Citation: Zhao Lu, Hu Lv, Qinzhuang Liu, Zhongliao Wang. Modulating NH₂ Lewis Basicity in CTF-NH₂ through Donor-Acceptor Groups for Optimizing Photocatalytic Water Splitting[J]. Acta Physico-Chimica Sinica, ;2024, 40(12): 240500. doi: 10.3866/PKU.WHXB202405005 shu

Modulating NH₂ Lewis Basicity in CTF-NH₂ through Donor-Acceptor Groups for Optimizing Photocatalytic Water Splitting

Zhao Lu ¹ ,
Hu Lv ² ,
Qinzhuang Liu ³ ,
Zhongliao Wang ^3,,

1.
HKUST Shenzhen-Hong Kong Collaborative Innovation Research Institute, Shenzhen 518000, Guangdong Province, China;
2.
School of Construction Engineering, Shenzhen Polytechnic University, Shenzhen 518000, Guangdong Province, China;
3.
Anhui Province Industrial Generic Technology Research Center for Alumics Materials, Anhui Province Key Laboratory of Pollutant Sensitive Materials and Environmental Remediation, School of Physics and Electronic Information, Huaibei Normal University, Huaibei 235000, Anhui Province, China

Corresponding author: Zhongliao Wang, wangzl@chnu.edu.cn
Received Date: 7 May 2024
Revised Date: 27 May 2024
Accepted Date: 28 May 2024

Fund Project: This work was supported by the Project of Hetao Shenzhen-Hong Kong Science and Technology Innovation Cooperation Zone (HZQB-KCZYB-2020083), Shenzhen Science and Technology Program (KCXFZ20211020163816023), Shenzhen Zhongdi Construction Engineering Co., Ltd. cooperation project (22100245), Key Research Project in Natural Sciences for Higher Education Institutions by the Ministry of Education (2022AH050396).

Photocatalytic water splitting (PWS) provides an optimal approach for the sustainable production of green hydrogen. NH₂-modified covalent triazine frameworks (CTFs-NH₂) hold potential in PWS due to robust light uptake, optimal charge separation, and considerable redox potential. However, the high surface reaction barriers hinder the efficiency of PWS owing to the conversion difficulty of intermediate products. Modulating the Lewis basicity of NH₂ on CTFs offers a feasible route for addressing this challenge. In this work, electron-donating ethyl (C₂H₅) and electron-withdrawing 5-fluoroethyl groups (C₂F₅) are introduced at the para position of amine groups, producing C₂H₅-CTF-NH₂ and C₂F₅-CTF-NH₂, to adjust the Lewis basicity of CTF-NH₂. Through DFT calculations, the optical properties, excited states, electronic structures, dipole moments, and surface reaction processes of the CTF-NH₂, C₂H₅-CTF-NH₂ and C₂F₅-CTF-NH₂ are simulated. The results indicate that the electron-withdrawing C₂F₅ group can decrease the electron density and Lewis basicity on NH₂, thereby lowering the energy barriers for hydrogen and oxygen evolution reactions, effectively ameliorating the PWS efficiency of CTF-NH₂. This work unveils an innovative approach for donor-acceptor-regulated CTFs for the application of PWS.
- Donor,
- Acceptor,
- Water splitting,
- CTFs,
- Lewis basicity
1. [1]
  (1) Bie, C.; Wang, L.; Yu, J. Chem 2022, 8, 1567. doi:10.1016/j.chempr.2022.04.013
2. [2]
  (2) Tao, S.; Wan, S.; Huang, Q.; Li, C.; Yu, J.; Cao, S. Chin. J. Struct. Chem. 2022, 41, 2206048. doi:10.14102/j.cnki.0254-5861.2022-0068
3. [3]
  (3) Yang, Y.; Wu, J.; Cheng, B.; Zhang, L.; Al-Ghamdi, A. A.; Wageh, S.; Li, Y. Chin. J. Struct. Chem. 2022, 41, 2206006. doi:10.14102/j.cnki.0254-5861.2022-0124
4. [4]
  (4) Gao, H.; Zhang, P.; Qin, H.; Zhang, S.; Guo, J. J. Materiomics 2024, 10, 601. doi:10.1016/j.jmat.2023.08.010
5. [5]
  (5) He, B.; Wang, Z.; Xiao, P.; Chen, T.; Yu, J.; Zhang, L. Adv. Mater. 2022, 34, 2203225. doi:10.1002/adma.202203225
6. [6]
  (6) Van Viet, P.; Nguyen, T.-D.; Bui, D.-P.; Thi, C.M. J. Materiomics 2022, 8, 1. doi:10.1016/j.jmat.2021.06.006
7. [7]
  (7) Zhu, B.; Tan, H.; Fan, J.; Cheng, B.; Yu, J.; Ho, W. J. Materiomics 2021, 7, 988. doi:10.1016/j.jmat.2021.02.015
8. [8]
  (8) Gao, R.; He, H.; Bai, J.; Hao, L.; Shen, R.; Zhang, P.; Li, Y.; Li, X. Chin. J. Struct. Chem. 2022, 41, 2206031. doi:10.14102/j.cnki.0254-5861.2022-0096
9. [9]
  (9) Hu, Y.; Li, X.; Wang, W.; Deng, F.; Han, L.; Gao, X.; Feng, Z.; Chen, Z.; Huang, J.; Zeng, F.; Dong, F. Chin. J. Struct. Chem. 2022, 41, 2206069. doi:10.14102/j.cnki.0254-5861.2022-0103
10. [10]
  (10) Wang, Z.; Wang, J.; Zhang, J.; Dai, K. Acta Phys. -Chim. Sin. 2023, 39, 2209037. doi:10.3866/PKU.WHXB202209037
11. [11]
  (11) Sun, G.; Zhang, J.; Cheng, B.; Yu, H.; Yu, J.; Xu, J. Chem. Eng. J. 2023, 476, 146818. doi:10.1016/j.cej.2023.146818
12. [12]
  (12) Liu, B.; Cai, J.; Zhang, J.; Tan, H.; Cheng, B.; Xu, J. Chin. J. Catal. 2023, 51, 204. doi:10.1016/s1872-2067(23)64466-3
13. [13]
  (13) Cao, S.; Zhong, B.; Bie, C.; Cheng, B.; Xu, F. Acta Phys. -Chim. Sin. 2024, 40, 2307016. doi:10.3866/PKU.WHXB202307016
14. [14]
  (14) Wu, X.; Chen, G.; Wang, J.; Li, J.; Wang, G. Acta Phys. -Chim. Sin. 2023, 39, 2212016. doi:10.3866/PKU.WHXB202212016
15. [15]
  (15) Cheng, C.; He, B.; Fan, J.; Cheng, B.; Cao, S.; Yu, J. Adv. Mater. 2021, 33, 2100317. doi:10.1002/adma.202100317
16. [16]
  (16) Zhang, Y.; Zhang, Z. J. Mater. Sci. Technol. 2024, 171, 147. doi:10.1016/j.jmst.2023.06.048
17. [17]
  (17) Li, Z.; Liu, W.; Chen, C.; Ma, T.; Zhang, J.; Wang, Z. Acta Phys. -Chim. Sin. 2023, 39, 202208030. doi:10.3866/PKU.WHXB202208030
18. [18]
  (18) Wang, X.; Zhang, Y.; Jiang, S.; Su, J.; Song, S. J. Mater. Sci. Technol. 2024, 171, 94. doi:10.1016/j.jmst.2023.06.041
19. [19]
  (19) Cheng, C.; Yu, J.; Xu, D.; Wang, L.; Liang, G.; Zhang, L.; Jaroniec, M. Nat. Commun. 2024, 15, 1313. doi:10.1038/s41467-024-45604-5
20. [20]
  (20) Sun, P.; Zhang, J.; Song, Y.; Mo, Z.; Chen, Z.; Xu, H. Acta Phys. -Chim. Sin. 2024, 40, 2311001. doi:10.3866/PKU.WHXB202311001
21. [21]
  (21) Wu, Y.; Qu, M.; Jiang, S.; Zhang, J.; Song, S. Sci. China Mater. 2024, 67, 524. doi:10.1007/s40843-023-2760-1
22. [22]
  (22) Hao, L.; Shen, R.; Qin, C.; Li, N.; Hu, H.; Liang, G.; Li, X. Sci. China Mater. 2024, 67, 504. doi:10.1007/s40843-023-2747-6
23. [23]
  (23) Sun, T.; Li, C.; Bao, Y.; Fan, J.; Liu, E. Acta Phys. -Chim. Sin. 2023, 39, 2212009. doi:10.3866/PKU.WHXB202212009
24. [24]
  (24) Wang, M.; Wang, P.; Wang, X.; Chen, F.; Yu, H. J. Mater. Sci. Technol. 2024, 174, 168. doi:10.1016/j.jmst.2023.06.065
25. [25]
  (25) Zhu, B.; Sun, J.; Zhao, Y.; Zhang, L.; Yu, J. Adv. Mater. 2024, 36, 2310600. doi:10.1002/adma.202310600
26. [26]
  (26) Zhao, B.; Zhong, W.; Chen, F.; Wang, P.; Bie, C.; Yu, H. Chin. J. Catal. 2023, 52, 127. doi:10.1016/s1872-2067(23)64491-2
27. [27]
  (27) Liu, D.; Sun, B.; Bai, S.; Gao, T.; Zhou, G. Chin. J. Catal. 2023, 50, 273. doi:10.1016/s1872-2067(23)64462-6
28. [28]
  (28) Yang, W.; Zhang, J.; Xu, Q.; Yang, Y.; Zhang, L. Acta Phys. -Chim. Sin. 2024, 40, 2312014. doi:10.3866/pku.Whxb202312014
29. [29]
  (29) Yu, W.; Bie, C. Acta Phys. -Chim. Sin. 2024, 40, 2307022. doi:10.3866/PKU.WHXB202307022
30. [30]
  (30) Wang, J.; Wang, Z.; Zhang, J.; Dai, K. Chin. J. Struct. Chem. 2023, 42, 100202. doi:10.1016/j.cjsc.2023.100202
31. [31]
  (31) Wang, G.; Lv, S.; Shen, Y.; Li, W.; Lin, L.; Li, Z. J. Materiomics 2024, 10, 315. doi:10.1016/j.jmat.2023.05.014
32. [32]
  (32) He, J.; Wang, X.; Jin, S.; Liu, Z.-Q.; Zhu, M. Chin. J. Catal. 2022, 43, 1306. doi:10.1016/s1872-2067(21)63936-0
33. [33]
  (33) Hao, L.; Shen, R.; Liang, G.; Kang, M.; Huang, C.; Zhang, P.; Li, X. Appl. Catal. B-Environ. Energy 2024, 348, 123837. doi:10.1016/j.apcatb.2024.123837
34. [34]
  (34) Qiu, J.; Meng, K.; Zhang, Y.; Cheng, B.; Zhang, J.; Wang, L.; Yu, J. Adv. Mater. 2024, 36, 2400288. doi:10.1002/adma.202400288
35. [35]
  (35) Sun, R.; Hu, X.; Shu, C.; Zheng, L.; Wang, S.; Wang, X.; Tan, B. Chin. J. Catal. 2023, 55, 159. doi:10.1016/s1872-2067(23)64552-8
36. [36]
  (36) Yu, Z.; Yue, X.; Fan, J.; Xiang, Q. ACS Catal. 2022, 12, 6345. doi:10.1021/acscatal.2c01563
37. [37]
  (37) Wang, N.; Cheng, L.; Liao, Y.; Xiang, Q. Small 2023, 19, 2300109. doi:10.1002/smll.202300109
38. [38]
  (38) Niu, Q.; Mi, L.; Chen, W.; Li, Q.; Zhong, S.; Yu, Y.; Li, L. Chin. J. Catal. 2023, 50, 45. doi:10.1016/s1872-2067(23)64457-2
39. [39]
  (39) Shen, R.; Hao, L.; Ng, Y.H.; Zhang, P.; Arramel, A.; Li, Y.; Li, X. Chin. J. Catal. 2022, 43, 2453. doi:10.1016/s1872-2067(22)64104-4
40. [40]
  (40) Zhu, B.; Zhang, L.; Cheng, B.; Yu, Y.; Yu, J. Chin. J. Catal. 2021, 42, 115. doi:10.1016/s1872-2067(20)63598-7
41. [41]
  (41) Huang, G.; Lin, G.; Niu, Q.; Bi, J.; Wu, L. J. Mater. Sci. Technol. 2022, 116, 41. doi:10.1016/j.jmst.2021.11.035
42. [42]
  (42) Li, Z.; Li, T.; Miao, J.; Zhao, C.; Jing, Y.; Han, F.; Zhang, K.; Yang, X. Sci. China Mater. 2023, 66, 2290. doi:10.1007/s40843-022-2394-6
43. [43]
  (43) Lu, Z.; Xu, X.; Wang, Z. Sep. Purif. Technol. 2024, 330, 125457. doi:10.1016/j.seppur.2023.125457
44. [44]
  (44) Huang, T.; Wang, R.; Zhang, J.; Wang, J.; Ge, H.; Ren, J.; Zheng, Z. Chem. Eng. J. 2023, 467, 143469. doi:10.1016/j.cej.2023.143469
45. [45]
  (45) Ju, Y.; Wang, Z.; Lin, H.; Hou, R.; Li, H.; Wang, Z.; Zhi, R.; Lu, X.; Tang, Y.; Chen, F. Chem. Eng. J. 2024, 479, 147800. doi:10.1016/j.cej.2023.147800
46. [46]
  (46) Zheng, L.-L.; Zhang, L.-S.; Chen, Y.; Tian, L.; Jiang, X.-H.; Chen, L.-S.; Xing, Q.-J.; Liu, X.-Z.; Wu, D.-S.; Zou, J.-P. Chin. J. Catal. 2022, 43, 811. doi:10.1016/s1872-2067(21)63892-5
47. [47]
  (47) Chen, D.; Wang, Z.; Fu, J.; Zhang, J.; Dai, K. Sci. China Mater. 2024, 67, 541. doi:10.1007/s40843-023-2770-8
48. [48]
  (48) Huang, R.; Zhang, Y.; Li, W.; Zhang, W.; Fang, Y.; Zhang, W.; Cui, A.; Ying, Y.; Shi, X. J. Mater. Sci. Technol. 2024, 170, 167. doi:10.1016/j.jmst.2023.05.065
49. [49]
  (49) Pan, J.; Zhang, A.; Zhang, L.; Dong, P. Chin. J. Catal. 2024, 58, 180. doi:10.1016/s1872-2067(23)64609-1
50. [50]
  (50) Wang, L.; Cheng, W.; Wang, J.; Yang, J.; Liu, Q. Chin. J. Catal. 2024, 58, 194. doi:10.1016/s1872-2067(23)64602-9
51. [51]
  (51) Gao, S.; Wan, S.; Yu, J.; Cao, S. Adv. Sustain. Syst. 2022, 7, 2200130. doi:10.1002/adsu.202200130
52. [52]
  (52) Wang, V.; Xu, N.; Liu, J.-C.; Tang, G.; Geng, W.-T. Comput. Phys. Commun. 2021, 267, 108033. doi:10.1016/j.cpc.2021.108033
53. [53]
  (53) Lu, T.; Chen, F. J. Comput. Chem. 2012, 33, 580. doi:10.1002/jcc.22885
1. [1]
  Yonghui ZHOU , Rujun HUANG , Dongchao YAO , Aiwei ZHANG , Yuhang SUN , Zhujun CHEN , Baisong ZHU , Youxuan ZHENG . Synthesis and photoelectric properties of fluorescence materials with electron donor-acceptor structures based on quinoxaline and pyridinopyrazine, carbazole, and diphenylamine derivatives. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 701-712. doi: 10.11862/CJIC.20230373
2. [2]
  Haiping Wang . A Streamlined Method for Drawing Lewis Structures Using the Valence State of Outer Atoms. University Chemistry, 2024, 39(8): 383-388. doi: 10.12461/PKU.DXHX202401073
3. [3]
  Hao WANG , Kun TANG , Jiangyang SHAO , Kezhi WANG , Yuwu ZHONG . Electro-copolymerized film of ruthenium catalyst and redox mediator for electrocatalytic water oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2193-2202. doi: 10.11862/CJIC.20240176
4. [4]
  Bo YANG , Gongxuan LÜ , Jiantai MA . Nickel phosphide modified phosphorus doped gallium oxide for visible light photocatalytic water splitting to hydrogen. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 736-750. doi: 10.11862/CJIC.20230346
5. [5]
  Xingyuan Lu , Yutao Yao , Junjing Gu , Peifeng Su . Energy Decomposition Analysis and Its Application in the Many-Body Effect of Water Clusters. University Chemistry, 2025, 40(3): 100-107. doi: 10.12461/PKU.DXHX202405074
6. [6]
  Renqing Lü , Shutao Wang , Fang Wang , Guoping Shen . Computational Chemistry Aided Organic Chemistry Teaching: A Case of Comparison of Basicity and Stability of Diazine Isomers. University Chemistry, 2025, 40(3): 76-82. doi: 10.12461/PKU.DXHX202404119
7. [7]
  Yan Xiao , Shuling Li , Yifan Li , Jianing Fan , Linlin Shi . Discovering the Beauty of Life: Adding Some “Ingredients” to Crystals. University Chemistry, 2024, 39(6): 366-372. doi: 10.3866/PKU.DXHX202312025
8. [8]
  Jingzhao Cheng , Shiyu Gao , Bei Cheng , Kai Yang , Wang Wang , Shaowen Cao . 4-氨基-1H-咪唑-5-甲腈修饰供体-受体型氮化碳光催化剂的构建及其高效光催化产氢研究. Acta Physico-Chimica Sinica, 2024, 40(11): 2406026-. doi: 10.3866/PKU.WHXB202406026
9. [9]
  Zhuo WANG , Junshan ZHANG , Shaoyan YANG , Lingyan ZHOU , Yedi LI , Yuanpei LAN . Preparation and photocatalytic performance of CeO₂-reduced graphene oxide by thermal decomposition. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1708-1718. doi: 10.11862/CJIC.20240067
10. [10]
  Lan Ma , Cailu He , Ziqi Liu , Yaohan Yang , Qingxia Ming , Xue Luo , Tianfeng He , Liyun Zhang . Magical Surface Chemistry: Fabrication and Application of Oil-Water Separation Membranes. University Chemistry, 2024, 39(5): 218-227. doi: 10.3866/PKU.DXHX202311046
11. [11]
  Supin Zhao , Jing Xie . Understanding the Vibrational Stark Effect of Water Molecules Using Quantum Chemistry Calculations. University Chemistry, 2025, 40(3): 178-185. doi: 10.12461/PKU.DXHX202406024
12. [12]
  Min LIU , Huapeng RUAN , Zhongtao FENG , Xue DONG , Haiyan CUI , Xinping WANG . Neutral boron-containing radical dimers. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 123-130. doi: 10.11862/CJIC.20240362
13. [13]
  Qin Hu , Liuyun Chen , Xinling Xie , Zuzeng Qin , Hongbing Ji , Tongming Su . Ni掺杂构建电子桥及激活MoS₂惰性基面增强光催化分解水产氢. Acta Physico-Chimica Sinica, 2024, 40(11): 2406024-. doi: 10.3866/PKU.WHXB202406024
14. [14]
  Jia Zhou . Constructing Potential Energy Surface of Water Molecule by Quantum Chemistry and Machine Learning: Introduction to a Comprehensive Computational Chemistry Experiment. University Chemistry, 2024, 39(3): 351-358. doi: 10.3866/PKU.DXHX202309060
15. [15]
  Gonglan Ye , Xia Yin , Feng Xu , Peng Yang , Yingpeng Wu , Huilong Fei . Innovations in “Four-in-One” Inorganic Chemistry Education. University Chemistry, 2024, 39(8): 136-141. doi: 10.3866/PKU.DXHX202401071
16. [16]
  Liang TANG , Jingfei NI , Kang XIAO , Xiangmei LIU . Synthesis and X-ray imaging application of lanthanide-organic complex-based scintillators. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1892-1902. doi: 10.11862/CJIC.20240139
17. [17]
  Chengbin Gong , Guona Zhang , Qian Tang , Hong Lei , Ling Kong , Wenshan Ren . Development of a Practical Teaching System for the Applied Chemistry Major Emphasizing “Industry-Education Integration, University-Enterprise Cooperation, and Multi-Dimensional Combination”. University Chemistry, 2024, 39(6): 220-225. doi: 10.3866/PKU.DXHX202309104
18. [18]
  Jiaxuan Zuo , Kun Zhang , Jing Wang , Xifei Li . 锂离子电池Ni-Co-Mn基正极材料前驱体的形核调控及机制. Acta Physico-Chimica Sinica, 2025, 41(1): 2404042-. doi: 10.3866/PKU.WHXB202404042
19. [19]
  Qiqi Li , Su Zhang , Yuting Jiang , Linna Zhu , Nannan Guo , Jing Zhang , Yutong Li , Tong Wei , Zhuangjun Fan . 前驱体机械压实制备高密度活性炭及其致密电容储能性能. Acta Physico-Chimica Sinica, 2025, 41(3): 2406009-. doi: 10.3866/PKU.WHXB202406009
20. [20]
  Jiahong ZHENG , Jingyun YANG . Preparation and electrochemical properties of hollow dodecahedral CoNi₂S₄ supported by MnO₂ nanowires. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1881-1891. doi: 10.11862/CJIC.20240170

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(413)
HTML views(89)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Modulating NH2 Lewis Basicity in CTF-NH2 through Donor-Acceptor Groups for Optimizing Photocatalytic Water Splitting

Metrics

通讯作者: 陈斌, bchen63@163.com

Modulating NH₂ Lewis Basicity in CTF-NH₂ through Donor-Acceptor Groups for Optimizing Photocatalytic Water Splitting