Mo2Ti2C3TX MXene performance in catalytic CO2 hydrogenation and its promotion with single Pt atoms

Mo2Ti2C3Tx MXene materials, bare or loaded with strongly anchored single Pt atoms, were investigated using various methods, including STEM, XPS, XAS and DFT calculations. Upon Pt impregnation, the delaminated Mo-rich MXene surface undergoes partial oxidation, which is reversed by an H2 thermal treatment at 400 °C. The optimized MXene shows high catalytic activity for CO2 hydrogenation to CO and smaller amounts of methane and methanol. Around and above the pretreatment temperature of 400 °C, the MXene is gradually defunctionalized from O- and F-containing groups and depleted in carbidic carbon, leading to deactivation. Single Pt atoms are cationic after impregnation, and reduce upon H2 treatment, filling surface Mo vacancies. Pt addition increases the MXene activity, in particular by facilitating H2 dissociation, but has little effect on the single-atom catalyst selectivity and on the rate dependence upon reactant partial pressures. The lowest Pt loading leads to the highest turnover frequency, indicating that the MXene surface sites are key to CO2 activation. [Display omitted] •In-depth investigation of (Pt1-)Mo2Ti2C3Tx MXene structure and composition.•Influence of reductive treatments on MXene stoichiometry and Pt oxidation state.•Upon H2 treatment at 400 °C, single Pt atoms mostly substitute surface Mo atoms.•Mo2Ti2C3Tx is intrinsically active for the reverse water-gas shift reaction.•Pt addition increases the CO2 hydrogenation activity of the MXene.