Reactivity Switch of Platinum with Gallium: From Reverse Water Gas Shift to Methanol Synthesis.

The development of efficient catalysts for the hydrogenation of CO 2 to methanol using "green" H 2 is foreseen to be a key step to close the carbon cycle. In this study, we show that small and narrowly distributed alloyed PtGa nanoparticles supported on silica, prepared via a surface organometallic chemistry (SOMC) approach, display notable activity for the hydrogenation of CO 2 to methanol, reaching a 7.2 mol CH3OH h -1 mol Pt -1 methanol formation rate with a 54% intrinsic CH 3 OH selectivity. This reactivity sharply contrasts with what is expected for Pt, which favors the reverse water gas shift reaction, albeit with poor activity (2.6 mol CO2 h -1 mol Pt -1 ). In situ XAS studies indicate that ca. 50% of Ga is reduced to Ga 0 yielding alloyed PtGa nanoparticles, while the remaining 50% persist as isolated Ga III sites. The PtGa catalyst slightly dealloys under CO 2 hydrogenation conditions and displays redox dynamics with PtGa-GaO x interfaces responsible for promoting both the CO 2 hydrogenation activity and methanol selectivity. Further tailoring the catalyst interface by using a carbon support in place of silica enables to improve the methanol formation rate by a factor of ∼5.