氰基取代的石墨炔材料的制备及其电催化性能  

Preparation of Nitrile-Substituted Graphyne and Its Electrocatalytic Performances

作　　者：孙昊天 刘洪煦 任世杰[1] SUN Haotian;LIU Hongxu;REN Shijie(State Key Laboratory of Polymer Materials Engineering,College of Polymer Science and Engineering,Sichuan University,Chengdu 610065,China)

机构地区：[1]四川大学高分子科学与工程学院,高分子材料工程国家重点实验室,成都610065

出　　处：《功能高分子学报》2024年第6期473-480,共8页Journal of Functional Polymers

基　　金：国家自然科学基金(51973128,22375136)。

摘　　要：为探究氮原子对石墨炔电催化性能的影响,从分子设计出发,通过1,3,5-三溴-2,4,6-三甲腈苯和2,4,6-三乙炔基-1,3,5-三嗪之间的Sonogashira偶联反应首次将氰基引入石墨单炔中,制备了氮掺杂型石墨炔(TCN-GY)。通过X射线光电子能谱技术(XPS)、扫描电子显微镜(SEM)等研究了热处理对石墨炔结构的影响。结果表明:通过热处理能够调节石墨炔的孔径结构,暴露活性位点,热处理后的氮掺杂型石墨炔衍生物(TCN-GY-800)具有较高的比表面积以及丰富的氮含量,在电催化氧还原测试中表现出较高催化活性,其半波电位(0.76 V)接近商业Pt/C催化剂的半波电位(0.78 V)。同时,在锌空气电池测试中,TCN-GY-800表现出接近Pt/C的功率密度(142.9 mW/cm^(2))和比容量(570.0 mA·h/g)。The development of electrochemical energy storage technology represented by zinc-air batteries is one of the effective methods to solve the current energy and environmental problems.The key to zinc-air batteries lies in the development of low-cost,high-activity catalysts for the oxygen reduction reaction(ORR).Graphyne(GY)is widely used in the field of electrocatalysis due to its high specific surface area and unique electronic structure.In order to investigate the effect of nitrogen atoms on the electrocatalytic properties of graphyne,a novel nitrogen-doped graphyne(TCN-GY)is prepared by molecular design,with the specific introduction of cyano groups into graphyne for the first time using the Sonogashira coupling reaction.The effect of heat treatment on the structure of graphyne is investigated.Results show that certain heat treatment can regulate the pore structure of graphyne and expose the active sites,and the heat-treated nitrogen-doped graphyne derivative(TCN-GY-800)has high specific surface area as well as abundant nitrogen content.In the electrocatalytic oxygen reduction reaction tests,TCN-GY-800 shows high catalytic activity.It has a half-wave potential of 0.76 V,which is similar to that of commercial Pt/C catalysts(0.78 V).In zinc-air battery tests,the TCN-GY-800-based zinc-air battery boasts a maximum power density(142.9 mW/cm^(2))and specific capacity(570.0 mA·h/g),which are comparable to those of Pt/C-based zinc-air batteries.This indicates that the in situ doping strategy to prepare nitrogen-doped graphyne has a broad development potential in the field of ORR,which is expected to be further applied in energy-and environment-related applications.

关 键 词：氮原子掺杂 石墨炔 热处理 氧还原反应 锌空气电池 

分 类 号：O63[理学—高分子化学]