Achieving High Selectivity in Photocatalytic Oxidation of Toluene on Amorphous BiOCl Nanosheets Coupled with TiO 2 .

The inert C( sp 3 )-H bond and easy overoxidation of toluene make the selective oxidation of toluene to benzaldehyde a great challenge. Herein, we present that a photocatalyst, constructed with a small amount (1 mol %) of amorphous BiOCl nanosheets assembled on TiO 2 (denoted as 0.01BOC/TiO 2 ), shows excellent performance in toluene oxidation to benzaldehyde, with 85% selectivity at 10% conversion, and the benzaldehyde formation rate is up to 1.7 mmol g -1 h -1 , which is 5.6 and 3.7 times that of bare TiO 2 and BOC, respectively. In addition to the charge separation function of the BOC/TiO 2 heterojunction, we found that the amorphous structure of BOC endows its abundant surface oxygen vacancies (Ov), which can further promote the charge separation. Most importantly, the surface Ov of amorphous BOC can efficiently adsorb and activate O 2 , and amorphous BOC makes the product, benzaldehyde, easily desorb from the catalyst surface, which alleviates the further oxidation of benzaldehyde, and results in the high selectivity. This work highlights the importance of the microstructure based on heterojunctions, which is conducive to the rational design of photocatalysts with high performance in organic synthesis.