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用密度泛函方法研究了一种均苯四甲酰亚胺桥联的聚酞菁亚铁的氧还原反应.设计了三个模型分子以研究此催化剂在不同聚合度时的氧还原催化反应性能.使用BP86泛函和SVP基组进行构型优化得到模型分子及其氧气复合物的电子和分子结构.此催化剂中心的铁原子和氧气以双键结合并发生电荷转移时,氧气被还原.这证明此催化剂具有良好的催化氧还原能力.通过前沿轨道分析以及模型分子氧气复合物稳定性分析证实,具有较高聚合度和较强吸电子取代基的催化剂具有更好的氧还原活性.催化剂的催化性能通过一个电催化循环来实现.在此循环过程中,氧气结合氢离子被还原为水,因此此催化剂需要在酸性介质中使用.
A density functional method was used to investigate the oxygen reduction of a pyromellitimide-bridged poly (phthalocyanine) ferrate. Three model molecules were designed to investigate the oxygen reduction catalytic activity of this catalyst at different degrees of polymerization Using the BP86 functional and SVP basis set to optimize the configuration of the molecule and its oxygen complex electronic and molecular structure of the catalyst center of the iron atom and oxygen double bond and the charge transfer occurs when the oxygen is reduced. It is proved that this catalyst has a good ability of catalytic oxygen reduction.By the analysis of the frontier orbital analysis and the stability analysis of model molecular oxygen complex, it is confirmed that the catalyst with higher degree of polymerization and stronger electron withdrawing substituent has better oxygen reduction activity. The catalytic performance is achieved by an electrocatalytic cycle, during which oxygen-bonded hydrogen ions are reduced to water, so this catalyst needs to be used in an acidic medium.