Methanol Dehydrogenation via Rutile TiO 2 -Based Single-Atom Catalysts: Structure, Stability, and Selectivity

Single-atom catalysts possessing distinct geometric and electronic structures have permitted the highly efficient performance and tunable catalytic property for methanol dehydrogenation. The structure and stability of rutile TiO 2 -based single-atom catalyst, and the selectivity for methanol dehydrogenation were addressed via DFT + U calculations. The stable single-atom catalysts: rutile Co 1 @TiO 2 and Ru 1 /TiO 2 , have been identified from all the possible terminations. Their interface structures, stabilities in thermodynamics, and selectivity for methanol dehydrogenation are determined by the two important parameters: metal-atom doping site and surficial oxygen stoichiometry. In particular, the substitutional rutile Co 1 @TiO 2 (110) facet can boost direct methanol dehydrogenation, activate O–H and C–H bonds, and then release formaldehyde, H 2 , and CO. The rutile Ru 1 /TiO _2 + x (110) one, a supported neutral Ru atom with additional oxygen on the stoichiometric rutile TiO 2 (110) facet, prefers to facilitate partial oxidation of methanol.