带有吸电子-Cl基团的供体-受体氮化碳的构建及其光催化性能

doi:10.1016/S1872-2067(20)63733-0

催化学报 ›› 2021, Vol. 42 ›› Issue (7): 1168-1175.DOI: 10.1016/S1872-2067(20)63733-0

带有吸电子-Cl基团的供体-受体氮化碳的构建及其光催化性能

张靖雯^a, 潘伦^a^,^b, 张香文^a^,^b, 史成香^a^,^#(), 邹吉军^a^,^b^,^*()

^a天津大学化学工程与技术学院, 绿色合成与转化教育部重点实验室, 天津300072
^b天津化学化工协同创新中心, 天津300072

收稿日期:2020-09-18 接受日期:2020-11-03 出版日期:2021-07-18 发布日期:2020-12-10
通讯作者: 史成香,邹吉军
基金资助:
国家自然科学基金(21676193);国家自然科学基金(21978200);国家自然科学基金(51661145026)

Donor-acceptor carbon nitride with electron-withdrawing chlorine group to promote exciton dissociation

Jing-Wen Zhang^a, Lun Pan^a^,^b, Xiangwen Zhang^a^,^b, Chengxiang Shi^a^,^#(), Ji-Jun Zou^a^,^b^,^*()

^aKey Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China
^bCollaborative Innovative Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China

Received:2020-09-18 Accepted:2020-11-03 Online:2021-07-18 Published:2020-12-10
Contact: Chengxiang Shi,Ji-Jun Zou
About author:^# Tel/Fax: +86-22-27892340; E-mail: cxshi@tju.edu.cn
^* Tel/Fax: +86-22-27892340; E-mail: jj_zou@tju.edu.cn;
Supported by:
National Natural Science Foundation of China(21676193);National Natural Science Foundation of China(21978200);National Natural Science Foundation of China(51661145026)

摘要/Abstract

摘要：

聚合物氮化碳(C₃N₄)因具有可见光响应特性、良好的化学稳定性、无毒性等优点而成为一类极具吸引力的光催化剂. 遗憾的是, 由于本征库仑相互作用, C₃N₄中的光生电子和空穴通常以激子的形式存在, 导致迁移到表面的光生电子和空穴数量减少, 从而降低了光催化活性, 因此人们做了大量的研究工作来促进激子解离成自由电子和空穴. D-A体系可以诱导内部电场的产生, 从而促进激子解离成自由电子和空穴, 因此, 构建供体-受体(D-A)体系是一种有效地促进激子解离的方法. 然后在内电场作用下, 自由电子和空穴也能够更加容易地转移到共聚物表面, 从而发生相应的光催化还原和氧化反应.
本文选择了2-氨基-4,6-二氯嘧啶(C₄H₃Cl₂N₃)作为单体, 与三聚氰胺共聚形成分子内共聚物(CNCl_x)来构建D-A体系. 由于分子结构相似, C₄H₃Cl₂N₃与C₃N₃(NH₂)₃分子具有良好的化学相容性. 在共聚过程中, C₄H₃Cl₂N₃在219~222 ºC升华, 三聚氰胺在300 °C升华, 在温度继续升高到550 ºC的过程中, 气相混合物充分混合并发生共聚反应. 在共聚过程中, 如果C₄H₃Cl₂N₃分子与C₃N₃(NH₂)₃反应, 那么三聚氰胺沿着这个方向的聚合将终止, 因此吸电子-Cl基团将全部位于共聚分子的末端.
相较于体相C₃N₄, CNCl_x样品活性均有所提高, 且随着-Cl基团数量的增加, CNCl_x样品活性先提高后降低, 其中CNCl_0.15样品活性最高. CNCl_0.15在可见光下的析氢速率是体相C₃N₄的15.3倍, 在420 nm处的表观量子效率为13.6%. 对RhB, MO和苯酚的降解速率分别为体相C₃N₄的5.82, 7.93和9.53倍. 构建分子内D-A体系以后, C₃N₄活性提高主要是因为随着末端-Cl基团的增加, 材料的吸光能力和激子解离效率提高. 而且-Cl基团也可以充当电子的俘获位点, 浓度进一步升高会降低电荷转移的效率使活性降低. EIS的奈奎斯特图和i-t曲线结果表明, CNCl_0.15的电弧半径最小, 光电流最大, 说明其具有最低的电阻和最高的载流子传输效率. 紫外光电子能谱测试结果表明, CNCl_x功函数值较小, 电子更容易在内部电场的作用下移动到表面, 而过量的-Cl基团增加了CNCl_0.2的功函数值, 导致CNCl_0.2样品的光催化活性降低.

关键词: 氮化碳, 供体-受体, 内电场, 激子, 产氢

Abstract:

Carbon nitride (C₃N₄) is promising for photocatalytic hydrogen production, but photogenerated electrons and holes in C₃N₄ usually tend to exist as excitons due to intrinsic Coulomb interactions making its photocatalytic activity unsatisfactory. Herein, a well-designed intramolecular C₃N₄-based donor-acceptor (D-A) photocatalytic system was constructed to promote exciton dissociation. Due to its good chemical compatibility with melamine and appropriate sublimation property, 2-amino-4,6-dichloropyrimidine unit was chosen as the monomer to react with melamine to construct intramolecular D-A system (CNCl_x). The hydrogen evolution rate of CNCl_0.15 is 15.3 times higher than that of bulk C₃N₄ under visible light irradiation, with apparent quantum efficiency of 13.6% at 420 nm. The enhanced activity is attributed to introduced electron-withdrawing -Cl group as terminal group in the resulted CNCl_x samples, which can build internal electric field to promote the exciton dissociation into free electron and hole. In addition, lower work function value of CNCl_x samples indicates that internal electric field can help free electrons and holes transfer to the surface of CNCl_x samples for photocatalytic reaction.

Key words: Carbon nitride, Donor-acceptor, Internal electric field, Exciton, Hydrogen production

张靖雯, 潘伦, 张香文, 史成香, 邹吉军. 带有吸电子-Cl基团的供体-受体氮化碳的构建及其光催化性能[J]. 催化学报, 2021, 42(7): 1168-1175.

Jing-Wen Zhang, Lun Pan, Xiangwen Zhang, Chengxiang Shi, Ji-Jun Zou. Donor-acceptor carbon nitride with electron-withdrawing chlorine group to promote exciton dissociation[J]. Chinese Journal of Catalysis, 2021, 42(7): 1168-1175.

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图/表 7

Fig. 1. (a) The XRD pattern BCN and CNClx; SEM images of BCN (b), CNCl0.05 (c), CNCl0.1 (d), CNCl0.15 (e), and CNCl0.2 (f).

Fig. 2. The TEM images of BCN (a), CNCl0.05 (b), CNCl0.1 (c), CNCl0.15 (d), CNCl0.2 (e); (f) BET surface area of bulk C3N4 and CNClx.

Fig. 3. (a) The FT-IR spectra and NMR spectra of bulk C3N4 and CNClx; (b) NMR spectra of bulk C3N4 and CNCl0.15.

Fig. 4. (a,b) High-resolution XPS spectra of the BCN and CNClx; (c) The structure of CNClx copolymer.

Fig. 5. (a) UV-vis absorption spectra; (b) Room-temperature EPR spectrum; (c) Time-resolution fluorescence spectra; (d) Electrochemical impedance spectroscopy of BCN and CNClx.

Fig. 6. (a) Photocatalytic hydrogen evolution rates of CN and CNClx samples under visible light irradiation; cycling stability test (b) and wavelength-dependent apparent quantum yield (c) of CNCl0.15; (d) Degradation of organic pollutants of CN and CNClx samples under visible light irradiation.

Fig. 7. Schematic illustration of proposed charge transfer in CNClx under visible-light irradiation.

参考文献

[1]	Y. Li, D. Zhang, J. Fan, Q. Xiang, Chin. J. Catal., 2021,42, 627-636.
[2]	Y. Li, D. Zhang, X. Feng, Q. Xiang, Chin. J. Catal., 2020,41, 21-30.
[3]	I. F. Teixeira, E. C. M Barbosa, S. C. E. Tsang, P. H. C. Camargo, Chem. Soc. Rev., 2018,47, 7783-7817.
[4]	H. Wang, X. Zhang, Y. Xie, Mater. Today, 2019,23, 72-86.
[5]	L. Lin, Z. Lin, J. Zhang, X. Cai, W. Lin, Z. Yu, X. Wang, Nat. Catal., 2020,3, 649-655.
[6]	G. Zhang, G. Li, Z.-A. Lan, L. Lin, A. Savateev, T. Heil, S. Zafeiratos, X. Wang, M. Antonietti, Angew. Chem. Int. Ed., 2017,56, 13445-13449.
[7]	C. T. Poon, D. Wu, V. W. Yam, Angew. Chem. Int. Ed., 2016,55, 3647-3651.
[8]	X. Fan, L. Zhang, R. Cheng, M. Wang, M. Li, Y. Zhou, J. Shi, ACS Catal., 2015,5, 5008-5015.
[9]	J. Zhang, G. Zhang, X. Chen, S. Lin, L. Mçhlmann, G. D. G Lipner, M. Antonietti, S. Blechert, X. Wang, Angew. Chem. Int. Ed., 2012,51, 3183-3187.
[10]	G. Zhang, X. Wang, J. Catal., 2013,307, 246-253.
[11]	S. Zhao, X. Zhao, H. Zhang, J. Li, Y. Zhu, Nano Energy, 2017,35, 405-414.
[12]	J. Li, D. Wu, J. Iocozzia, H. Du, X. Liu, Y. Yuan, W. Zhou, Z. Li, Z. Xue, Z. Lin, Angew. Chem. Int. Ed., 2019,58, 1985-1989.
[13]	J. Zhang, X. Chen, K. Takanabe, K. Maeda, K. Domen, J. D. Epping, X. Fu, M. Antonietti, X. Wang, Angew. Chem. Int. Ed., 2010,49, 441-444.
[14]	H. Kim, S. Gim, T. H. Jeon, H. Kim, W. Choi, ACS Appl. Mater. Interfaces, 2017,9, 40360-40368.
[15]	Y. Yu, W. Yan, W. Gao, P. Li, X. Wang, S. Wu, W. Song, K. Ding, J. Mater. Chem. A, 2017,5, 17199-17203.
[16]	K. Li, M. Sun, W.-D. Zhang, Carbon, 2018,134, 134-144.
[17]	C. Ye, X.-Z. Wang, J.-X. Li, Z.-J. Li, X.-B. Li, L.-P. Zhang, B. Chen, C.-H. Tung, L.-Z. Wu, ACS Catal., 2016,6, 8336-8341.
[18]	M. Marple, J. Badger, I. Hung, Z. Gan, K. Kovnir, S. Sen, Angew. Chem. Int. Ed., 2017,56, 9777-9781.
[19]	G. Liu, G. Zhao, W. Zhou, Y. Liu, H. Pang, H. Zhang, D. Hao, X. Meng, P. Li, T. Kako, J. Ye, Adv. Funct. Mater., 2016,26, 6822-6829.
[20]	H. Ou, X. Chen, L. Lin, Y. Fang, X. Wang, Angew. Chem. Int. Ed., 2018,57, 8729-8733.
[21]	F. Li, M. Han, Y. Jin, L. Zhang, T. Li, Y. Gao, C. Hu, Appl. Catal. B, 2019,256, 117705.
[22]	X. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin, J. M. Carlsson, K. Domen, M. Antonietti, Nat. Mater., 2009,8, 76-80.
[23]	X. Mamtimin, R. Matsidik, I. Nurulla, Polymer, 2010,51, 437-446.
[24]	J. Sehnert, K. Baerwinkel, J. Senker, J. Phys. Chem. B, 2007,111, 10671-10680.
[25]	Y. Hu, Y. Shim, J. Oh, S. Park, S. Park, Y. Ishii, Chem. Mater., 2017,29, 5080-5089.
[26]	Z. -F. Huang, J. Song, L. Pan, Z. Wang, X. Zhang, J.-J. Zou, W. Mi, X. Zhang, L. Wang, Nano Energy, 2015,12, 646-656.
[27]	R. Gao, L. Pan, H. Wang, X. Zhang, L. Wang, J.-J. Zou, ACS Catal., 2018,8, 8420-8429.
[28]	R. Gao, L. Pan, H. Wang, Y. Yao, X. Zhang, L. Wang, J.-J. Zou, Adv. Sci., 2019,6, 1900054.
[29]	Q. Yang, S. Hu, Y. Yao, X. Lin, H. Du, Y. Yuan, Chin. J. Catal., 2021,42, 217-224.
[30]	L. Hao, L. Kang, H. Huang, L. Ye, K. Han, S. Yang, H. Yu, M. Batmunkh, Y. Zhang, T. Ma, Adv. Mater., 2019,31, 1900546.
[31]	P. Pasman, F. Rob, J. W. Verhoeven, J. Am. Chem. Soc., 1982,104, 5127-5133.
[32]	Z. Sun, Y. Jiang, L. Zeng, L. Huang, ChemSusChem, 2019,12, 1325-1333.
[33]	H. Yu, J. Li, Y. Zhang, S. Yang, K. Han, F. Dong, T. Ma, H. Huang, Angew. Chem. Int. Ed., 2019,58, 3880-3884.
[34]	Q. Han, Z. Cheng, B. Wang, H. Zhang, L. Qu, ACS Nano, 2018,12, 5221-5227.
[35]	F. Chen, Z. Ma, L. Ye, T. Ma, T. Zhang, Y. Zhang, H. Huang, Adv. Mater., 2020,32, 1908350.
[36]	H. Wang, S. Jiang, S. Chen, X. Zhang, W. Shao, X. Sun, Z. Zhao, Q. Zhang, Y. Luo, Y. Xie, Chem. Sci., 2017,8, 4087-4092.
[37]	F. Liu, R. Shi, Z. Wang, Y. Weng, C. M. Che, Y. Chen, Angew. Chem. Int. Ed., 2019,58, 11791-11795.
[38]	A. Kahn, Mater. Horizons, 2016,3, 7-10.
[39]	Y. Zhou, C. Fuentes-Hernandez, J. Shim, J. Meyer, A. J. Giordano, H. Li, P. Winget, T. Papadopoulos, H. Cheun, J. Kim, M. Fenoll, A. Dindar, W. Haske, E. Najafabadi, T. M. Khan, H. Sojoudi, S. Barlow, S. Graham, J.-L. Brédas, S. R. Marder, A. Kahn, B. Kippelen, Science, 2012,336, 327.

带有吸电子-Cl基团的供体-受体氮化碳的构建及其光催化性能

Donor-acceptor carbon nitride with electron-withdrawing chlorine group to promote exciton dissociation

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