Expediting Ethylbenzene Oxidation via a Bimetallic Cobalt–Manganese Spinel Structure with a Modulated Electronic Environment

Abstract

The catalytic oxidation of ethylbenzene (EB) into acetophenone (AP) is a vibrant area, with a growing number of researchers paying attention to this thematic investigation. Herein, we demonstrate that spinel-type (Co,Mn)(Co,Mn) 2 O 4 can function as an efficient catalyst for the solvent-free oxidation of EB with molecular oxygen. The incorporation of Mn into the Co 3 O 4 network can break the local structural symmetry of Co−O−Co linkages due to the bond competition, inducing the formation of an asymmetrical Co−O−Mn configuration with an electron local exchange interaction. The Co−O−Mn sites can facilitate the perturbation of nonpolar O 2 and thus contribute to the generation of abundant •O 2− species for initiating the oxidation of EB. We envision that this study not only provides a promising catalyst for EB oxidation but also affords a new insight into the design of advanced spinel oxides for selective oxidation reactions.

Manipulation of Electronic Effect and Assembly Architecture to Invoke Oxidation of Ethylbenzene by Hierarchical Co3O4 Wreaths

“…Hence, the redox properties of the samples were investigated by H 2 -TPR as shown in Figure g,h. The two peaks in the H 2 -TPR curves can be assigned mainly to the reduction of Co 3+ to Co 2+ and then Co 2+ to Co 0 , respectively . Significantly, the reduction peaks in the CCW are shifted to a much lower reduction temperature of 309 and 399 °C than that in the CCP (390 and 452 °C).…”

Coupled Interface and Oxygen-Defect Engineering in Co3O4/CoMoO4 Heterostructures toward Active Oxidation of Ethylbenzene

“…Various oxygen donors, such as hydrogen peroxide, , alkyl peroxides, , and molecular oxygen, − have been extensively used in many selective oxidation reactions. Regarding on the environmental, economic, and handling factors, molecular oxygen is definitely the most attractive oxidant, and there is substantial interest in the aerobic oxidation of hydrocarbons for a cheaper, safer, and atom economic oxidation protocol. , Unfortunately, molecular oxygen is unreactive and difficult to activate, and thus the direct use of oxygen for selective oxidation reactions remains challenging. − Bearing all these considerations in mind, one can realize that the most desired oxidation strategy should be processed under environmentally benign reaction conditions (avoid the use of any solvents and additives) and directly employ molecular oxygen as the only oxidant.…”

A judicious injection and abstraction of a hetero-dopant in a Co3O4 catalyst for efficient methane oxidation

“…of different atomic sizes and valence states has been proven to be an effective means to stimulate the reactivity of Co 3 O 4 . 31–33 The formation of an asymmetric M–O–Co structure in the doped Co 3 O 4 induces crystal distortion and an electronic imbalance, which promotes the formation of oxygen vacancies and promotes the active participation of the lattice oxygen in the oxidation reaction. 34–38…”