A High Nucleus Cu-Incorporated Giant Phosphotungstate with Photocatalytic Oxidation C-H of Toluene.

Exploring a novel photocatalyst for catalytic oxidation of toluene is a sustainable strategy for energy conversion in times of an energy crisis. However, designing an effective photocatalyst for the conversion of toluene remains challenging. Herein, a novel organic monophosphonate-modified high nucleus Cu-incorporated polyoxotungstate, KH[{Cu(HO)}{Cu(OPCHCOO)(1,4,9-α-PWO)}]·Cl·60HO (), has been intentionally synthesized by a self-assembly process utilizing conventional aqueous method. It reveals that contains a polyanion of [{Cu(HO)}{Cu(OPCHCOO)(1,4,9-α-PWO)}] composed of four Dawson-type {1,4,9-α-PW} subunits, forming an oval-shaped structure and further connecting into a three-dimensional (3D) framework by lateral {Cu(HO)}. Interestingly, the trivacant {1,4,9-α-PW} subunits were observed in the organophosphonate acid-functionalized polyoxometalates for the first time. Notably, exhibits a wonderful performance in catalytic oxidation of the recalcitrant C(sp)-H bond of toluene to benzoic acid with a conversion as high as 97% under visible light utilizing O as an oxidant.