New insight into the selective photocatalytic oxidation of RhB through a strategy of modulating radical generation.

Rhodamine B (RhB) has often been used as a model pollutant, but its photocatalytic mechanism is still controversial. Herein, Ag NPs were sandwiched between CdS QDs and amorphous-TiO 2 (a-TiO 2 ) with the intent to build a CdS/Ag/a-TiO 2 catalyst with highly selective oxidation activity. When rhodamine B (RhB) was used as the model organic compound, the CdS/Ag/a-TiO 2 composite can not only modulate radical generation but also improve the conversion ratio of RhB to rhodamine 110 (Rh-110) to as high as 82% at 80 min during the visible-light irradiation. A series of the radical scavenging experiments revealed that CdS/Ag/a-TiO 2 composites could modulate the effects of hydroxyl radicals (·OH) and superoxide anion radicals (·O 2 - ) at different reaction stages so that the overoxidation of RhB and Rh-110 were repressed. Therefore, the transient state protection mechanism of selective oxidation of RhB was proposed to explain the reaction selectivity for Rh-110. Although the effects of both ·O 2 - and ·OH are important during the photocatalytic selective oxidation of RhB, it is shown that the selective oxidation of RhB would be performed when the effect of ·O 2 - is bigger than the ·OH, if not, RhB would be oxidized unselectively. Meanwhile, this may provide a new strategy for modulating radical generation in the photocatalysis of water phases.