物理化学学报 >> 2010, Vol. 26 >> Issue (10): 2647-2652.doi: 10.3866/PKU.WHXB20100940

电化学 上一篇    下一篇

Schiff 碱基过渡金属镍络合物的电化学聚合: 阳极电聚合中扫描速率的影响

李建玲, 高飞, 张雅琨, 和丽志, 韩桂梅, 王新东   

  1. 北京科技大学物理化学系, 北京100083
  • 收稿日期:2010-05-04 修回日期:2010-06-12 发布日期:2010-09-27
  • 通讯作者: 李建玲 E-mail:lijianling@ustb.edu.cn
  • 基金资助:

    北京市自然科学基金(2093039)和新世纪优秀人才支持计划资助项目

Electropolymerization of Nickel Complexes with Schiff Bases: Effect of Sweep Rate on Anodic Polymerization

LI Jian-Ling, GAO Fei, ZHANG Ya-Kun, HE Li-Zhi, HAN Gui-Mei, WANG Xin-Dong   

  1. Department of Physical Chemistry, University of Science and Technology Beijing, Beijing 100083, P. R. China
  • Received:2010-05-04 Revised:2010-06-12 Published:2010-09-27
  • Contact: LI Jian-Ling E-mail:lijianling@ustb.edu.cn
  • Supported by:

    The project was supported by the Natural Science Foundation of Beijing, China (2093039) and Programfor New Century Excellent Talents in University, China.

摘要:

采用线性电位扫描法制备了水杨醛-Schiff 碱基过渡金属镍络合物的聚合物poly[Ni(salen)], 扫描速率为5-150 mV·s-1. 采用场发射显微镜观察了聚合物poly [Ni(salen)]的表面形貌. 研究了电聚合中扫描速率对聚合物生长的影响, 电聚合速率(dΓ/dm)与扫描速率(v)呈指数衰退关系, 通过库仑电量分析指出电聚合扫描速率在20 mV·s-1 时聚合产物中含有最多的氧化还原活性点. 扫描速率提高时单体的扩散步骤限制了聚合物的生长, 所以氧化还原活性点总量随着扫描速率的提高而开始下降. 利用循环伏安法分析了聚合物poly[Ni(salen)] 的扩散动力学, 结果表明在20 mV·s-1 时制备的聚合物具有较大的电荷扩散系数.

关键词: 电化学聚合, 希夫碱, 过渡金属络合物, 掺杂度, 电荷扩散系数

Abstract:

Anodic electrochemical polymerization of N,N'-ethylenbis (salicylideneaminato) nickel(II) ([Ni(salen)]) in tetrabutylammonium perchlorate (TBAP)/acetonitrile (AN) was investigated by the linear sweep potential method. The sweep rate ranged from 5 to 150 mV·s-1. The effect of sweep rate on the growth of poly[Ni(salen)] was studied by Coulomb analysis. The morphologies of poly[Ni(salen)] were characterized by field emission scanning electron microscopy (FESEM). The relationship between the growth rate of poly[Ni(salen)] (dΓ/dm) and the sweep rate (v) fits the exponential degradation equation. The content of the redox center for poly[Ni(salen)], grown at sweep rate of 20 mV·s-1, reaches a maximum and then decreases as the sweep rate increases because monomer diffusion restricts the growth of poly[Ni(salen)]. We studied the effect of polymerization sweep rate on the kinetics of the as-grown poly[Ni (salen)] by cyclic voltammetry. The charge diffusion coefficient (D) of poly[Ni(salen)] grown at a sweep rate of 20 mV·s-1 was found to be the highest.

Key words: Electropolymerization, Schiff base, Transition metal complex, Doping level, Charge diffusioncoefficient

MSC2000: 

  • O643