n?p Electron Transitions and Directional Charge Migration Synergistically Promoting O2 Activation and Holes Utilization on Carbon Nitride for Efficiently Photocatalytic Degradation of Organic Contaminants

被引：35
作者：
Zhang, Qiang [1 ]
Chen, Juan [1 ]
Che, Huinan [1 ]
Liu, Bin [2 ]
Ao, Yanhui [1 ]
机构：
[1] Hohai Univ, Coll Environm, Key Lab Integrated Regulat & Resource Dev Shallow, Minist Educ, 1, Xikang Rd, Nanjing 210098, Peoples R China
[2] City Univ Hong Kong, Dept Mat Sci & Engn, Hong Kong 999077, Peoples R China
来源：
SMALL | 2023年 / 19卷 / 42期
关键词：
density-functional theory (DFT) calculations; holes oxidation; n?p* electron transitions; O-2; activation; spontaneous polarized electric field; G-C3N4; PERFORMANCE; FIELDS;
D O I：
10.1002/smll.202302510
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Stimulating electron transitions and promoting exciton dissociation are crucial for improving the photocatalytic performance of polymeric carbon nitride (CN) yet still challenging. Herein, a novel CN with C dopant and asymmetric structure (CC-UCN2) is ingeniously synthesized. The obtained CC-UCN2 not only reinforces the intrinsic p?p* electron transitions, but also successfully awakens additional n?p* electron transitions. Besides, charge centers dislocation caused by symmetry breaking induces a spontaneous polarized electric field, effectively breaking the constraints of Coulomb electrostatic interaction between electrons and holes and driving their directional migration. Along with the spatial separation of reduction and oxidation sites, CC-UCN2 shows exceptional O-2 activation and holes oxidation efficiency, thus exhibits a high degradation rate constant (0.201 min(-1)) and mineralization rate (80.1%) for bisphenol A (BPA)(far outperforming pristine and other modified CNs). This work proposes a novel perspective for developing high-efficiency photocatalysts and comprehending the underlying mechanism of O-2 activation and holes oxidation for pollutant degradation.
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页数：13
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共 57 条
[1]   MnOx-decorated 3D porous C3N4 with internal donor-acceptor motifs for efficient photocatalytic hydrogen production [J].
Ai, Minhua ;
Zhang, Jing-Wen ;
Gao, Ruijie ;
Pan, Lun ;
Zhang, Xiangwen ;
Zou, Ji-Jun .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2019, 256
[2]   Self-Supporting 3D Carbon Nitride with Tunable n → π* Electronic Transition for Enhanced Solar Hydrogen Production [J].
An, Sufeng ;
Zhang, Guanghui ;
Li, Keyan ;
Huang, Zhennan ;
Wang, Xiang ;
Guo, Yongkang ;
Hou, Jungang ;
Song, Chunshan ;
Guo, Xinwen .
ADVANCED MATERIALS, 2021, 33 (49)
[3]   Enhanced Hydrogen Evolution Performance of Carbon Nitride Using Transition Metal and Boron Co-Dopants [J].
Baktash, Ardeshir ;
Fang, Yuan ;
Xiao, Mu ;
Hunter, Michelle ;
Yuan, Qinghong ;
Wang, Lianzhou .
SMALL STRUCTURES, 2023, 4 (06)
[4]   Rational design of donor-acceptor conjugated polymers with high performance on peroxydisulfate activation for pollutants degradation [J].
Che, Huinan ;
Wang, Peifang ;
Chen, Juan ;
Gao, Xin ;
Liu, Bin ;
Ao, Yanhui .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2022, 316
[5]   Iodide-Induced Fragmentation of Polymerized Hydrophilic Carbon Nitride for High-Performance Quasi-Homogeneous Photocatalytic H2O2 Production [J].
Che, Huinan ;
Gao, Xin ;
Chen, Juan ;
Hou, Jun ;
Ao, Yanhui ;
Wang, Peifang .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2021, 60 (48) :25546-25550
[6]   Simultaneously Tuning Band Structure and Oxygen Reduction Pathway toward High-Efficient Photocatalytic Hydrogen Peroxide Production Using Cyano-Rich Graphitic Carbon Nitride [J].
Chen, Lei ;
Chen, Cheng ;
Yang, Zhi ;
Li, Shan ;
Chu, Chiheng ;
Chen, Baoliang .
ADVANCED FUNCTIONAL MATERIALS, 2021, 31 (46)
[7]   Activation of n → π* Transitions in Two-Dimensional Conjugated Polymers for Visible Light Photocatalysis [J].
Chen, Yan ;
Wang, Bo ;
Lin, Sen ;
Zhang, Yongfan ;
Wang, Xinchen .
JOURNAL OF PHYSICAL CHEMISTRY C, 2014, 118 (51) :29981-29989
[8]   Steering the interlayer energy barrier and charge flow via bioriented transportation channels in g-C3N4: Enhanced photocatalysis and reaction mechanism [J].
Cui, Wen ;
Li, Jieyuan ;
Cen, Wanglai ;
Sun, Yanjuan ;
Lee, S. C. ;
Dong, Fan .
JOURNAL OF CATALYSIS, 2017, 352 :351-360
[9]   Carbon self-doping induced high electronic conductivity and photoreactivity of g-C3N4 [J].
Dong, Guohui ;
Zhao, Kun ;
Zhang, Lizhi .
CHEMICAL COMMUNICATIONS, 2012, 48 (49) :6178-6180
[10]   Highly efficient removal of organic contaminant with wide concentration range by a novel self-cleaning hydrogel: Mechanism, degradation pathway and DFT calculation [J].
Du, Yuanjing ;
Che, Huinan ;
Wang, Peifang ;
Chen, Juan ;
Ao, Yanhui .
JOURNAL OF HAZARDOUS MATERIALS, 2022, 440
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