Morphology-tuned exceptional catalytic activity of porous-polymer-supported Mn₃O₄ in aerobic sp³ C-H bond oxidation of aromatic hydrocarbons and alcohols

Mn₃O₄ nanomaterials with different morphologies (sphere, nanowire, and octahedron) embedded into functionalized nanoporous polymers were developed by a facile one-pot solvothermal technique at different temperatures. These Mn₃O₄-based hybrid materials could behave as heterogeneous nanocatalysts to perform sp³ C-H bond oxidation of aromatic hydrocarbons and alcohols with molecular oxygen as an economic oxidant. Catalytic activity could be effectively tuned by changing the morphology of incorporated Mn₃O₄ in nanoporous polymer. These Mn₃O₄-based hybrid materials exhibited remarkable catalytic performance for sp³ C-H bond oxidation as compared with bare Mn₃O₄ nanoparticles. Mn₃O₄ with octahedral morphology in nanoporous polymer exhibited the highest catalytic activity on account of its more exposed crystallographic planes and edges. These Mn₃O₄-based nanocatalysts could be recycled and reused for consecutive catalytic cycles without a significant loss of catalytic activity. Exceptional crystal facets: Nanoporous-polymer-supported Mn₃O₄ nanocatalysts (Mn@DVTA, DVTA=divinyltriallyl) with different morphologies are developed to catalyze aerobic sp³ C-H bond oxidation of aromatic hydrocarbons and alcohols. Among the different nanocatalysts, those with octahedral crystallite morphology exhibit outstanding catalytic performance.