Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
Inorg Chem. 2013 Aug 19;52(16):9206-15. doi: 10.1021/ic4002048. Epub 2013 Aug 5.
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.
本文报道了 Co(II) 和 Fe(II) 四(吡啶-3-氧基)酞菁的合成及电子性质研究，以及相应的季铵化配合物。季铵化反应后，化合物在水中的溶解度增加，并通过改变溶液浓度、pH 值和组成来分析其聚集平衡。四种化合物的循环伏安图显示了金属和环中心的氧化还原过程，其中前者对吡啶基的甲基化非常敏感。通过循环伏安法（CV）和旋转圆盘伏安法（RDV）研究了酞菁在玻碳电极上吸附在氧气还原反应（ORR）中的催化作用。在碱性介质中，观察到 Fe(II) 配合物具有最高的催化活性，并提出了一个 2 + 2 机制，该机制由第一个完整的 O2 到 H2O2 过程和随后的不完整的 H2O2 到 H2O 过程组成。
