催化学报

催化学报 ›› 2015, Vol. 36 ›› Issue (6): 845-854.DOI: 10.1016/S1872-2067(15)60859-2

• 论文 • 上一篇    下一篇

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

Changjiu Xiaa,b, Long Jub, Yi Zhaob, Hongyi Xua, Bin Zhub, Feifei Gaoa, Min Linb, Zhenyu Daib, Xiaodong Zoua, Xingtian Shub   

  1. a Department of Materials and Environmental Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden;
    b State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, SINOPEC, Beijing100083, China
  • 收稿日期:2015-02-26 修回日期:2015-04-02 出版日期:2015-05-21 发布日期:2015-05-21
  • 通讯作者: Min Lin,Tel/Fax: +86-10-82368801; E-mail: minlin@tom.com;Min Lin,Tel: +46-8162389; Fax: +46-8152187; E-mail: xzou@mmk.su.se
  • 基金资助:

    This work was supported by the National Basic Research Program of China (973 Program, 2006CB202508), China Petrochemical Corporation (SINOPEC Group 20673054), Swedish Research Council (VR), and Knut and Alice Wallenberg Foundation (Catalysis in Selective Organic Synthesis).

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

Changjiu Xiaa,b, Long Jub, Yi Zhaob, Hongyi Xua, Bin Zhub, Feifei Gaoa, Min Linb, Zhenyu Daib, Xiaodong Zoua, Xingtian Shub   

  1. a Department of Materials and Environmental Chemistry, Stockholm University, SE-106 91 Stockholm, Sweden;
    b State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, SINOPEC, Beijing100083, China
  • Received:2015-02-26 Revised:2015-04-02 Online:2015-05-21 Published:2015-05-21
  • Supported by:

    This work was supported by the National Basic Research Program of China (973 Program, 2006CB202508), China Petrochemical Corporation (SINOPEC Group 20673054), Swedish Research Council (VR), and Knut and Alice Wallenberg Foundation (Catalysis in Selective Organic Synthesis).

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摘要：

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.

关键词: Titanium silicate, Zeolite, Cyclohexanone, Baeyer-Villiger oxidation, Hydrogen peroxide, Lewis acid catalysis

Abstract:

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.

Key words: Titanium silicate, Zeolite, Cyclohexanone, Baeyer-Villiger oxidation, Hydrogen peroxide, Lewis acid catalysis