碳纳米管/杂多酸/聚吡咯复合催化剂的制备及催化烯烃环氧化性能

doi:10.7503/cjcu20160926

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (7): 1223.doi: 10.7503/cjcu20160926

碳纳米管/杂多酸/聚吡咯复合催化剂的制备及催化烯烃环氧化性能

高洪成^1,²(), 王振旅², 牛桂玲¹, 温守东¹, 吴效楠¹, 张晓飞¹, 苏鹏辰¹, 闫欣¹, 祁强¹, 郜镔滨¹

1. 承德石油高等专科学校化学工程系, 承德 067000
2. 吉林大学化学学院, 吉林省表面与界面化学重点实验室, 长春 130021

收稿日期:2016-12-22 出版日期:2017-07-10 发布日期:2017-06-02
作者简介:联系人简介: 高洪成, 男, 博士, 讲师, 主要从事杂多酸多相催化方面的研究. E-mail: gaohcdpc2014@163.com
基金资助:
承德市科技计划项目(批准号: 201601A002)和河北省自然科学基金(批准号: B2017411009)资助

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

GAO Hongcheng^1,^2,^*(), WANG Zhenlu², NIU Guiling¹, WEN Shoudong¹, WU Xiaonan¹, ZHANG Xiaofei¹, SU Pengchen¹, YAN Xin¹, QI Qiang¹, GAO Binbin¹

1. Department of Chemical Engineering, Chengde Petroleum College, Chengde 067000, China
2. College of Chemistry, Jilin University, Key Laboratory of Surface and Interface Chemistry of Jilin Province,Changchun 130021, China

Received:2016-12-22 Online:2017-07-10 Published:2017-06-02
Contact: GAO Hongcheng E-mail:gaohcdpc2014@163.com
Supported by:
† Supported by the Chengde Science and Technology Plan Project, China(No.201601A002) and the Natural Science Foundation of Hebei Province, China(No;B2017411009)

摘要/Abstract

摘要：

以磷钼酸(PMo)、吡咯(Py)和碳纳米管(CNTs)为原料, 通过原位聚合方法制备了PPy-PMo@CNTs复合材料. 采用傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)等手段对材料进行了结构表征. 结果表明, 磷钼酸和聚吡咯被引入到碳纳米管载体上, 且聚吡咯在碳纳米管表面形成了一层薄层. N₂吸附-脱附测试结果表明, PPy-PMo@CNTs为介孔材料. 将以乙腈为溶剂, 过氧化氢为氧化剂的烯烃环氧化反应作为模型反应, 考察了催化剂PPy-PMo@CNTs的催化活性. 结果表明, 在60 ℃, 反应底物为1 mmol, 催化剂投量为10 mg的条件下, 该催化剂表现出较好的催化活性. 中断和循环实验结果表明, 催化剂具有较好的稳定性, 在相同的反应条件下经过5次循环后, 环辛烯的转化率依然保持在约65%.

关键词: 碳纳米管, 多金属氧酸盐, 过氧化氢, 多相催化, 烯烃环氧化

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

中图分类号:

O643.3

TrendMD:

高洪成, 王振旅, 牛桂玲, 温守东, 吴效楠, 张晓飞, 苏鹏辰, 闫欣, 祁强, 郜镔滨. 碳纳米管/杂多酸/聚吡咯复合催化剂的制备及催化烯烃环氧化性能. 高等学校化学学报, 2017, 38(7): 1223.

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^†. Chem. J. Chinese Universities, 2017, 38(7): 1223.

图/表 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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碳纳米管/杂多酸/聚吡咯复合催化剂的制备及催化烯烃环氧化性能

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

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碳纳米管/杂多酸/聚吡咯复合催化剂的制备及催化烯烃环氧化性能

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

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