共价有机聚合物(COPs)作为一种具有可预先设计的结构和明确活性点位的新型材料,对于氧还原电催化剂的研究具有重要意义。通过在COPs中引入官能团调节其电子结构是优化其电催化氧还原性能的有效策略。以碳纳米管为载体,四氨基酞菁钴[CoPc(NH2)4]、氨基酞菁铁(FePc-NH2)以及具有不同吸电子基团或供电子基团的对苯二甲醛(BDA)为构建单元,通过希夫碱缩聚,合成了一系列共价有机聚合物/碳纳米管复合材料。结果表明:随着COPs中吸电子基团(氟)的引入,其相应的催化剂表现出逐渐提高的电催化氧还原性能。其中,以2,3,5,6-四氟对苯二甲醛(BDA-F4)为构建单元合成的催化剂(FeCo-COP-BDA-F4@CNT)表现出最好的电催化氧还原性能,远远优于商业Pt/C催化剂。此外,FeCo-COP-BDA-F4@CNT具有优异的抗甲醇性能和电化学稳定性,在金属-空气电池和燃料电池中具有巨大的应用潜力。
Covalent organic polymers (COPs),as a new kind of material with pre-designed structures and clear active sites,are of great significance for the study of oxygen reduction electrocatalysts.Introducing functional groups into COPs to regulate their electronic structure is an effective strategy for optimizing their electrocatalytic oxygen reduction performance.Here,a series of covalent organic polymer/carbon nanotube composites were synthesized by Schiff base condensation using carbon nanotubes as carriers,CoPc(NH2)4,FePc-NH2,and terephthalaldehyde with different electron withdrawing or donating groups as building units.The results showed that with the introduction of electron withdrawing groups (fluorine) in COPs,their corresponding catalysts exhibited gradually improved electrocatalytic oxygen reduction performance.Among them,the catalyst synthesized using 2,3,5,6-tetrafluoroterephthalaldehyde (BDA-F4) as the building unit (named FeCo-COP-BDA-F4@CNT) exhibited the best electrocatalytic oxygen reduction performance,significantly outperforming commercial Pt/C catalysts.In addition,FeCo-COP-BDA-F4@CNT had excellent methanol resistance and electrochemical stability,demonstrating great potential for application in metal-air batteries and fuel cells.
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基金资助
国家自然科学基金(22202181);浙江省自然科学基金项目(LQ21B030015)
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