A theoretical study of the oxidation of benzene by manganese oxide clusters: formation of quinone intermediates

• Published in: Physical chemistry chemical physics : PCCP 2024-07, Vol.26 (27), p.18629-18648
• Main Authors: Vu, Giang Huong Thi, Phan, Thuy Thi, Nguyen, Tho Huu, Le, Thang Minh, Nguyen, Minh Tho, Nguyen, Hue Minh Thi
• Format: Article
• Language: English
• Subjects: Benzene; Benzoquinone; Chemical bonds; Clusters; Density functional theory; Electron distribution; Electron spin; Hydrocarbons; Hydroquinone; Manganese dioxide; Manganese oxides; Molecular structure; Oxidation; Oxygen; Potential energy; Quantum chemistry; Quantum theory; Quinones; Softness; Vapor phases; VOCs; Volatile organic compounds
• ISSN: 1463-9076; 1463-9084; 1463-9084
• DOI: 10.1039/d3cp05207a

Manganese oxides (Mn x O y ) have been widely applied in various chemical industrial processes owing to their long lifetime, low cost and high abundance. They have been used as co-reactants for the elimination of volatile organic compounds (VOCs); however, their oxidation mechanism is not clearly established. In this theoretical study, interaction capacities between benzene (C 6 H 6 ) and Mn x O y clusters, which were modeled with MnO 2 and Mn 2 O 3 molecules, were investigated by quantum chemical computations using density functional theory (DFT) with the PBE-D3 functional. The interaction capacity between C 6 H 6 and Mn x O y was evaluated, and the probing of the initial stage of the C 6 H 6 oxidation at a molecular level offers an in-depth oxidation reaction path. Interaction energies computed in several spin states, along with the analysis of the electron distribution using the quantum theory of atoms in molecules, natural bond orbital and Wiberg bond index techniques as well as local softness values and MO energies of fragments, point out that the interaction between C 6 H 6 and Mn 2 O 3 is stronger than that with MnO 2 , amounting to −43 and −35 kcal mol −1 , respectively, and the metal atom is identified as the primary active site. During the oxide cluster-assisted oxidation, benzene firstly undergoes an oxidation reaction by active oxygen to generate intermediates such as hydroquinone and benzoquinone. The pathway involving p -benzoquinone as the product (noted as PR1) is the most energetically favored one through a transition structure lying at 19 kcal mol −1 , below the energy reference of the reactants, leading to an energy barrier significantly lower than that of 36 kcal mol −1 found for the gas phase oxidation reaction with molecular oxygen without the assistance of the oxide clusters. Potential energy profiles illustrating the reaction paths and molecular mechanisms were described in detail. The association between Mn x O y clusters and C 6 H 6 exhibits high affinity, particularly in the presence of Mn 2 O 3 , resulting in a notable decrease in the activation energy of the formation the main product p -benzoquinone of the reaction C 6 H 6 + O 2 .