Understanding of Cumene Oxidation Catalyzed by Metal–Nitrogen–Carbon through Theoretical Simulations and Kinetic Validation

M–N–C materials as catalysts are widely used in hydrocarbon oxidation, the intrinsic role of which has not been well illustrated. In this study, M–N–C (M = Fe, Co, Cu, Zn) as model catalysts for cumene oxidation through theoretical calculations and experiment validation are studied. The changes of Gibbs free energy (ΔG) for the elementary steps demonstrate that the activation of cumene/O2 molecules and the decomposition of cumene hydroperoxide (CHP) play a significant role in cumene oxidation. The interactions between M–N–C and cumene, O2, and CHP are fully investigated. There are strong interactions between FeNC/CoNC and O2, cumene, and CHP, in which the activation of cumene and O2 and the decomposition of CHP occurred more easily, thereby promoting the catalytic activity. Although the adsorption energy over CuNC (ΔECuNC) for cumene is comparable to ΔECoNC, the O2 molecule is physically adsorbed on CuNC, which leads to a lower activity than those of FeNC and CoNC. Metal tetraphenyl-porphyrins (MTPPs) with the corresponding structure of M–N–C as the catalysts are used to catalyze the oxidation of cumene. A volcanic curve correlation between the average adsorption energy (ΔEav.) and the conversion rate of cumene catalyzed by MTPPs is observed. The kinetic experiments confirmed that CoTPP displays the best catalytic activity, due to the high k80 and low activation energy for the crucial steps of cumene oxidation, which is consistent with the theoretical results.