Exchange of CO2 with CO as Reactant Switches Selectivity in Photoreduction on Co−ZrO2 from C1–3 Paraffin to Small Olefins

Photocatalytic reduction of CO2 into C2,3 hydrocarbons completes a C‐neutral cycle. The reaction pathways of photocatalytic generation of C2,3 paraffin and C2H4 from CO2 are mostly unclear. Herein, a Co0−ZrO2 photocatalyst converted CO2 into C1–3 paraffin, while selectively converting CO into C2H4 and C3H6 (6.0±0.6 μmol h−1 gcat−1, 70 mol %) only under UV/Visible light. The photocatalytic cycle was conducted under 13CO and H2, with subsequent evacuation and flushing with CO. This iterative process led to an increase in the population of C2H4 and C3H6 up to 61–87 mol %, attributed to the accumulation of CH2 species at the interface between Co0 nanoparticles and the ZrO2 surface. CO2 adsorbed onto the O vacancies of the ZrO2 surface, with resulting COH species undergoing hydrogenation on the Co0 surface to yield C1–3 paraffin using either H2 or H2O (g, l) as the reductant. In contrast, CO adsorbed on the Co0 surface, converted to HCOH species, and then split into CH and OH species at the Co and O vacancy sites on ZrO2, respectively. This comprehensive study elucidates intricate photocatalytic pathways governing the transformation of CO2 into paraffin and CO to olefins. Pathways from CO2 to paraffin while from CO to C2H4 and C3H6 using Co−ZrO2 photocatalyst were switched. CO2 at the O vacancy on ZrO2 transformed into COH and hopped onto Co0 to be paraffin while CO and H competed on Co0 leading to preferable coupling of CH2 to olefins.