Hierarchically Porous Hydrothermal Carbon Microspheres Supported N-Hydroxyphthalimide as a Green and Recyclable Catalyst for Selective Aerobic Oxidation of Alcohols.

Abstract

A novel metal-free, reusable, and green catalytic system comprising hydrothermal carbon microspheres (HCMSs) supporting N-hydroxyphthalimide (NHPI) was developed and employed in the aerobic oxidation of alcohol. Hierarchically porous HCMSs with good monodispersity were produced by the hydrothermal carbonization of sucrose and designed NaOH-impregnated calcination under a static air atmosphere. The meso- and macroporous pores on HCMSs make up 71% of the total pore volume. The covalent immobilization of NHPI onto HCMSs was first accomplished by grafting hyperbranched polyquaternary amine via repetitive ring-opening reactions of diglycidyl ether and subsequent amidation with 4-carboxy-NHPI. Owing to the cocatalysis of grafted quaternary ammonium salt, a designed heterogeneous catalyst has superior performance to free NHPI in the oxidation of 2-phenylethanol. The established catalytic system achieved 42% conversion and up to 96% selectivity of acetophenone at 90 °C under 1 atm O2 for 20 h and presented a versatile catalytic effect for diversified alcohols. Immobilized NHPI could be facilely recycled via simple filtration and displayed good stability for six cycles without a discernible decrease of reactivity or damage of catalyst morphology in repeated oxidation test.