文献类型：期刊文献

英文题名：Vinylene-Linked Covalent Organic Frameworks (COFs) with Symmetry-Tuned Polarity and Photocatalytic Activity

作者：Xu, Junsong[1];Yang, Can[2];Bi, Shuai[1];Wang, Wenyan[2];He, Yafei[1];Wu, Dongqing[1];Liang, Qifeng[3];Wang, Xinchen[2];Zhang, Fan[1]

机构：[1]Shanghai Jiao Tong Univ, State Key Lab Met Matrix Composites, Sch Chem & Chem Engn, Shanghai 200240, Peoples R China;[2]Fuzhou Univ, State Key Lab Photocatalysis Energy & Environm, Coll Chem, Fuzhou 350002, Peoples R China;[3]Shaoxing Univ, Dept Phys, Shaoxing 312000, Peoples R China

年份：2020

卷号：59

期号：52

起止页码：23845

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：SCI-EXPANDED(收录号：WOS:000583787800001)、、EI(收录号：20223112454632)、Scopus(收录号：2-s2.0-85093643826)、WOS

基金：We thank National Natural Science Foundation of China (21720102002, 21774072). Open Project Program of the State Key Laboratory of Inorganic Synthesis and Preparative Chemistry (2019-01, Jilin University). The project was also funded by State Key Laboratory for Modification of Chemical Fibers and Polymer Materials (No. KF2019, Donghua University). We thank Xinqiu Guo, Guihua Han, Chong Lu and Yao Han in the Instrumental Analysis Center of SJTU for some experiments.

语种：英文

外文关键词：covalent organic frameworks (COFs); photocatalysis; semiconducting properties; vinylene covalent organic framework; water splitting

外文摘要：The polarity of a semiconducting molecule affects its intrinsic photophysical properties, which can be tuned by varying the molecular geometry. Herein, we developed a D-3h-symmetric tricyanomesitylene as a new monomer which could be reticulated into a vinylene-linked covalent organic framework (g-C54N6-COF) via Knoevenagel condensation with another D-3h-symmetric monomer 2,4,6-tris(4 '-formyl-biphenyl-4-yl)-1,3,5-triazine. Replacing tricyanomesitylene with a C-2v-symmetric 3,5-dicyano-2,4,6-trimethylpyridine gave a less-symmetric vinylene-linked COF (g-C52N6-COF). The octupolar conjugated characters of g-C54N6-COF were reflected in its scarce solvatochromic effects either in ground or excited states, and endowed it with more promising semiconducting behavior as compared with g-C52N6-COF, such as enhanced light-harvesting and excellent photo-induced charge generation and separation. Along with the matched energy level, g-C54N6-COF enabled the two-half reactions of photocatalytic water splitting with an average O-2 evolution rate of 51.0 mu mol h(-1) g(-1) and H-2 evolution rate of 2518.9 mu mol h(-1) g(-1). Such values are among the highest of state-of-the-art COF photocatalysts.