Triggering photocatalytic performance of La 2 Co x Mn 2-x O 6 via heat activation.
Cheng ChenMingge WuBolei ChenChunyan MaMaoyong SongGuibin JiangPublished in: Proceedings of the National Academy of Sciences of the United States of America (2023)
The La-based perovskite (LaBO 3 ) exhibits excellent optical properties. However, its valence band (VB) potential is not sufficiently positive to reach the oxidation potential required for the cleavage of chemical bonds (such as benzylic C-H), limiting its application in photocatalysis. Herein, we report the unconventional effects of heat activation on the reduction of the dissociation energy of benzylic C-H and aqueous H-O, thereby triggering the photocatalytic activity of La 2 Co x Mn 2-x O 6 perovskites. Additionally, we demonstrate that photocatalysis is the main contributor to substrate conversion in the selective oxidation of toluene and reduction of CO 2 . Particularly, La 2 Co 1.5 Mn 0.5 O 6 shows excellent performance with a product yield of 550.00 mmol g cat -1 and a toluene conversion of 22,866.67 μmol g cat -1 h -1 . To the best of our knowledge, this is the highest reported product yield for the selective oxidation of benzylic C-H bond of toluene. Our findings provide insight into the specific role of heat activation in photocatalysis, which is crucial for breaking and overcoming the VB barrier to realize challenging reactions.