In-situ formatting donor-acceptor polymer with giant dipole moment and ultrafast exciton separation

被引:97
作者
Cheng, Chang [1 ]
Yu, Jiaguo [1 ,2 ]
Xu, Difa [3 ]
Wang, Lei [4 ]
Liang, Guijie [4 ]
Zhang, Liuyang [2 ]
Jaroniec, Mietek [5 ]
机构
[1] Wuhan Univ Technol, State Key Lab Adv Technol Mat Synth & Proc, Wuhan 430070, Peoples R China
[2] China Univ Geosci, Fac Mat Sci & Chem, Lab Solar Fuel, 388 Lumo Rd, Wuhan 430074, Peoples R China
[3] Changsha Univ, Hunan Key Lab Appl Environm Photocatalysis, 98 Hongshan Rd, Changsha 410022, Peoples R China
[4] Hubei Univ Arts & Sci, Hubei Key Lab Low Dimens Optoelect Mat & Devices, Xiangyang 441053, Peoples R China
[5] Kent State Univ, Dept Chem & Biochem, Kent, OH 44242 USA
基金
美国国家科学基金会; 中国国家自然科学基金;
关键词
COVALENT ORGANIC FRAMEWORK; BAND-GAP; PHOTOCATALYST;
D O I
10.1038/s41467-024-45604-5
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
Donor-acceptor semiconducting polymers present countless opportunities for application in photocatalysis. Previous studies have showcased their advantages through direct bottom-up methods. Unfortunately, these approaches often involve harsh reaction conditions, overlooking the impact of uncontrolled polymerization degrees on photocatalysis. Besides, the mechanism behind the separation of electron-hole pairs (excitons) in donor-acceptor polymers remains elusive. This study presents a post-synthetic method involving the light-induced transformation of the building blocks of hyper-cross-linked polymers from donor-carbon-donor to donor-carbon-acceptor states, resulting in a polymer with a substantial intramolecular dipole moment. Thus, excitons are efficiently separated in the transformed polymer. The utility of this strategy is exemplified by the enhanced photocatalytic hydrogen peroxide synthesis. Encouragingly, our observations reveal the formation of intramolecular charge transfer states using time-resolved techniques, confirming transient exciton behavior involving separation and relaxation. This light-induced method not only guides the development of highly efficient donor-acceptor polymer photocatalysts but also applies to various fields, including organic solar cells, light-emitting diodes, and sensors. Donor-acceptor polymers have potential for application in photocatalysis, but often harsh synthetic conditions are required. Here, the authors report a post-synthetic method for conversion to donor-acceptor states, to give a polymer capable of enhancing photocatalytic hydrogen peroxide synthesis.
引用
收藏
页数:12
相关论文
共 48 条
[11]   Verifying the Charge-Transfer Mechanism in S-Scheme Heterojunctions Using Femtosecond Transient Absorption Spectroscopy [J].
Cheng, Chang ;
Zhang, Jianjun ;
Zhu, Bicheng ;
Liang, Guijie ;
Zhang, Liuyang ;
Yu, Jiaguo .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2023, 62 (08)
[12]   Rational Design of Covalent Heptazine Frameworks with Spatially Separated Redox Centers for High-Efficiency Photocatalytic Hydrogen Peroxide Production [J].
Cheng, Hao ;
Lv, Haifeng ;
Cheng, Jun ;
Wang, Lei ;
Wu, Xiaojun ;
Xu, Hangxun .
ADVANCED MATERIALS, 2022, 34 (07)
[13]   Dibenzothiophene-S,S-Dioxide-Based Conjugated Polymers: Highly Efficient Photocatalyts for Hydrogen Production from Water under Visible Light [J].
Dai, Chunhui ;
Xu, Shidang ;
Liu, Wei ;
Gong, Xuezhong ;
Panahandeh-Fard, Majid ;
Liu, Zitong ;
Zhang, Deqing ;
Xue, Can ;
Loh, Kian Ping ;
Liu, Bin .
SMALL, 2018, 14 (34)
[14]  
Glass R. S., 1999, ORGANOSULFUR CHEM 2
[15]   Conjugated Electron Donor-Acceptor Hybrid Polymeric Carbon Nitride as a Photocatalyst for CO2 Reduction [J].
Hayat, Asif ;
Rahman, Mati Ur ;
Khan, Iltaf ;
Khan, Javid ;
Sohail, Muhammad ;
Yasmeen, Humaira ;
Liu, Shu-yuan ;
Qi, Kezhen ;
Lv, Wenxiu .
MOLECULES, 2019, 24 (09)
[16]   Production of Hydrogen Peroxide by Photocatalytic Processes [J].
Hou, Huilin ;
Zeng, Xiangkang ;
Zhang, Xiwang .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2020, 59 (40) :17356-17376
[17]   A Donor-Acceptor [2]Catenane for Visible Light Photocatalysis [J].
Jiao, Yang ;
Dordevic, Luka ;
Mao, Haochuan ;
Young, Ryan M. ;
Jaynes, Tyler ;
Chen, Hongliang ;
Qiu, Yunyan ;
Cai, Kang ;
Zhang, Long ;
Chen, Xiao-Yang ;
Feng, Yuanning ;
Wasielewski, Michael R. ;
Stupp, Samuel, I ;
Stoddart, J. Fraser .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2021, 143 (21) :8000-8010
[18]   Engineering donor-acceptor conjugated organic polymers with boron nitride to enhance photocatalytic performance towards visible-light-driven metal-free selective oxidation of sulfides [J].
Lan, Xingwang ;
Li, Qing ;
Zhang, Yize ;
Li, Qi ;
Ricardez-Sandoval, Luis ;
Bai, Guoyi .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2020, 277
[19]   Reducing the Exciton Binding Energy of Donor-Acceptor-Based Conjugated Polymers to Promote Charge-Induced Reactions [J].
Lan, Zhi-An ;
Zhang, Guigang ;
Chen, Xiong ;
Zhang, Yongfan ;
Zhang, Kai A., I ;
Wang, Xinchen .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2019, 58 (30) :10236-10240
[20]   Photocatalytic Oxygen Evolution from Functional Triazine-Based Polymers with Tunable Band Structures [J].
Lan, Zhi-An ;
Fang, Yuanxing ;
Zhang, Yongfan ;
Wang, Xinchen .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2018, 57 (02) :470-474