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

引用本文: 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]. 催化学报, 2015, 36(6): 845-854. doi: 10.1016/S1872-2067(15)60859-2 shu

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,

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

基金项目:
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)

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:

English

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,Tel/Fax: +86-10-82368801; E-mail: minlin@tom.com;Min Lin,Tel: +46-8162389; Fax: +46-8152187; E-mail: xzou@mmk.su.se

Received Date: 26 February 2015
Available Online: 20 June 2015
Fund Project:
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).

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:

1. [1] Thangaraj A, Eapena M J, Sivasankera S, Ratnasamy P. Zeolites, 1992, 12: 943[1] Thangaraj A, Eapena M J, Sivasankera S, Ratnasamy P. Zeolites, 1992, 12: 943
2. [2] ASTM D5758-01(2007) e-1 Standard Test Method for Determination of Relative Crystallinity of Zeolite ZSM-5 by X-Ray Diffraction, http://www.astm.org/Standards/D5758.htm.[2] ASTM D5758-01(2007) e-1 Standard Test Method for Determination of Relative Crystallinity of Zeolite ZSM-5 by X-Ray Diffraction, http://www.astm.org/Standards/D5758.htm.
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5. [5] Thangaraj A, Sivasanker S. J Chem Soc, Chem Commun, 1992: 123[5] Thangaraj A, Sivasanker S. J Chem Soc, Chem Commun, 1992: 123
6. [6] Stöcker M. Microporous Mater, 1996, 6: 235[6] Stöcker M. Microporous Mater, 1996, 6: 235
7. [7] Langerame F, Salvi A M, Silletti M, Moretti G. Surf Interf Anal, 2008, 40: 695[7] Langerame F, Salvi A M, Silletti M, Moretti G. Surf Interf Anal, 2008, 40: 695
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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

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

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

English

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

Corresponding author: 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

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

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

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

English

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

Corresponding author: 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

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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