催化学报

催化学报 ›› 2011, Vol. 32 ›› Issue (1): 166-171.DOI: 10.3724/SP.J.1088.2010.00722

• 研究论文 • 上一篇    下一篇

Co(III) 官能化 SBA-15 的制备、表征及其催化环己烯环氧化

高鹏飞, 张铁明, 周媛, 赵永祥   

  1. 山西大学化学化工学院精细化学品教育部工程研究中心, 山西太原 030006
  • 收稿日期:2010-07-21 修回日期:2010-10-18 出版日期:2011-01-13 发布日期:2014-05-22

Co(III)-Modified SBA-15: Preparation, Characterization and Catalytic Performance for Epoxidation of Cyclohexene

GAO Pengfei, ZHANG Tieming, ZHOU Yuan, ZHAO Yongxiang*   

  1. Engineering Research Center of Ministry of Education for Fine Chemicals, School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, Shanxi, China
  • Received:2010-07-21 Revised:2010-10-18 Online:2011-01-13 Published:2014-05-22

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摘要： 通过环戊二烯基修饰的 SBA-15 (SBA-15-Cp) 与马来酸酐的 Diels-Alder 反应及水解合成了邻二羧酸官能化的 SBA-15, 并将原位生成的 Co(III) 络合物负载于其上制得 Co(III) 官能化 SBA-15 样品 SBA-15-Co(III). 傅里叶变换红外光谱、元素分析和 X 射线光电子能谱法结果证实羧酸官能团和 Co(III) 成功地引入到介孔材料中. X 射线粉末衍射、N2 物理吸附-脱附和高分辨透射电镜等表征结果表明, 在制备过程中, 材料仍较好地保持 SBA-15 的孔结构. 以异丁醛为牺牲剂, 乙腈为溶剂, 氧气流速 5 ml/min, 在 40 ?C 反应 6 h 时, SBA-15-Co(III) 在环己烯环氧化反应中表现出较高的活性和稳定性, 环氧环己烷产率和选择性分别达 58% 和 63.7%, 且经过 6 次循环后, 仍分别可达 51.6% 和 56.5%.

关键词: Diels-Alder 反应, 邻二羧酸, SBA-15, 介孔材料, Co(III), 环己烯环氧化

Abstract: A Co(III)-modified mesoporous material (SBA-15-Co(III)) was prepared by supporting an in situ formed Co(III) complex on o-dicarboxylic acid modified SBA-15 (SBA-15-(COOH)2) that was synthesized by first the Diels-Alder reaction between maleic anhydride and cyclopentadienyl-modified SBA-15 (SBA-15-Cp) and then the hydrolysis of resulting anhydride. Fourier transform infrared spectroscopy, elemental analysis (ICP-AES), and X-ray photoelectron spectroscopy confirmed the successful incorporation of carboxyl and Co(III) in the mesopores. The results of X-ray powder diffraction, N2-sorption, and high resolution transmission electron microscopy showed that SBA-15-Co(III) well maintained the mesostructure of SBA-15. In the presence of isobutylaldehyde, SBA-15-Co(III) showed moderate activity and stability in the epoxidation of cyclohexene when the flow rate of O2 was 5 ml/min, the solvent was acetonitrile, the reaction temperature was 40 °C, and time was 6 h. The yield and selectivity of cyclohexene oxide could reach 58% and 63.7%, respectively. The yield and selectivity of cyclohexene oxide could still maintained 51.6% and 56.5% after six catalytic cycles.

Key words: Diels-Alder reaction, o-dicarboxylic acid, SBA-15, mesoporous material, trivalent cobalt, cyclohexene epoxidation