Photo‐Induced Switching of CO₂ Hydrogenation Pathway towards CH₃OH Production over Pt@UiO‐66‐NH₂(Co)

It is highly desired to achieve controllable product selectivity in CO 2 hydrogenation. Herein, we report light‐induced switching of reaction pathways of CO 2 hydrogenation towards CH 3 OH production over actomically dispersed Co decorated Pt@UiO‐66‐NH 2 . CO, being the main product in the reverse water gas shift (RWGS) pathway under thermocatalysis condition, is switched to CH 3 OH via the formate pathway with the assistance of light irradiation. Impressively, the space‐time yield of CH 3 OH in photo‐assisted thermocatalysis (1916.3 μmol g cat −1 h −1 ) is about 7.8 times higher than that without light at 240 °C and 1.5 MPa. Mechanism investigation indicates that upon light irradiation, excited UiO‐66‐NH 2 can transfer electrons to Pt nanoparticles and Co sites, which can efficiently catalyze the critical elementary steps (i.e., CO 2 ‐to‐*HCOO conversion), thus suppressing the RWGS pathway to achieve a high CH 3 OH selectivity.