还原氧化石墨烯负载球形金属酞菁电催化阴极氧还原反应性能  

Electrocatalysis Performance of Reduced Graphene Oxide Wrapped Ball⁃Type Metallophthalocyanine for Oxygen Reduction Reaction

作　　者：谭阿敏 何洋 刘布雷 杨正超 田敏[1] 张改[1] TAN A-Min;HE Yang;LIU Bu-Lei;YANG Zheng-Chao;TIAN Min;ZHANG Gai(School of Materials and Chemical Engineering,Xi'an Technological University,Xi'an 710021,China;China Petroleum Dushanzi Petrochemical Company,Karamay,Xinjiang 833699,China)

机构地区：[1]西安工业大学材料与化工学院,西安710021 [2]中国石油独山子石化公司,克拉玛依833699

出　　处：《无机化学学报》2022年第1期21-30,共10页Chinese Journal of Inorganic Chemistry

基　　金：陕西省自然科学基金面上项目(No.2020JM⁃563)资助。

摘　　要：针对阴极氧还原反应(ORR)动力学缓慢和Pt/C类贵金属催化剂成本高等关键难题,我们设计、合成了醛基取代的球形金属酞菁M_(2)Pc_(2)(TA)_(4)(M=Zn、Co、Fe),采用“π⁃π组装”技术将其负载到还原氧化石墨烯(rGO)上得到复合催化剂M_(2)Pc_(2)(TA)_(4)/rGO,并对其形貌和结构进行表征。结果表明:通过“π⁃π堆积”作用将球形金属酞菁负载在rGO表面上后,金属酞菁的团聚现象得到明显改善。利用循环伏安法和线性扫描伏安法对材料催化ORR活性进行评价。结果表明:rGO能与球形金属酞菁产生协同效应,促进ORR过程中电子的转移,有效提升电催化活性。机理研究发现催化ORR过程为4电子过程且催化活性与中心金属d电子有关,催化ORR反应活性顺序为Fe_(2)Pc_(2)(TA)_(4)/rGO>Zn_(2)Pc_(2)(TA)_(4)/rGO>Co_(2)Pc_(2)(TA)_(4)/rGO。There are some key problems for oxygen reduction reaction(ORR),such as the slow kinetic process and high cost of Pt/C catalysts.To overcome this problem,the ball⁃type metallophthalocyanines containing aldehyde substituents M_(2)Pc_(2)(TA)_(4)(M=Zn,Co,Fe)were synthesized.The metallophthalocyanine was then supported on the reduced graphene oxide(rGO)surface to obtain a composite catalyst M_(2)Pc_(2)(TA)_(4)/rGO using the“π⁃πassembly”technology,and the morphology and microstructure were characterized.The results showed that the metallophthalo⁃cyanine was loaded on the surface of rGO through the“π⁃πstacking”effect,and the agglomeration phenomenon of the metallophthalocyanines was prevented.Cyclic voltammetry and linear sweep voltammetry were used to evaluate the catalytic activity of composites for ORR.The results suggested that rGO promotes the transfer of electrons in ORR and effectively enhances the electrocatalytic activity,based on the synergistic effect between rGO and ball⁃type metallophthalocyanine.The catalytic mechanism reveals that the ORR is a four⁃electron electrocatalytic process.The catalytic activity is related to the d electron of the central metal.The electrocatalytic activity test was displayed in the order of Fe_(2)Pc_(2)(TA)_(4)/rGO>Zn_(2)Pc_(2)(TA)_(4)/rGO>Co_(2)Pc_(2)(TA)_(4)/rGO.

关 键 词：球形金属酞菁 还原氧化石墨烯 π⁃π组装 氧还原反应 仿生电催化 

分 类 号：O614.811[理学—无机化学] O614.812[理学—化学]