调控共价有机框架供-受体促进光催化水析氧  

Donor-acceptor regulation in covalent organic frameworks promoting photocatalytic water oxidation

作　　者：姜雨 陈铭晖 李翔宇 冯亚青[1,2,3] 张宝 JIANG Yu;CHEN Minghui;LI Xiangyu;FENG Yaqing;ZHANG Bao(School of Chemical Engineering and Technology,Tianjin University,Tianjin 300350,China;Collaborative Innovation Center of Chemical Science and Engineering,Tianjin 300072,China;Material Green Creation and Manufacturing Haihe Laboratory,Tianjin 300192,China)

机构地区：[1]天津大学化工学院,天津300350 [2]天津大学化工协同创新中心,天津300072 [3]物质绿色创造与制造海河实验室,天津300192

出　　处：《精细化工》2024年第8期1701-1709,共9页Fine Chemicals

基　　金：国家自然科学基金项目(22078241);中央高校基本科研业务费专项资金;物质绿色创造与制作海河实验室项目。

摘　　要：为探究电子供体-受体结构对共价有机框架(COFs)材料光催化性能的影响,以N,N'-对乙腈苯基-1,4,5,8-萘二酰亚胺(NBA)为基础构筑单体,分别与供电子的三(4-甲酰基)苯胺(N-CHO)、吸电子的1,3,5-三(4-甲酰苯基)三嗪(TFPT)脱水缩合,构筑了由C=C连接的NN-COF和NT-COF。采用XRD、FTIR、^(13)CNMR、XPS、SEM、TEM、EDS和紫外光电子能谱(UPS)表征了两种COFs材料的结构、形貌和光电性能,并测试其光催化水分子氧化反应(OER)性能。结果表明,与NN-COF相比,NT-COF中三嗪单元的吸电子能力和高度平面性使其具有更紧密的层间π-π堆积、更宽的可见光吸收范围和更强的光生载流子产生能力;Co(NO_(3))_(2)·6H_(2)O作为助催化剂添加后,NN-COF和NT-COF在连续6 h内平均析氧速率分别为303.73和449.53μmol/(g·h);NT-COF中相对缺电子的萘酰亚胺单元更有利于光生空穴在其杂原子上的积累,从而更高效地催化水分子OER的进行。In order to explore the influence of electron donor-acceptor structure on the photocatalytic performance of covalent organic frameworks(COFs),C==C linked NN-COF and NT-COF were synthesized form the condensation reaction of basic building monomer N,N'-p-acetonitrile-phenyl-1,4,5,8-naphthalimide(NBA)with electron-donating tri(4-formyl)aniline(N-CHO)and electron-withdrawing 1,3,5-tri-(4-formyl)triazine(TFPT),respectively.The structure,morphology and photoelectric properties of the two COFs were characterized by XRD,FTIR,^(13)CNMR,XPS,SEM,TEM,EDS and UV photoelectron spectroscopy(UPS),and their photocatalytic water oxidation(OER)performance were investigated.The results showed that,compared with NN-COF,NT-COF exhibited closer interlayerπ-πpacking,wider visible light absorption range and stronger photogenerated carrier generation ability due to their electron absorbing ability and high planarity of the triazine units.When Co(NO_(3))_(2)·6H_(2)O was added as cocatalyst,the average oxygen evolution rates of NN-COF and NT-COF were 303.73 and 449.53μmol/(g·h).The electron-deficient naphthalimide unit of NT-COF was more conducive to the accumulation of photogenerated holes on its heteroatoms,thus demonstrating higher catalysis efficiency for the oxidation reaction of water molecules.

关 键 词：光催化 共价有机框架 供体-受体 水分子分解 析氧反应 功能材料 

分 类 号：TQ630[化学工程—精细化工] O643.36[理学—物理化学]