炭黑负载酞菁共价有机框架衍生催化剂的制备及其氧还原性能  

Preparation and oxygen reduction performance of carbon black-loaded phthalocyanine covalent organic framework derived catalyst

作　　者：肖龙飞 李楠[1] XIAO Longfei;LI Nan(National Engineering Lab for Textile Fiber Materials and Processing Technology,Zhejiang Sci-Tech University,Hangzhou 310018,China)

机构地区：[1]浙江理工大学纺织纤维材料与加工技术国家地方联合工程实验室,杭州310018

出　　处：《浙江理工大学学报（自然科学版）》2021年第4期453-461,共9页Journal of Zhejiang Sci-Tech University(Natural Sciences)

基　　金：国家自然科学基金项目(51703201)。

摘　　要：以四氨基钴酞菁(Cobalt tetraaminophthalocyanine,CoPc(NH2)4)为结构单元,4,4′-联苯二甲醛为连接基团,通过希夫碱反应在炭黑表面原位生长得到Co-COFs/CB前驱体,然后高温热解得到高效氧还原活性的过渡金属/氮/碳(M-N-C)催化剂:Co-COFs/CB-X(X=600、700、800℃)。使用透射电子显微镜、傅里叶红外光谱和X射线光电子能谱等对样品的微观形貌、官能团结构以及表面成分等进行表征。测试表明:Co-COFs/CB-700催化剂存在暴露的Co-N/C、吡啶氮以及石墨氮的活性位点,有效提高了氧还原活性和稳定性。Co-COFs/CB-700催化剂的半波电位达到0.841 V,极限电流密度为5.96 mA/cm2,电子转移数为3.78~3.96,HO_(2)^(-)产率为2.5%~14.1%。这表明Co-COFs/CB-700催化剂具有接近20%Pt/C的氧还原活性,氧还原途径为接近4电子的反应途径,且稳定性和抗甲醇性能均优于20%Pt/C。这说明Co-COFs/CB-700催化剂在燃料电池和金属空气电池领域具有潜在的应用前景。With cobalt tetraaminophthalocyanine(CoPc(NH2)4)as the structural unit and 4,4′-biphenyldicarbaldehyde as the linking group,the Co-COFs/CB precursor is grown in situ on the surface of carbon black by Schiff’s base reaction.After that,the transition metal/nitrogen/carbon(M-N-C)catalyst with high oxygen reduction activity is obtained through high-temperature pyrolysis:Co-COFs/CB-X(X=600,700℃and 800℃).Transmission electron microscopy,Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy,etc.are used to characterize the microstructure,functional group structure and surface composition,etc.of samples.The characterization test shows that exposed active sites of Co-N/C,pyridine nitrogen and graphite nitrogen exist in the Co-COFs/CB-700 catalyst and effectively enhance its oxygen reduction activity and stability.The half-wave potential of the Co-COFs/CB-700 catalyst reaches 0.841 V,the limiting current density is 5.96 mA/cm2,the number of electrons transferred is 3.78~3.96 and the HO_(2)^(-)yield is 2.5%~14.1%,indicating s that the Co-COFs/CB-700 catalyst has an oxygen reduction activity of nearly 20%Pt/C.The oxygen reduction pathway is a reaction pathway close to 4 electrons,whose stability and methanol resistance are better than 20%Pt/C.This shows that Co-COFs/CB-700 catalyst has a potential application prospect in the fields of fuel cells and metal-air batteries.

关 键 词：四氨基钴酞菁 炭黑 共价有机框架 氧还原 

分 类 号：O643.36[理学—物理化学]