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Citation: Changjiu Xia, Long Ju, Yi Zhao, Hongyi Xu, Bin Zhu, Feifei Gao, Min Lin, Zhenyu Dai, Xiaodong Zou, Xingtian Shu. Heterogeneous oxidation of cyclohexanone catalyzed by TS-1: Combined experimental and DFT studies[J]. Chinese Journal of Catalysis, ;2015, 36(6): 845-854. doi: 10.1016/S1872-2067(15)60859-2 shu

Heterogeneous oxidation of cyclohexanone catalyzed by TS-1: Combined experimental and DFT studies

Changjiu Xia ^a,b ,
Long Ju ^b ,
Yi Zhao ^b ,
Hongyi Xu ^a ,
Bin Zhu ^b ,
Feifei Gao ^a ,
Min Lin ^b,, ,
Zhenyu Dai ^b ,
Xiaodong Zou ^a ,
Xingtian Shu ^b

1.
a Department of Materials and Environmental Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden;

Corresponding author: Min Lin,
Received Date: 26 February 2015
Available Online: 2 April 2015
Fund Project: This work was supported by the National Basic Research Program of China (973 Program, 2006CB202508) (973 Program, 2006CB202508) China Petrochemical Corporation (SINOPEC Group 20673054) (SINOPEC Group 20673054) Swedish Research Council (VR) (VR) and Knut and Alice Wallenberg Foundation (Catalysis in Selective Organic Synthesis). (Catalysis in Selective Organic Synthesis)

The reaction mechanism of the oxidation of cyclohexanone catalyzed by titanium silicate zeolite TS-1 using aqueous H₂O₂ as the oxidant was investigated by combining density function theory (DFT) calculations with experimental studies. DFT calculations showed that H₂O₂ was adsorbed and activated at the tetrahedral Ti sites. By taking into account the adsorption energy, molecular size, steric hindrance and structural information, a reaction mechanism of Baeyer-Villiger oxidation catalyzed by TS-1 that involves the activation of H₂O₂ was proposed. Experimental studies showed that the major products of cyclohexanone oxidation by H₂O₂ catalyzed by a hollow TS-1 zeolite were ε-carprolactone, 6-hydroxyhexanoic acid, and adipic acid. These products were analyzed by GC-MS and were in good agreement with the proposed mechanism. Our studies showed that the reaction mechanism on TS-1 zeolite was different from that on Sn-beta zeolite.
- Titanium silicate,
- Zeolite,
- Cyclohexanone,
- Baeyer-Villiger oxidation,
- Hydrogen peroxide,
- Lewis acid catalysis
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