【作者】 宝玥；

【导师】 吴霞琴；

【作者基本信息】 上海师范大学 ， 物理化学， 2005， 硕士

【摘要】 本文主要应用循环伏安法研究了杂多酸、金属钴卟啉和双核Schiff 碱的电化学行为,并考察和比较了对氧气还原的电催化性能。首先,测量了一系列含过度金属离子的杂多酸在氮气和氧气氛下的循环伏安图。实验结果表明,杂多酸具有相似的电化学行为。然而,它们电催化还原氧的性能存在很大的差异,其中,杂多酸CuW₄ 和FeW₇ 等具有很好的电催化还原氧的性能。电催化性能方面的差异可归因于杂多酸中配位的中心离子的不同。接着,研究了金属钴卟啉修饰电极的电化学行为及对氧还原的催化性能。先后采用了几种方法实施对金属钴卟啉在电极上的修饰,实验中发现,将金属钴卟啉嵌入Nafion 膜修饰金电极上对氧气具有很好的电催化还原性能。同时混合了杂多酸CuW₄后,对氧的催化还原能力更显著。研究了类卟啉化合物双核Schiff 碱对氧的电催化还原。初步的实验结果表明,双核Schiff 碱配合物对氧还原有一定的催化作用,但不太显著。通过以上的实验,筛选出了相对较好的氧还原的电催化剂,这就是同时掺杂金属钴卟啉和杂多酸CuW₄的Nafion 膜修饰电极。本实验的结果为继续深入研究燃料电池或生物燃料电池中阴极上催化氧的四电子还原反应提供了有价值的参考信息。更多还原

【Abstract】 The electrochemical behaviors of the transition metal-containing polymetalates,metal porphyrins and Schiff base metal complexes, as well as their electrocatalyticactivities for oxygen reduction were studied by cyclic voltammetry.Except for the copper-containing polymetalates, all the other transitionmetal-containing polymetalates studied in this research showed similar cyclicvoltammetric behavior, while their electrocatalytic activities for oxygen reduction werequite different. Within them the CuW_n and FeW₇ showed the highest catalytic activities.These results suggested that the transition metal ions incorporated into thepolymetalates structure worked as the electrocatalytic centers of the polymetalates.The polymetalates modified electrode showed good electrocatalytic activity forthe reduction of H₂O₂ to H₂O, and the Co（Ⅱ） porphyrin modified electrode showedgood electrocatalytic activity for the reduction of O₂ to H₂O₂. To achieve the reductionof O₂ to H₂O, the electrode was modified with both polymetalates and Co（Ⅱ）porphyrins. Such modified electrode showed much higher electrocatalytic activity forthe oxygen reduction, compared with that modified with only polymetalates or Co（Ⅱ）porphyrins.The results from this thesis can provide information for exploration of the oxygenreduction on the cathode.更多还原