Absorption and electrochemical properties of cobalt and iron phthalocyanines and their quaternized derivatives: aggregation equilibrium and oxygen reduction electrocatalysis.
Absorption and electrochemical properties of cobalt and iron phthalocyanines and their quaternized derivatives: aggregation equilibrium and oxygen reduction electrocatalysis.
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DOI：
10.1021/ic4002048
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发表时间：
2013-08
影响因子：
4.6
通讯作者：
Thiago T Tasso;Taniyuki Furuyama;N. Kobayashi
中科院分区：
文献类型：
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作者：
Thiago T Tasso;Taniyuki Furuyama;N. Kobayashi
本文报道了Co（II）和Fe（II）四akis（pyridine-3-yloxy）酞菁及其季铵化配合物的合成和电子性质的研究。经过季铵化反应后，化合物在水中的溶解度增加，通过改变溶液浓度、pH和组成来分析它们的聚集平衡。四种化合物的循环伏安图显示金属和环中心氧化还原过程，前者对吡啶基甲基化高度敏感。采用循环伏安法（CV）和旋转盘伏安法（RDV）研究了吸附在玻碳电极上的酞菁在氧还原反应（ORR）中的催化作用。Fe（II）配合物在碱性介质中的催化活性最高，并提出了一个2 + 2机制，即由第一个完整的O2制H2O2过程和随后一个不完整的H2O2制H2O过程组成。
The synthesis and investigation of the electronic properties of Co(II) and Fe(II)tetrakis(pyridine-3-yloxy)phthalocyanines, as well as the respective quaternized complexes, are reported here. After quaternization reaction, the compounds showed increased solubility in water, and their aggregation equilibrium was analyzed by varying the solution concentration, pH, and composition. Cyclic voltammograms of the four compounds showed both metal and ring centered redox processes, with the former being highly sensitive to methylation of the pyridyl groups. The catalytic effect of the phthalocyanines adsorbed on glassy carbon electrodes in the oxygen reduction reaction (ORR) was investigated by cyclic voltammetry (CV) and rotating disk voltammetry (RDV). The highest catalytic activities were observed for the Fe(II) complexes in alkaline media, and a 2 + 2 mechanism, which consists of a first complete O2 to H2O2 process and a subsequent incomplete H2O2 to H2O process, is proposed.