Optimizing reaction paths for methanol synthesis from CO2 hydrogenation via metal-ligand cooperativity

As diversified reaction paths exist over practical catalysts towards CO 2 hydrogenation, it is highly desiderated to precisely control the reaction path for developing efficient catalysts. Herein, we report that the ensemble of Pt single atoms coordinated with oxygen atoms in MIL-101 (Pt 1 @MIL) induces distinct reaction path to improve selective hydrogenation of CO 2 into methanol. Pt 1 @MIL achieves the turnover frequency number of 117 h −1 in DMF under 32 bar at 150 °C, which is 5.6 times that of Pt n @MIL. Moreover, the selectivity for methanol is 90.3% over Pt 1 @MIL, much higher than that (13.3%) over Pt n @MIL with CO as the major product. According to mechanistic studies, CO 2 is hydrogenated into HCOO* as the intermediate for Pt 1 @MIL, whereas COOH* serves as the intermediate for Pt n @MIL. The unique reaction path over Pt 1 @MIL not only lowers the activation energy for the enhanced catalytic activity, but also contributes to the high selectivity for methanol. Controlling the reaction path is instrumental for developing efficient catalysts for CO 2 hydrogenation. Here, the authors report that the ensemble of Pt single atoms coordinated with oxygen atoms in MIL-101 induces distinct reaction path to improve selective hydrogenation of CO 2 into methanol relative to nanocrystal counterparts.