Overturned Loading of Inert CeO2 to Active Co3O4 for Unusually Improved Catalytic Activity in Fenton‐Like Reactions

In the past decades, numerous efforts have been devoted to improving the catalytic activity of nanocomposites by either exposing more active sites or regulating the interaction between the support and nanoparticles while keeping the structure of the active sites unchanged. Here, we report the fabrication of a Co3O4−CeO2 nanocomposite via overturning the loading direction, i.e., loading an inert CeO2 support onto active Co3O4 nanoparticles. The resultant catalyst exhibits unexpectedly higher activity and stability in peroxymonosulfate‐based Fenton‐like reactions than its analog prepared by the traditional impregnation method. Abundant oxygen vacancies (Ov with a Co⋅⋅⋅Ov⋅⋅⋅Ce structure instead of Co⋅⋅⋅Ov) are generated as new active sites to facilitate the cleavage of the peroxide bond to produce SO4.− and accelerate the rate‐limiting step, i.e., the desorption of SO4.−, affording improved activity. This strategy is a new direction for boosting the catalytic activity of nanocomposite catalysts in various scenarios, including environmental remediation and energy applications. A unique overturned loading strategy for the preparation of Co3O4 nanocomposites by loading inert CeO2 onto active Co3O4 is described. Such a design generates abundant surface oxygen vacancies neighboring Co and Ce as new active sites, resulting in unusually improved catalytic activity in both Fenton‐like reaction and beyond, for instance, CO oxidation.