羧基苯基卟啉的合成及其复合物的光催化性能  

Synthesis of Carboxyphenyl Porphyrins and Photocatalytic Properties of Their Composites

作　　者：王禹婷 陈辉 李艳婷 林万明 WANG Yu-ting;CHEN Hui;LI Yan-ting;LIN Wan-ming(School of New Energy and Materials Engineering,Shanxi University of Electronic Science and Technology,Linfen 041000,China)

机构地区：[1]山西电子科技学院新能源与材料工程学院,山西临汾041000

出　　处：《分子催化（中英文）》2024年第5期437-447,I0002,共12页Journal of Molecular Catalysis(China)

基　　金：山西省教育厅高等学校科技创新项目(2023L455,杂化锌电池钴基多功能阴极材料的可控制备及储能特性研究)。

摘　　要：卟啉具有较强的结构可修饰性和可见光吸收能力,被广泛应用于新型光催化剂和光敏剂的设计研究中.但是,不同结构的卟啉材料催化活性差异较大,且卟啉单体催化稳定性较差,无法充分发挥出高效的光催化活性.为探究影响卟啉光催化活性产生差异的本征原因以及增强卟啉在光催化过程中的稳定性,我们设计合成了三种不同分子结构的羧基卟啉TCPP、TmCPP和H8OCPP.实验结果表明,H8OCPP催化剂光催化产氢速率为4111μmol·g^(−1)·h^(−1),远高于另外两种羧基卟啉.利用胺基与羧基间的静电相互作用,将g-C_(3)N_(4)和TDPP负载于H8OCPP表面,大幅提高了羧基卟啉的光催化稳定性.强极性羧基基团数目的增加,有利于卟啉分子光生空穴-电子的分离,提升光催化分解水产氢性能,另外胺基修饰分子的引入提高了羧基卟啉在催化反应体系中的稳定性和催化活性.Porphyrins have strong structural modifiability and visible light absorption ability,and are widely used in the design and research of novel photocatalysts and photosensitizers.However,the catalytic activity of porphyrins with different structures varies greatly,and the catalytic stability of porphyrins monomers is poor,so they cannot fully play the efficient photocatalytic activity.In order to explore the intrinsic reasons for the difference in photocatalytic activity of porphyrins and enhance the stability of porphyrins in the photocatalytic process,three kinds of carboxyl porphyrins with different molecular structures TCPP,TmCPP and H8OCPP were synthesized.The results showed that H8OCPP exhibited the highest photocatalytic water splitting activity with the hydrogen evolution rate of 4111μmol·g^(−1)·h^(−1).In addition,by utilizing the electrostatic interaction between amine and carboxyl groups,g-C_(3)N_(4)and TDPP were loaded onto the surface of H8OCPP,significantly boosting the photocatalytic stability of carboxyl porphyrin.The increase in the number of strong polar carboxyl groups is beneficial for the separation of photogenerated hole-electron pairs of porphyrin molecules,leading to improve the photocatalytic hydrogen production performance.The introduction of amine group modified molecules enhances the stability and catalytic activity of carboxyl porphyrin in the photocatalytic reaction system.

关 键 词：光催化 羧基卟啉 复合材料 

分 类 号：O643.32[理学—物理化学]