催化学报

催化学报 ›› 2006, Vol. 27 ›› Issue (11): 971-975.

• 研究论文 • 上一篇    下一篇

新型铜配合物修饰热解石墨电极上的氧电催化还原

王明艳1,许兴友1,高健1,贾能勤2   

  1. 1 淮海工学院化学工程系, 江苏连云港 222005; 2 上海师范大学化学系, 上海 200234
  • 收稿日期:2006-11-25 出版日期:2006-11-25 发布日期:2006-11-25

Electrocatalytic Reduction of Oxygen at Pyrolytic Graphite Electrode Modified with Novel Copper(Ⅱ) Complex

WANG Mingyan1*, XU Xingyou1, GAO Jian1, JIA Nengqin2   

  1. 1 Department of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005, Jiangsu, China; 2 Department of Chemistry, Shanghai Normal University, Shanghai 200234, China
  • Received:2006-11-25 Online:2006-11-25 Published:2006-11-25

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摘要： 采用新型单核铜配合物高氯酸咪唑N-2-羟基乙基二乙烯三胺合铜(Ⅱ)(Cu［L(ImH)］(ClO4)2)修饰热解石墨(PG)电极表面制得了Cu［L(ImH)］/PG电极,并采用循环伏安法和电位阶跃实验研究了该电极对氧的催化还原作用. 结果表明,该电极在中性和碱性条件下对氧气的催化还原具有良好的稳定性,还原峰电流随电位扫描速度的增大而增强,Ip～v1/2呈线性关系. 根据电位阶跃实验的I～t-1/2曲线,计算出电极反应的电子转移数约为4, 推断氧气在该电极上的还原是经历了4电子过程还原为水,催化机理属于混合控制的ECE (E电极反应, C化学反应)过程.

关键词: 铜, 配合物, 修饰电极, 电催化, 氧还原, 机理

Abstract: A novel five-coordinated copper(Ⅱ) complex (Cu［L(ImH)］(ClO4)2), which was self-assembled with imidazole, Cu2+ center, and 2-［bis(2-aminoethyl)amino］ethanol (L), was synthesized. The ligand L bearing an O atom at the hydroxyethyl arm with proper flexibility provided enough variability to adapt the different configuration requirement of Cu2+/Cu+ in the redox process. The pyrolytic graphite (PG) electrode modified with the Cu［L(ImH)］(ClO4)2 complex was constructed. The electrochemical behavior and electrocatalytic activity of the Cu［L(ImH)］/PG electrode for oxygen reduction were studied by cyclic voltammetry and chronoamperometry. The Cu［L(ImH)］/PG electrode exhibited high electrocatalytic activity and stability for oxygen reduction. The reduction current increased with the increase in scan rate, and the plot of Ip to v1/2 was linear. According to the results of potential step chronoamperometry, the electrocatalytic mechanism of oxygen reduction at the modified electrode might be similar to the ECE (E: electrode reaction, C: chemical reaction) process, the number of electron transfer in the reduction process was about 4, and the oxygen was finally reduced to H2O at the modified electrode.

Key words: copper, complex, modified electrode, electrocatalysis, oxygen reduction, mechanism