文献类型：期刊文献

英文题名：Constructing Photocatalytic Covalent Organic Frameworks with Aliphatic Linkers

作者：Xu, Ting[1,2];Wang, Zhiqiang[3,4];Zhang, Weiwei[1,2];An, Shuhao[1,2];Wei, Lei[5];Guo, Shaomeng[1,2];Huang, Yanlin[5];Jiang, Shan[5];Zhu, Minghui[6];Zhang, Yue-Biao[5];Zhu, Wei-Hong[1,2]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Frontiers Sci Ctr Materiobiol & Dynam Chem, Key Lab Adv Mat,Feringa Nobel Prize Scientist Join, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Frontiers Sci Ctr Materiobiol & Dynam Chem, Joint Int Res Lab Precis Chem & Mol Engn, Sch Chem & Mol Engn,Shanghai Key Lab Funct Mat Che, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Key Lab Adv Mat, Ctr Computat Chem, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[4]East China Univ Sci & Technol, Res Inst Ind Catalysis, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[5]ShanghaiTech Univ, Sch Phys Sci & Technol, Shanghai 201210, Peoples R China;[6]East China Univ Sci & Technol, Sch Chem Engn, State Key Lab Chem Engn, Shanghai 200237, Peoples R China

年份：2024

卷号：146

期号：29

起止页码：20107

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20242416258775);WOS:【SCI-EXPANDED(收录号:WOS:001240795800001)】；

基金：We gratefully acknowledge funding from the National Natural Science Foundation of China (NSFC 22338006, 92356301, 2233000296, 22208100, and 22375062); the Shanghai Municipal Science and Technology Major Project (21JC1401700); the Shanghai Sailing Program (22YF1410400); the Shanghai Pilot Program for Basic Research (22TQ1400100-10); the Fundamental Research Funds for the Central Universities; the Shanghai Pujiang Program (22PJ1402400); the "Chenguang Program" (22CGA32); and the Young Elite Scientists Sponsorship Program by CAST (2023QNRC001). T.X. thanks for the valuable discussions on TAS analyses with Dr. Muyu Cong (East China University of Science and Technology).

语种：英文

外文关键词：Aromatic compounds - Electrolytic reduction - Energy gap - Hydrogen bonds - Hydrophilicity - Light absorption - Photocatalytic activity

摘要：Photocatalytic covalent organic frameworks (COFs) are typically constructed with rigid aromatic linkers for crystallinity and extended pi-conjugation. However, the essential hydrophobicity of the aromatic backbone can limit their performances in water-based photocatalytic reactions. Here, we for the first time report the synthesis of hydrophilic COFs with aliphatic linkers [tartaric acid dihydrazide (TAH) and butanedioic acid dihydrazide] that can function as efficient photocatalysts for H2O2 and H-2 evolution. In these hydrophilic aliphatic linkers, the specific multiple hydrogen bonding networks not only enhance crystallization but also ensure an ideal compatibility of crystallinity, hydrophilicity, and light harvesting. The resulting aliphatic linker COFs adopt an unusual ABC stacking, giving rise to approximately 0.6 nm nanopores with an improved interaction with water guests. Remarkably, both aliphatic linker-based COFs show strong visible light absorption, along with a narrow optical band gap of similar to 1.9 eV. The H2O2 evolution rate for TAH-COF reaches up to 6003 mu mol h(-1) g(-1), in the absence of sacrificial agents, surpassing the performance of all previously reported COF-based photocatalysts. Theoretical calculations reveal that the TAH linker can enhance the indirect two-electron oxygen reduction reaction for H2O2 production by improving the O-2 adsorption and stabilizing the *OOH intermediate. This study opens a new avenue for constructing semiconducting COFs using nonaromatic linkers.