高等学校化学学报 ›› 1993, Vol. 14 ›› Issue (9): 1222.

• 研究论文 • 上一篇    下一篇

钴(Ⅱ,Ⅲ)与meso-四(4-苯基磺基)卟啉(TPPS)络合物的伏安行为研究

侯建敏, 高小霞   

  1. 北京大学化学系, 北京 100871
  • 收稿日期:1993-01-19 修回日期:1993-04-18 出版日期:1993-09-24 发布日期:1993-09-24
  • 通讯作者: 高小霞
  • 作者简介:第一作者:男, 31岁, 博士研究生.
  • 基金资助:

    国家自然科学基金

Studies of Voltammetric Behaviour on Cobalt(Ⅱ, Ⅲ) Complexes of meso-Tetra(p-sulfonatophenyl)porphyrin in Aqueous Solution

HOU Jian-Min, GAO Xiao-Xia   

  1. Department of Chemistry, Peking University, Beijing, 100871
  • Received:1993-01-19 Revised:1993-04-18 Online:1993-09-24 Published:1993-09-24

摘要: 木文报道了钴(Ⅱ,Ⅲ)与meso-四(4-苯基磺基)卟啉(TPPS)络合物的形成条件和电还原行为.结果表明在醋酸缓冲溶液(pH3.5)中,Co2+-TPPS还原同时产生催化氢波.在氨性缓冲溶液(pH9.0)中,Co2+-TPPS产生络合吸附波,讨论了其伏安行为,认为络合物中Co2+和TPPS是一步同时还原.溶解氧可以把Co2+-TPPS氧化为Co3+-TPPS,对比Mn3+-TPPS讨论了络合物的形成和溶解氧的作用,认为氧对卟啉络合物中心离子价态变化和电子转移起着重要作用.

关键词: 钴-卟啉, 锰-卟啉, 伏安法

Abstract: The formation and electrochemical behavior of cobalt (Ⅱ,Ⅲ) complexes of meso-te-tra(p-sulfonatophenyl)porphyrin(TPPS) in aqueous solution have been investigated.It has been shown that Co(Ⅱ)-TPPSmay produce a polarographic catalytic hydrogen wave in HAc-NaAc buffer, pH 3.5.In ammoniacal buffer solution (pH 9.0) a absorptive complex wave of Co(Ⅱ)-TPPSwas observed, which is attributed to the reduction of both Co(Ⅱ) and TPPS π-ring in the complex.The formation of Co(Ⅲ)-TPPScomplex and the effect of dissolved oxygen in solution comparing with that of Mn (Ⅲ)-TPPScomplex were discussed.It is considered that oxygen plays an important role in the valence of central metal atom and the rate of electron transfer in metalloporphyrins.The reductive wave of Co(Ⅱ)-TPPSin ammoniacal buffer solution (pH 10.7) can be used to determine trace cobalt in the range of 2.0×10-7 mol/Lto 6.0×10-6mol/ Lwith a detection limit of 1.0×10-7 mol/L.

Key words: Cobalt porphyrin, Manganese porphyrin, Voltammetry

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