The history of aerobic catalytic oxidation mediated by a subclass of polyoxometalates, the phosphovanadomolybdates of the Keggin structure, [PV_xMo_12−xO₄₀]^(3+x)−, is described. In the earlier research it was shown that phosphovanadomolybdates catalyze oxydehydrogenation reactions through an electron-transfer oxidation of a substrate by the polyoxometalate that is then reoxidized by oxygen. These aerobic oxidations are selective and synthetically useful in various transformations, notably diene aromatization, phenol dimerization and alcohol oxidation. Oxygen transfer from the polyoxometalate to arenes and alkylarenes was also discussed as a homogeneous analog of a Mars–van Krevelen oxidation. “Second generation” catalysts include binary complexes of the polyoxometalate and a organometallic compound useful, for example, for methane oxidation and nanoparticles stabilized by polyoxometalates effective for aerobic alkene epoxidation.

The H₅PV₂Mo₁₀O₄₀ polyoxometalate in a polyethylene glycol solvent was effective for a series of aerobic oxidation reactions including oxydehydrogenation of alcohols and cyclic dienes, oxidation of sulfides and the Wacker reaction; the solvent-catalyst phase can be recovered and recycled.