物理化学学报 >> 2004, Vol. 20 >> Issue (08S): 939-945.doi: 10.3866/PKU.WHXB200408zk09

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温和条件下新型铜基磷酸盐在氧化反应中的高催化活性

孟祥举;肖丰收   

  1. 吉林大学化学学院, 无机合成与制备化学国家重点实验室, 长春 130012
  • 收稿日期:2003-06-04 修回日期:2003-08-08 发布日期:2004-08-15
  • 通讯作者: 肖丰收 E-mail:fsxiao@mail.jlu.edu.cn

Novel Copper Phosphates with High Catalytic Activities under Mild Conditions

Meng Xiang-Ju;Xiao Feng-Shou   

  1. State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012
  • Received:2003-06-04 Revised:2003-08-08 Published:2004-08-15
  • Contact: Xiao Feng-Shou E-mail:fsxiao@mail.jlu.edu.cn

摘要: 系统综述了以新型铜基磷酸盐(Cu2(OH)PO4)为代表的催化剂在一些典型的氧化反应中的活性.本文涉及的反应类型主要包括以过氧化氢为氧化剂,苯、苯酚、2,3,6-三甲基苯酚的羟化,烯烃的环氧化反应和以氧气为氧化剂,烯烃和醇的氧化反应,结果显示Cu2(OH)PO4的比表面积较小,但是在这一系列的反应中展示了很高的催化活性.同时利用电子自旋共振(ESR)、红外(IR)等表征手段对催化反应的机理和反应路径进行了讨论,羟基自由基和铜的过氧物种被认为是催化反应的重要中间体.

关键词: 磷酸铜, 过氧化氢, 氧气, 苯酚羟化, 烯烃环氧化, 醇的氧化, 羟基自由基

Abstract: Conventionally, heterogeneous catalysts are mainly focused on the materials with large surface area such as TS-1 (350 m2•g-1),and the materials with relatively small surface area ( < 10 m2•g-1) are generally ignored. This review summarized the catalytic activities and mechanism in a series of oxidations by H2O2 or oxygen as oxidants over novel copper phosphates with very small surface area less than 1.4 m2•g-1.In the hydroxylation of phenol and benzene by H2O2, the high activities of this catalyst are comparable to those of TS-1. In epoxidation of styrene by H2O2, the selectivity for epoxide is much higher than that of TS-1. In hydroxylation of 2,3,6-trimethylphenol by H2O2, it showed good activity and high selectivity for trimethylhydroquinone. In oxidation of olefins and alcohols by O2, the catalysts exhibited remarkable catalytic results. The characterization of ESR and IR spectroscopy shows that hydroxyl radicals and peroxide species are important intermediates in these oxidations.

Key words: Copper phosphate, H2O2, O2, Phenol hydroxylation, Olefins epoxidation,  Alcohol oxidation, Hydroxyl radicals