Photo-Induced Switching of CO₂ Hydrogenation Pathway towards CH₃ OH Production over Pt@UiO-66-NH₂ (Co)

It is highly desired to achieve controllable product selectivity in CO₂ hydrogenation. Herein, we report light-induced switching of reaction pathways of CO₂ hydrogenation towards CH₃ OH production over actomically dispersed Co decorated Pt@UiO-66-NH₂ . CO, being the main product in the reverse water gas shift (RWGS) pathway under thermocatalysis condition, is switched to CH₃ OH via the formate pathway with the assistance of light irradiation. Impressively, the space-time yield of CH₃ 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-NH₂ can transfer electrons to Pt nanoparticles and Co sites, which can efficiently catalyze the critical elementary steps (i.e., CO₂ -to-*HCOO conversion), thus suppressing the RWGS pathway to achieve a high CH₃ OH selectivity.