高等学校化学学报 ›› 1993, Vol. 14 ›› Issue (12): 1710.

• 研究论文 • 上一篇    下一篇

联氨在d-过渡金属配合物MTP(o-NO2)TBP修饰石墨电极上的催化氧化研究

朱珍平, 任建国, 秦子斌   

  1. 武汉大学化学系, 武汉 430072
  • 收稿日期:1993-01-13 修回日期:1993-07-28 出版日期:1993-12-24 发布日期:1993-12-24
  • 通讯作者: 秦子斌.
  • 作者简介:朱珍平, 男, 27岁, 硕士, 助工.
  • 基金资助:

    国家自然科学基金;南京大学配位化学国家重点实验室研究基金

Studies on Catalytic Electro-oxidation of Hydrazine on Modified Graphite Electrode by Coordination Compounds of d-Transition Metals with TP(ο-NO2)TBP

ZHU Zhen-Ping, REN Jian-Guo, QIN Zi-Bin   

  1. Department of Chemistry, Wuhan University, Wuhan, 430072
  • Received:1993-01-13 Revised:1993-07-28 Online:1993-12-24 Published:1993-12-24

摘要: 研究了N2H4在间-四(邻-硝基苯基)四苯并卟啉铁(Ⅲ)、钴(Ⅱ)、锌(Ⅱ)和镍(Ⅱ)配合物[MTP(o-NO2)TBP,简称MTBP]修饰石墨电极上的催化电氧化反应,测得该系列金属四苯并卟啉的催化活性的顺序为Co(Ⅱ)TBP>ClFe(Ⅲ)TBP>Ni(Ⅱ)TBP>Zn(Ⅱ)TBP≈石墨,考察了Co(Ⅱ)TBP和ClFe(Ⅲ)TBP催化联氨电氧化反应的动力学过程.结果表明,OH-和N2H4在ClFe(Ⅱ)TBP修饰电极上的反应级数分别为2和1,而在Co(Ⅱ)TBP修饰电极上的均为1.根据电化学参数提出了可能的反应机理.

关键词: 四苯并卟啉, 催化电氧化, 修饰石墨电极, 反应动力学

Abstract: The catalytic properties of coordination compounds of Co(Ⅱ), Fe(Ⅲ), Ni(Ⅱ), andZn(Ⅱ) with meso-tetrakis (ο-nitrophenyl) tetrabenzoporphyrin [MTP(ο-NO2)TBPor MTBP] on modified graphite electrode for the electro-oxidation of hydrazine have been examined.The results indicate that the oxidation peak potentials shift to more cathodic direction360 mVfor Co (Ⅱ)TBPand 250 mVfor ClFe(Ⅲ)TBPcomparing with graphite electrode, respectively, but shift very little for Ni(Ⅱ)TBPand Zn(Ⅱ)TBP.The catalytic activity was found to decrease in the order:Co(Ⅱ)TBP>ClFe(Ⅲ)TBP>Ni(Ⅱ)TBP>Zn(Ⅱ)TBP.The catalytic kinetics with Co(Ⅱ)TBPand ClFe(Ⅲ)TBPwas studied.The reaction order in OH- is 1 for Co(Ⅱ)TBPand 2 for ClFe(Ⅲ)TBP, respectively.The order in N2H4 is 1 for both complexes.Tafel slopes of 118 mVfor Co(Ⅱ)TBPand 86 mVfor ClFe(Ⅲ)TBPwere obtained.

Key words: Tetrabenzoporphyrin, Catalytic electro-oxidation, Modified graphite electrode, Reaction kinetics

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