3OH.•On both Pt10/TiO2(110) and Ni10/TiO2(110) surfaces, the most favorable hydrogen production pathway is located at the interface.•The unique adsorption of CH3O*, interface charge transfer, and metal cluster fluxionality are key in CH3OH decomposition. Methanol adsorption and decomposition on Pt- and Ni-decorated TiO2(110) surfaces were examined using density functional theory (DFT) calculations. Furthermore, the impact of oxygen vacancies was studied. Results indicated that the Pt10/TiO2(110) and Ni10/TiO2(110) surfaces possessed distinct active centers and exhibited varying catalytic activities for the adsorption and decomposition of CH3OH. Additionally, at the interfacial site, the energy barrier for CH3OH decomposition on the Pt10/TiO2(110) surface was lower than that on the Ni10/TiO2(110) surface, indicating that the catalytic activity of Pt10/TiO2(110) was higher than that of Ni10/TiO2(110). An analysis revealed that the unique adsorption structure of CH3O* and charge transfer at the interfacial site, along with the fluxionality of metal clusters, played decisive roles in the decomposition of CH3OH. This work not only contributes to the development of efficient CH3OH photocatalysts but is also crucial for understanding the basic mechanism of supported catalysts for CH3OH decomposition.