Magnetic field effect on the cathodic reduction of oxygen utilizing metalloporphyrins as the electrocatalyst

电化学反应中的磁场效应导致不对称产率的增加，电解质的磁流体动力学（MHD）流动影响反应路径和扩散极限电流。然而，直接参与电极反应的反应物和催化剂的磁性尚未引起足够的重视。研究了金属卟啉作为电催化剂的磁性对磁场中氧阴极还原的影响。作为金属卟啉，Co（III）、Mn（III）和Fe（III）的配合物（1）水不溶性meso-四苯基卟啉（TPP-M），和（2）水溶性meso-四（4-磺酸基苯基）卟啉（TPPS-M）和meso-四（1-甲基吡啶-4-基）卟啉（TMPyP-M）在本研究中被选择。对电解体系中的不同状态进行了比较。(1)非水溶性金属卟啉的磁场效应 ...更多信息 循环伏安法，使用金属卟啉涂层的玻碳电极。在氧饱和的0.1M氢氧化钠溶液中，有磁场和无磁场时的循环伏安图几乎相同。磁场（0.8特斯拉）似乎对固定化金属卟啉上的氧分子的活化几乎没有影响。(2)水溶性金属卟啉的磁场效应用0.1M NaOH溶解金属卟啉，在裸玻碳电极上用循环伏安法研究了磁场效应。有磁场和无磁场的循环伏安图显示出差异，特别是在扩散极限电流。溶解态金属卟啉作为催化剂参与电极反应，随着磁化率的增加，氧还原的扩散极限电流增大。结果表明，金属卟啉的磁流体流动有效地促进了氧的扩散，氧的还原发生在金属卟啉的分子表面，可能发生在金属位上.少

Magnetic field effect in the electrochemical reactions has been reported to lead to the increase in asymmetric yield, and the MHD (magnetohydrodynamic) flow of electrolyte which affects the reaction pathway and the diffusion limiting current. However, much attention has not been given to the magnetic property of reactant and catalyst taking part in the electrode reaction directly. It was studied how the magnetic property of metalloporphyrin as the electrocatalyst affected the cathodic reduction of oxygen in the magnetic field. As the metalloporphyrin, Co(III), Mn(III), and Fe(III) complexes of (1) water-insoluble meso-tetraphenylporphyrin (TPP-M), and (2) water-soluble meso-tetrakis (4-sulfonatophenyl) porphyrin (TPPS-M) and meso-tetrakis (l-methylpyridinium-4-yl) porphyrin (TMpyP-M) were chosen in the present research. The different states in the electrolytic system were compared.(1) Magnetic field effect at water-insoluble metalloporphyrinsThe magnetic field effect was examined by th … More e cyclic voltammetry, using a metalloporphyrin-coated glassy carbon electrode. The cyclic voltammograms in oxygen-saturated 0.1M NaOH with and without magnetic field were almost the same. The magnetic field (0.8 tesla) seems to have scarce effect on the activation of oxygen molecule at the immobilized metalloporphyrin.(2) Magnetic field effect at water-soluble metalloporphyrinsThe magnetic field effect was examined by the cyclic voltammetry in 0.1M NaOH dissolved metalloporphyrin, using a bare glassy carbon electrode. The cyclic voltammograms with and without magnetic field showed a difference, especially at the diffusion limiting current. The diffusion limiting current for oxygen reduction increased with increasing the magnetic susceptibility of dissolved metalloporphyrin, which take part in the electrode reaction as the catalyst. The results suggest that the diffusion of oxygen is effectively promoted by the MHD flow of metalloporphyrin, and the oxygen reduction occurs on the molecular surface of metalloporphyrin, probably on the metal site. Less