Citation: Mingzhou Wu, Wangcheng Zhan, Yun Guo, Yunsong Wang, Yanglong Guo, Xueqing Gong, Li Wang, Guanzhong Lu. Solvent-free selective oxidation of cyclohexane with molecular oxygen over manganese oxides: Effect of the calcination temperature[J]. Chinese Journal of Catalysis, ;2016, 37(1): 184-192. doi: 10.1016/S1872-2067(15)60983-4 shu

Solvent-free selective oxidation of cyclohexane with molecular oxygen over manganese oxides: Effect of the calcination temperature

1.
Key Laboratory for Advanced Materials and Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, China

Corresponding author: Wangcheng Zhan, Guanzhong Lu,
Received Date: 9 August 2015
Available Online: 22 September 2015
Fund Project: 国家重点基础研究发展计划(2010CB732300) (2010CB732300) 国家自然科学基金(21103048). (21103048)

The effects of calcination temperature on the physicochemical properties of manganese oxide catalysts prepared by a precipitation method were assessed by X-ray diffraction, N₂ adsorption-desorption, X-ray photoelectron spectroscopy, H₂ temperature-programmed reduction, O₂ temperature-programmed desorption, and thermogravimetry-differential analysis. The catalytic performance of each of these materials during the selective oxidation of cyclohexane with oxygen in a solvent-free system was subsequently examined. It was found that the MnO_x-500 catalyst, calcined at 500 ℃, consisted of a Mn₂O₃ phase in addition to Mn₅O₈ and Mn₃O₄ phases and possessed a low surface area. Unlike MnO_x-500, the MnO_x-400 catalyst prepared at 400 ℃ was composed solely of Mn₃O₄ and Mn₅O₈ and had a higher surface area. The pronounced catalytic activity of this latter material for the oxidation of cyclohexene was determined to result from numerous factors, including a higher concentration of surface adsorbed oxygen, greater quantities of the surface Mn⁴⁺ ions that promote oxygen mobility and the extent of O₂ adsorption and reducibility on the catalyst. The effects of various reaction conditions on the activity of the MnO_x-400 during the oxidation of cyclohexane were also evaluated, such as the reaction temperature, reaction time, and initial oxygen pressure. Following a 4 h reaction at an initial O₂ pressure of 0.5 MPa and 140 ℃, an 8.0% cyclohexane conversion and 5.0% yield of cyclohexanol and cyclohexanone were achieved over the MnO_x-400 catalyst. In contrast, employing MnO_x-500 resulted in a 6.1% conversion of cyclohexane and 75% selectivity for cyclohexanol and cyclohexanone. After being recycled through 10 replicate uses, the catalytic activity of the MnO_x-400 catalyst was unchanged, demonstrating its good stability.
- Manganese oxide catalyst,
- Selective oxidation of cyclohexane,
- Oxygen,
- Calcination temperature,
- Solvent-free reaction
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