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

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

doi:10.1016/S1872-2067(15)60859-2

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

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

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

28 Citations (Scopus)

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.

Original language	English
Pages (from-to)	845-854
Number of pages	10
Journal	Cuihua Xuebao/Chinese Journal of Catalysis
Volume	36
Issue number	6
DOIs	https://doi.org/10.1016/S1872-2067(15)60859-2
Publication status	Published - 20 Jun 2015
Externally published	Yes

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title = "Heterogeneous oxidation of cyclohexanone catalyzed by TS-1: Combined experimental and DFT studies",

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.",

keywords = "Baeyer-Villiger oxidation, Cyclohexanone, Hydrogen peroxide, Lewis acid catalysis, Titanium silicate, Zeolite",

author = "Changjiu Xia and Long Ju and Yi Zhao and Hongyi Xu and Bin Zhu and Feifei Gao and Min Lin and Zhenyu Dai and Xiaodong Zou and Xingtian Shu",

year = "2015",

month = jun,

day = "20",

doi = "10.1016/S1872-2067(15)60859-2",

language = "English",

volume = "36",

pages = "845--854",

journal = "Cuihua Xuebao/Chinese Journal of Catalysis",

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publisher = "Science Press",

number = "6",

}

TY - JOUR

T1 - Heterogeneous oxidation of cyclohexanone catalyzed by TS-1

T2 - Combined experimental and DFT studies

AU - Xia, Changjiu

AU - Ju, Long

AU - Zhao, Yi

AU - Xu, Hongyi

AU - Zhu, Bin

AU - Gao, Feifei

AU - Lin, Min

AU - Dai, Zhenyu

AU - Zou, Xiaodong

AU - Shu, Xingtian

PY - 2015/6/20

Y1 - 2015/6/20

N2 - 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.

AB - 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.

KW - Baeyer-Villiger oxidation

KW - Cyclohexanone

KW - Hydrogen peroxide

KW - Lewis acid catalysis

KW - Titanium silicate

KW - Zeolite

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U2 - 10.1016/S1872-2067(15)60859-2

DO - 10.1016/S1872-2067(15)60859-2

M3 - Article

AN - SCOPUS:84932130600

SN - 0253-9837

VL - 36

SP - 845

EP - 854

JO - Cuihua Xuebao/Chinese Journal of Catalysis

JF - Cuihua Xuebao/Chinese Journal of Catalysis

IS - 6

ER -

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

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