Highly catalytic performance for the selective C–H bond oxidation of p-chlorotoluene over Co, Cr co-doped OMS-2 catalyst

[Display omitted] •Co, Cr co-doped OMS-2 catalyst was prepared for the selective C–H bond oxidation of p-chlorotoluene with O2.•94.8% PCT conversion and 94.3% PCB selectivity were achieved over CoCr/OMS-2.•Co-doping of Co, Cr facilitated the adsorption of p-chlorotoluene and O2, and decreased the energy barrier of rate-determining step.•The presence of H2O promoted the hydrolysis of p-chlorobenzyl bromide and inhibited further oxidation of p-chlorobenzaldehyde. Using O2 as an oxidant, developing a non-noble metal catalyst for the selective catalytic C–H bond oxidation of p-chlorotoluene is desirable and challenging. In this work, a series of Co, Cr co-doped OMS-2 (Octahedral Molecular Sieve-2) catalysts were prepared by a conventional refluxing method. It was found that the incorporation of Co and Cr improved the catalytic activity for the selective oxidation of p-chlorotoluene to p-chlorobenzaldehyde. Among these catalysts, CoCr/OMS-2 (Co: Cr = 1: 1, mass ratio), the best catalyst, shows that the conversion and the selectivity of p-chlorobenzaldehyde is 94.8 % and 94.3 %, respectively. The enhanced catalytic activity was due to the larger specific surface area and even dispersion of active components. The characterization results also disclosed that the co-doping of Co and Cr increased the oxygen vacancy and enhanced the ability to activate the surface lattice oxygen. Additionally, density functional theory calculations demonstrated that co-doping of Co and Cr promoted the adsorption of p-chlorotoluene and O2, and decreased the energy barrier of rate-determining step (the conversion of p-chlorobenzyl alcohol to p-chlorobenzaldehyde). Besides, when H2O was added to the reaction system as the second solvent, the activation and dissociation of O2, and the formation of p-chlorobenzaldehyde were facilitated, in agreement with the experimental results. This work demonstrated the promotional effect of Co, Cr co-doped into OMS-2 catalyst and the role of H2O for the selective oxidation of p-chlorotoluene.