文献类型：期刊文献

英文题名：Vinylene-Linked Covalent Organic Frameworks with Ammonium-Promoted-Proton Transfer for Photocatalysis of H2O2 Evolution

作者：Hu, Xiang[1];Wang, Jinghui[1];Zhu, Hao[1];Zhang, Heng[1];Zhu, Lin[1,2];Liang, Qifeng[1];Zhang, Fan[2]

机构：[1]Shaoxing Univ, Dept Phys, 508 Huanchengxi Rd, Shaoxing 312000, Peoples R China;[2]Shanghai Jiao Tong Univ, Sch Chem & Chem Engn, 800 Dongchuan Rd, Shanghai 200240, Peoples R China

年份：2025

卷号：31

期号：36

外文期刊名：CHEMISTRY-A EUROPEAN JOURNAL

收录：SCI-EXPANDED(收录号：WOS:001498540100001)、、EI(收录号：20252318538168)、Scopus(收录号：2-s2.0-105007026580)、WOS

基金：We thank the National Natural Science Foundation of China (22271188, 82272821 and 22005189), Natural Science Foundation of Shanghai (No. 22ZR1467600), Zhejiang Provincial Postdoctoral Research program (ZJ2021108).

语种：英文

外文关键词：covalent organic frameworks; hydrogen peroxide; ion introduction; photocatalysis; vinylene linkage

外文摘要：Covalent organic frameworks (COFs) have emerged as effective photocatalysts for the environmentally friendly synthesis of hydrogen peroxide (H2O2) through the oxygen reduction reaction (ORR) under solar sunlight. Besides electron transfer in an ORR process, proton transport also serves as an important role in promoting kinetic rate, which was majorly improved via modifying the chemical structures of COFs, but seldom to be explored through a simple additive composition. In work, we report the preparation of two new vinylene-linked COFs termed g-TDM-COF and g-TBD-COF, respectively, by Knoevenagel condensation of trimethylpyridine (TMP) and 2,5-Dimethoxyterephthalaldehyde (DMTP) or 3,3 '-dimethoxy-[1,1 '-biphenyl]-4,4 '-dicarbaldehyde (DMBD). They were crystalized in a hexagonal lattice and adopting AA stacking modes. Their porous structures with high surface areas and micro-/nano-channels were revealed. The methoxyl substituents pended on and pyridine atoms embedded in the backbones of these COFs rendered them with hydrogen bond donating capabilities. Combined with their substantial semiconducting properties, the COFs enable photocatalysis of hydroperoxide (H2O2) production. Simply compositing these COFs with ammonium ions markedly improved the photoelectric properties, leading to an over eightfold enhancement of photocatalytic H2O2 production relative to the neat COFs, and an increase in apparent quantum yields (AQYs) from 0.70% to 4.22% at 500 nm. Such a phenomenon could be attributed to the efficient interaction of ammonium ions with the COFs via hydrogen-bond interaction, thus favorable for broadening light-harvesting, narrowing band gaps, and strengthening proton conductivity. As a consequence, their photocatalytic performance could be distinctly enhanced.