Preparation and Catalytic Olefin Epoxidation Properties of Carbon Nanotube/Polyoxometalates/Polypyrrole Composite Catalyst†

doi:10.7503/cjcu20160926

Abstract

Abstract:

The PPy-PMo@CNTs composite materials were prepared via in situ polymerization with PMo, polypyrrole and carbon nanotube. The multiple characteristics of FTIR, SEM and TEM were used to characterize the catalysts. The results indicated that both PMo and polypyrrole were incorporated into the CNTs, and polypyrrole formed a layer on the surface of CNTs. N₂-adsorption results showed that PPy-PMo@CNTs obtain uniform mesoporous structure. The catalytic properties of PPy-PMo@CNTs were investigated in olefin epoxidation using H₂O₂ as the oxidant and acetonitrile as the solvent. The catalytic reaction results indicated that PPy-PMo@CNTs exhibits good catalytic activity at temperature of 60 ℃ when reaction substrate was 1 mmol and dosage of catalyst was 10 mg. Leaching and recycling experiments exhibited that PPy-PMo@CNTs have excellent stability, there was no obvious decrease of cyclooctene conversion after five reaction cycles under identical reaction conditions, and the conversion of cyclooctene retains around 65%.

Key words: Carbon nanotubes, Polyoxometalate, Hydrogen peroxide, Heterogeneous catalysis, Olefin epoxidation

CLC Number:

O643.3

TrendMD:

GAO Hongcheng, WANG Zhenlu, NIU Guiling, WEN Shoudong, WU Xiaonan, ZHANG Xiaofei, SU Pengchen, YAN Xin, QI Qiang, GAO Binbin. Preparation and Catalytic Olefin Epoxidation Properties of Carbon Nanotube/Polyoxometalates/Polypyrrole Composite Catalyst^†[J]. Chem. J. Chinese Universities, 2017, 38(7): 1223.

Figures/Tables 7

Fig.1 FTIR spectra of catalysts PMo(a), PMo/PPy(b) and PPy-PMo@CNTs(c)

Fig.2 N2-adsorption-desorption isotherms and pore size distribution(inset) of PPy-PMo@CNTs catalyst

Fig.3 SEM images of catalysts PMo/CNTs(A), PMo/PPy(B) and PPy-PMo@CNTs(C, D)

Fig.4 TEM images of catalysts PMo/CNTs(A), PMo/PPy(B) and PPy-PMo@CNTs(C, D)

Table 1 Cyclooctene epoxidation results over different kinds of catalysts in MeCN*

Catalyst	Time/h	Conversion(%)
PMo	4	89.8
PMo/PPy	1	40.9
	2	67.2
	4	71.2
PMo/CNTs	1	42.2
	2	56.1
	4	69.8
PPy-PMo@CNTs	1	36.5
	2	45.6
	4	65.9

Fig.5 Kinetic profiles of epoxidation of cyclooctene with H2O2 over catalyst PPy-PMo@CNTsLeaching experiment of catalysts: solid circle indicates conversion of cyclooctene with the catalysts removed after 1.5 h at reaction temperature. Reaction condition: 1.0 mmol cyclooctene; 1.0 mmol H2O2; 10 mg catalyst; 2.0 mL MeCN; temperature: 60 ℃. All selectivities for the epoxide are nearly 100%.

Fig.6 Recycled experiments of PPy-PMo@CNTs for the conversion of cyclooctene after 4 h reactionAll selectivities for the epoxide are greater than 99%. Reaction condition: 10 mg catalyst; 1.0 mmol cyclooctene; 2.0 mL MeCN; 1.0 mmol H2O2; temperature 60 ℃.

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