文献类型：期刊文献

英文题名：Spatial confinement of nitrogen through carboxyl-induced hydrogen bond networks in covalent organic frameworks for efficient overall ammonia photosynthesis

作者：Zhang, Xiaolong[1,2];Liu, Ying[3,4];Feng, Shufan[1,2];Gu, Xixin[1,2];Zhou, Min[3,4];Wang, Haifeng[3,4];Hua, Jianli[1,2]

机构：[1]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Key Lab Adv Mat, Meilong Rd 130, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Joint Int Res LabPrecis Chem &, Meilong Rd 130, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Ctr Computat Chem, State Key Lab Green Chem Engn & Ind Catalysis, Meilong Rd 130, Shanghai 200237, Peoples R China;[4]East China Univ Sci & Technol, Res Inst Ind Catalysis, Meilong Rd 130, Shanghai 200237, Peoples R China

年份：2025

卷号：366

外文期刊名：APPLIED CATALYSIS B-ENVIRONMENT AND ENERGY

收录：;EI(收录号：20250117635259);WOS:【SCI-EXPANDED(收录号:WOS:001410185200001)】；

基金：For financial support of this research, the authors thank the projects supported by the National Natural Science Foundation of China (22271093 and 21971064) , Shanghai Municipal Science and Technology Major Project (Grant No. 2018SHZDZX03) , the Fundamental Research Funds for the Central Universities (222201717003 and 50321101918001) and the Programme of Introducing Talents of Discipline to Universities (B16017) . The authors thank Research Center of Analysis and Test of East China University of Science and Technology for the help on the characterization. The authors thank Prof. Jing Xu of East China University of Science and Technology for the help with the In situ FTIR spectra experiment.

语种：英文

外文关键词：Carboxyl group; Covalent organic framework; Ammonia; Photocatalysis; Hydrogen bond network; N2 adsorption

摘要：Covalent organic frameworks (COFs) have gained attention as promising candidates for photocatalytic nitrogen (N2) reduction to ammonia (NH3) due to their highly ordered structures and customizable molecule design. However, their efficiency in photocatalytic NH3 synthesis is limited by the generally weak affinity for N2. Inspired by spatial confinement effects, hydrophilic carboxyl groups were incorporated into a diketopyrrolopyrrole-based COF ( DPPCOOH-COF ) to form a localized hydrogen bond network that retains N2near the active sites. This structural modification significantly boosts N2adsorption and activation on COFs and lowers the energy cost for NH3 production, facilitating a more efficient reaction pathway. Remarkably, DPPCOOH-COF achieves a record NH3 production rate of 521.37 mu mol g-1 h-1 without any sacrificial agents, outperforming its structural counterpart, DPPC-COF, which lacks carboxyl groups. This study provides the first successful demonstration of COFs enabling overall NH3 photosynthesis, presenting a molecular-level design approach that effectively addresses solid-liquid-gas interactions within photocatalytic processes.