Bridging green light photocatalysis over hierarchical Nb2O5 for the selective aerobic oxidation of sulfides

Nb2O5 is a colourless metal oxide that is very promising in areas such as energy storage and optical glasses. These applications depend on the superior redox properties of Nb2O5 compared to those of other metal oxides, which in turn endow it with great potential in semiconductor photocatalysis. Herein, a hierarchical Nb2O5 was synthesized by the L-arginine-assisted hydrothermal method. Thereafter, visible light photocatalysis was bridged over hierarchical Nb2O5 with a common organic dye, namely alizarin red S (ARS), significantly renovating Nb2O5-based photocatalysis from ultraviolet (UV) into the green light region. The surface of hierarchical Nb2O5 was chemically modified with ARS to harvest 520 nm green light and facilitate the oxidation of organic sulfides with aerial O2. The O-atom transfer from O2 into sulfoxides with very high selectivity occurs via an intermediate of superoxide radical anions (O2˙−). Importantly, the electron transfer from activated ARS to sulfides is mediated by an electron transfer mediator, namely (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), to deter the attack of quenched ARS by reactive oxygen species (ROS). This study represents the first foray of dye-semiconductor assemblies based on a semiconductor other than TiO2 for the selective aerobic oxidation, affirming the generality of cooperative photocatalysis and implying the great potential of hierarchical Nb2O5 in platforming the visible-light-induced selective transformation of organic molecules.