SCI和EI收录∣中国化工学会会刊

›› 2014, Vol. 22 ›› Issue (11/12): 1220-1225.DOI: 10.1016/j.cjche.2014.09.041

• 催化、动力学与反应工程 • 上一篇    下一篇

Hydroxylation of Benzene to Phenol by H2O2 over an Inorganic-Organic Dual Modified Heteropolyacid

Li Jing, Fumin Zhang, Yijun Zhong, Weidong Zhu   

  1. Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua 321004, China
  • 收稿日期:2013-01-10 修回日期:2013-03-11 出版日期:2014-12-28 发布日期:2014-12-24
  • 通讯作者: Fumin Zhang, Weidong Zhu
  • 基金资助:
    Supported by the National Natural Science Foundation of China (20806075, 20971109, 21036006) and the Program for Changjiang Scholars and Innovative Research Team in Chinese Universities (IRT0980).

Hydroxylation of Benzene to Phenol by H2O2 over an Inorganic-Organic Dual Modified Heteropolyacid

Li Jing, Fumin Zhang, Yijun Zhong, Weidong Zhu   

  1. Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua 321004, China
  • Received:2013-01-10 Revised:2013-03-11 Online:2014-12-28 Published:2014-12-24
  • Supported by:
    Supported by the National Natural Science Foundation of China (20806075, 20971109, 21036006) and the Program for Changjiang Scholars and Innovative Research Team in Chinese Universities (IRT0980).

摘要: Various catalysts, including the heteropolyacid (HPA) H4PMo11VO40, its cesiumsalts, and inorganic-organic dual modified HPA catalyst,were prepared and characterized by Fourier transform infrared spectroscopy (FT-IR), nuclearmagnetic resonance (13C NMR), N2 adsorption, acid-base titration, electron spin resonance (ESR) and X-ray diffraction (XRD) techniques as well as elemental analysis. These prepared catalysts were used in the hydroxylation of benzene to phenol by H2O2 as oxidant. The inorganic-organic dual modified HPA Cs2.5(MIMPS)1.5 PMo11VO40, prepared by partially exchanging Cs+ with protons in H4PMo11VO40 and followed by the immobilization of 3-(1-methylimidazolium-3-yl)propane-1-sulfonate (MIMPS), led to a liquid-solid biphasic catalysis system in the hydroxylation, which showed the best catalytic performance in terms of reusability and catalytic activity. The high reusability of Cs2.5(MIMPS)1.5PMo11VO40 in the heterogeneous hydroxylation was probably due to its high resistance in leaching of bulk HPA into the reaction medium. The slightly enhanced catalytic activity for the catalyst was due to the acid sites available from MIMPS beneficial to the hydroxylation.

关键词: Heteropolyacids, Hydroxylation, Phenols, Hydrophobic interaction, Liquid-phase oxidation

Abstract: Various catalysts, including the heteropolyacid (HPA) H4PMo11VO40, its cesiumsalts, and inorganic-organic dual modified HPA catalyst,were prepared and characterized by Fourier transform infrared spectroscopy (FT-IR), nuclearmagnetic resonance (13C NMR), N2 adsorption, acid-base titration, electron spin resonance (ESR) and X-ray diffraction (XRD) techniques as well as elemental analysis. These prepared catalysts were used in the hydroxylation of benzene to phenol by H2O2 as oxidant. The inorganic-organic dual modified HPA Cs2.5(MIMPS)1.5 PMo11VO40, prepared by partially exchanging Cs+ with protons in H4PMo11VO40 and followed by the immobilization of 3-(1-methylimidazolium-3-yl)propane-1-sulfonate (MIMPS), led to a liquid-solid biphasic catalysis system in the hydroxylation, which showed the best catalytic performance in terms of reusability and catalytic activity. The high reusability of Cs2.5(MIMPS)1.5PMo11VO40 in the heterogeneous hydroxylation was probably due to its high resistance in leaching of bulk HPA into the reaction medium. The slightly enhanced catalytic activity for the catalyst was due to the acid sites available from MIMPS beneficial to the hydroxylation.

Key words: Heteropolyacids, Hydroxylation, Phenols, Hydrophobic interaction, Liquid-phase oxidation