酰胺功能化共价三嗪骨架增强光催化析氢  

Amide-functionalized covalent triazine framework for enhanced photocatalytic hydrogen evolution

作　　者：李昭霖 李天春 缪佳明 赵呈孝 荆宇 韩峰燕 张侃 杨小飞 Zhaolin Li;Tianchun Li;Jiaming Miao;Chengxiao Zhao;Yu Jing;Fengyan Han;Kan Zhang;Xiaofei Yang(College of Science,Nanjing Forestry University,Nanjing 210037,China;College of Chemical Engineering,Nanjing Forestry University,Nanjing 210037,China;School of Materials Science and Engineering,Nanjing University of Science and Technology,Nanjing 210094,China)

机构地区：[1]College of Science,Nanjing Forestry University,Nanjing 210037,China [2]College of Chemical Engineering,Nanjing Forestry University,Nanjing 210037,China [3]School of Materials Science and Engineering,Nanjing University of Science and Technology,Nanjing 210094,China

出　　处：《Science China Materials》2023年第6期2290-2298,共9页中国科学（材料科学（英文版）

基　　金：financially supported by the National Natural Science Foundation of China(22005149,21975129,and 22172077);the Natural Science Foundation of Jiangsu Province(BK20200777 and BK20211573);the Natural Science Foundation of the Higher Education Institutions of Jiangsu Province,China(20KJB430034);the Science Fund for Distinguished Young Scholars,Nanjing Forestry University(JC2019002)。

摘　　要：具有富氮共轭骨架的共价三嗪骨架(CTFs)是一类典型的共价有机骨架(COFs)多孔材料,因其优异的化学和物理稳定性、结构可调性和低骨架密度等特性,在光催化氧化还原反应研究方面逐渐受到重视.与众多COFs材料一样,CTFs的光催化活性与材料的结晶性和官能团修饰密切相关.然而,CTFs的合成途径较为单一,主要通过强有机酸催化氰基不可逆热聚合,以致CTFs较难通过结晶和官能团修饰协同提升催化活性.在本工作中,我们发现CF_(3)SO_(3)H催化热聚合制备的CTF-1具有很高的结晶度且晶粒表面含有大量未反应的氰基.将CTF-1浸没在盐酸溶液中,通过超声辅助促使表面氰基水解成酰胺基团,获得了酰胺功能化的高结晶性CTFs(CTF-amide).研究表明,随着盐酸处理时间的增加,更多的氰基转化为酰胺基团,相应材料的光催化活性增强越明显.其中CTF-amide-16的光催化分解水析氢速率为1133μmol g^(-1)h^(-1),远高于原始的CTF-1(520μmol g^(-1)h^(-1)).电化学和瞬态吸收结果表明,酰胺基团功能化有利于CTF中光生载流子的分离和迁移.The crystallinity and building blocks or functional groups of covalent organic frameworks(COFs)are key points to tuning their photocatalytic performance.However,the functional groups and crystallinity remain difficult to coordinate.Herein,we report an amide-functionalized highly crystalline covalent triazine framework(CTF-amide-X),where the CF_(3)SO_(3)H-catalyzed trimerization strategy was applied to synthesize CTF^(-1),leading to a highly crystalline structure and numerous surface cyano groups.Through a simple HCl treatment,CTF^(-1)is amide-functionalized while maintaining high crystallinity,which substantially enhances photocatalytic activity in water splitting.Particularly,CTF-amide-16 exhibits a hydrogen-evolving rate of 1133μmol g^(-1)h^(-1),far higher than that of pristine CTF^(-1).The superior activity of CTF-amide in photocatalysis can be obtained by promoting amide groups to separate photocarriers and promoting long-lived photoelectrons to aggregate on the material surface while maintaining the crystalline structure.

关 键 词：氧化还原反应 光生载流子 瞬态吸收 三嗪 酰胺基团 热聚合 物理稳定性 盐酸处理 

分 类 号：TQ116.2[化学工程—无机化工] TQ426