Functionalizing carbon nitride with heavy atom-free spin converters for enhanced 1O2 generation

被引:26
|
作者
Wu, Wenting [1 ,2 ]
Han, Congcong [1 ]
Zhang, Qinhua [1 ]
Zhang, Qinggang [1 ]
Li, Zhongtao [1 ]
Gosztola, David J. [2 ]
Wiederrecht, Gary P. [2 ]
Wu, Mingbo [1 ]
机构
[1] China Univ Petr East China, Coll Chem Engn, State Key Lab Heavy Oil Proc, Qingdao 266580, Peoples R China
[2] Argonne Natl Lab, Ctr Nanoscale Mat, Argonne, IL 60439 USA
关键词
Carbon nitride; Heavy atom-free spin converters; Singlet oxygen; Intersystem crossing; Selective photooxidation; INTRAMOLECULAR CHARGE-TRANSFER; SINGLET OXYGEN; TRIPLET PHOTOSENSITIZERS; PHOTOPHYSICAL PROPERTIES; ELECTRON-TRANSFER; PHOTOOXIDATION; DESIGN; NANOSHEETS; FRAMEWORK;
D O I
10.1016/j.jcat.2018.03.006
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Carbon nitride as a metal-free conjugated polymer exhibits an intriguing prospect for the design of advanced photosensitizers for singlet oxygen (O-1(2)) generation. However, the intersystem crossing (ISC) process is quite insufficient in carbon nitride, limiting the O-1(2) generation. Here, we report a facile and general strategy to confined benzophenone as a heavy atom-free spin converter dopant in carbon nitride via the facile copolymerization. With proper energy level matching between the heavy atom-free spin converter and various ligands based on carbon nitride precursors, the proper combination can decrease the singlet-triplet energy gap (Delta EsT) and hence generate O-1(2) effectively. Due to its significant and selectivity for O-1(2) generation, the as-prepared carbon nitride-based photosensitizer shows a high selective photooxidation activity for 1,5-dihydroxy-naphthalene (1,5-DHN). The product yield reached 71.8% after irradiation for 60 min, which was higher than that of cyclometalated re complexes (53.6%) in homogeneous photooxidation. This study can broaden the application of carbon nitride in the field of selective heterogeneous photooxidation due to simple operation, low cost, and high efficiency, making it a strong candidate for future industrialization. (C) 2018 Elsevier Inc. All rights reserved.
引用
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页码:222 / 229
页数:8
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