SBA-15模板化共价三嗪框架增强光催化产氢

doi:10.1016/j.actphy.2025.100149

摘要/Abstract

摘要：

共价三嗪框架(CTFs)是一类极具吸引力的可见光响应无金属共价有机框架(COFs)，因其具有大比表面积、高氮含量、永久孔隙率以及高耐热性和化学稳定性等特性，被认为在光催化水分解制氢方面具有潜在的应用前景。然而，大多数CTFs在化学合成方面面临一定困难，且在光催化析氢反应(HER)过程中普遍表现出低电导率和严重的光生载流子复合现象。因此，材料的析氢性能高度依赖于CTFs的π-共轭结构及其合成方法，且实现具有明确结构的COFs纳米材料的可控合成仍具有高度挑战性。在本研究中，我们报道了以介孔二氧化硅分子筛SBA-15为模板，通过有机酸催化合成多孔CTF纳米结构的方法。SBA-15模板法制备的多孔网状CTF-S2在光催化HER中表现显著增强的催化活性，相较于微米级块体CTF-1 (4.1 μmol h⁻¹)提升了14倍。这种显著的HER性能提升主要归因于扩展的可见光吸收、加速的载流子转移以及优化的能带结构。

关键词: 光催化, 析氢反应, 共价有机框架, 模板合成, 多孔结构

Abstract:

Covalent triazine frameworks (CTFs) represent an attractive family of metal-free visible light-responsive covalent organic frameworks (COFs), possessing promising characteristics such as large specific surface area, rich nitrogen content, permanent porosity, and high thermal and chemical stability for photocatalytic hydrogen production via water splitting. Nevertheless, the majority of CTFs are confronted with difficulty in chemical synthesis and generally suffer from low electric conductivity and severe photogenerated charge carrier recombination during photocatalytic hydrogen evolution reaction (HER). The hydrogen-evolving performance highly depends on the structure of π-conjugated CTFs and the synthetic methods, and controlled synthesis of well-defined nanostructures is still highly challenging. In this work, we report the organic acid-catalyzed synthesis of porous CTF nanoarchitectures templated by mesoporous silica molecular sieve SBA-15 with a highly ordered hexagonal structure. The SBA-15-templated CTF-S2 nanorods exhibited a substantial increase in photocatalytic HER efficiency, with an impressive 14-fold enhancement compared to the micro-sized bulk CTF-1 (4.1 μmol h⁻¹). This remarkable improvement in the photocatalytic HER over SBA-templated CTF-S2 nanostructure is attributed to the extended visible light absorption, accelerated charge carrier transfer and the optimized band structure.

Key words: Photocatalysis, Hydrogen evolution reaction, Covalent organic frameworks, Template synthesis, Porous structure

赵呈孝, 李昭霖, 吴东方, 杨小飞. SBA-15模板化共价三嗪框架增强光催化产氢[J]. 物理化学学报, 2026, 42(1), 100149. doi: 10.1016/j.actphy.2025.100149

Chengxiao Zhao, Zhaolin Li, Dongfang Wu, Xiaofei Yang. SBA-15 templated covalent triazine frameworks for boosted photocatalytic hydrogen production[J]. Acta Phys. -Chim. Sin. 2026, 42(1), 100149. doi: 10.1016/j.actphy.2025.100149

链接本文: https://www.whxb.pku.edu.cn/CN/10.1016/j.actphy.2025.100149

https://www.whxb.pku.edu.cn/CN/Y2026/V42/I1/100149

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参考文献 44

1	T. Zhang, G. Zhang, L. Chen. Acc. Chem. Res. 2022, 55, 795. doi: 10.1021/acs.accounts.1c00693
2	C. Qian, L. Feng, W.L. Teo, J. Liu, W. Zhou, D. Wang, Y. Zhao. Nat. Rev. Chem. 2022, 6, 881. doi: 10.1038/s41570-022-00437-y
3	L. Wang, Y. Zhang. Small 2025, 21, 2408395. doi: 10.1002/smll.202408395
4	A. Rodríguez-Camargo, K. Endo, B.V. Lotsch. Angew. Chem. Int. Ed. 2024, 63, e202413096. doi: 10.1002/anie.202413096
5	L. Yuan, Y. Peng, Z.-J. Guan, Y. Fang. Acta Phys. Chim. Sin. 2025, 41, 100086. doi: 10.1016/j.actphy.2025.100086
6	Z. Lu, H. Lv, Q. Liu, Z. Wang. Acta Phys. Chim. Sin. 2024, 40, 2405005. doi: 10.3866/PKU.WHXB202405005
7	C. Zhuang, W. Li, Y. Chang, S. Li, Y. Zhang, Y. Li, J. Gao, G. Chen, Z. Kang. J. Mater. Chem. A 2024, 12, 5711. doi: 10.1039/D3TA07951A
8	J. Zhang, G. Yu, C. Yang, S. Li. Curr. Opin. Chem. Eng. 2024, 45, 101040. doi: 10.1016/j.coche.2024.101040
9	C. Krishnaraj, H.S. Jena, K. Leus, P. Van der Voort. Green Chem. 2020, 22, 1038. doi: 10.1039/C9GC03482J
10	A.J. Liang, W.B. Li, A.B. Li, H. Peng, G.F. Ma, L. Zhu, Z.Q. Lei, Y.X. Xu. Nano Res. 2024, 17, 7830. doi: 10.1007/s12274-024-6779-y
11	R. Sun, B. Tan. Chem. Eur. J. 2023, 29, e202203077. doi: 10.1002/chem.202203077
12	S.Y. Yu, J. Mahmood, H.J. Noh, J.M. Seo, S.M. Jung, S.H. Shin, Y.K. Im, I.Y. Jeon, J.B. Baek. Angew. Chem. Int. Ed. 2018, 57, 8438. doi: 10.1002/anie.201801128
13	T. Sun, Y. Liang, W. Luo, L. Zhang, X. Cao, Y. Xu. Angew. Chem. Int. Ed. 2022, 61, e202203327. doi: 10.1002/anie.202203327
14	Z. Yang, H. Chen, S. Wang, W. Guo, T. Wang, X. Suo, D.-E. Jiang, X. Zhu, I. Popovs, S. Dai. J. Am. Chem. Soc. 2020, 142, 6856. doi: 10.1021/jacs.0c00365
15	C. Zhao, Z. Li, X. Wu, H. Su, F.-Q. Bai, X. Ran, L. Yang, W. Fang, X. Yang. Small 2024, 20, 2400541. doi: 10.1002/smll.202400541
16	Z. Li, T. Li, J. Miao, C. Zhao, Y. Jing, F. Han, K. Zhang, X. Yang. Sci. China Mater. 2023, 66, 2290. doi: 10.1007/s40843-022-2394-6
17	T. Sun, Y. Liang, Y. Xu. Angew. Chem. Int. Ed. 2022, 61, e202113926. doi: 10.1002/anie.202113926
18	C.X. Wang, P. Lyu, Z. Chen, Y.X. Xu. J. Am. Chem. Soc. 2023, 145, 12745. doi: 10.1021/jacs.3c02874
19	Z.-A. Lan, M. Wu, Z. Fang, Y. Zhang, X. Chen, G. Zhang, X. Wang. Angew. Chem. Int. Ed. 2022, 61, e202201482. doi: 10.1002/anie.202201482
20	S.Q. Zhang, G. Cheng, L.P. Guo, N. Wang, B.E. Tan, S.B. Jin. Angew. Chem. Int. Ed. 2020, 59, 6007. doi: 10.1002/anie.201914424
21	K. Huang, D. Chen, X. Zhang, R. Shen, P. Zhang, D. Xu, X. Li. Acta Phys. Chim. Sin. 2024, 40, 2407020. doi: 10.3866/PKU.WHXB202407020
22	C.X. Wang, H.L. Zhang, W.J. Luo, T. Sun, Y.X. Xu. Angew. Chem. Int. Ed. 2021, 60, 25381. doi: 10.1002/anie.202109851
23	S. Li, M.-F. Wu, T. Guo, L.-L. Zheng, D. Wang, Y. Mu, Q.-J. Xing, J.-P. Zou. Appl. Catal. B Environ. 2020, 272, 118989. doi: 10.1016/j.apcatb.2020.118989
24	K. Shen, L. Zhang, X. Chen, L. Liu, D. Zhang, Y. Han, J. Chen, J. Long, R. Luque, Y. Li, B. Chen. Science 2018, 359, 206. doi: 10.1126/science.aao3403
25	H. Luo, Y.V. Kaneti, Y. Ai, Y. Wu, F. Wei, J. Fu, J. Cheng, C. Jing, B. Yuliarto, M. Eguchi, J. Na, Y. Yamauchi, S. Liu. Adv. Mater. 2021, 33, 2007318. doi: 10.1002/adma.202007318
26	R.-R. Liang, S.-Y. Jiang, R.-H. A, X. Zhao. Chem. Soc. Rev. 2020, 49, 3920. doi: 10.1039/D0CS00049C
27	F. Heck, L. Grunenberg, N. Schnabel, T. Sottmann, L. Yao, B.V. Lotsch, ChemRxiv Version 1 (2024), https://doi.org/10.26434/chemrxiv-2024-wd9ft.
28	I.E. Khalil, P. Das, H. Küçükkeçeci, V. Dippold, J. Rabeah, W. Tahir, J. Roeser, J. Schmidt, A. Thomas. Chem Mater 2024, 36, 8330. doi: 10.1021/acs.chemmater.4c01298
29	N. He, Y. Zou, C. Chen, M. Tan, Y. Zhang, X. Li, Z. Jia, J. Zhang, H. Long, H. Peng, K. Yu, B. Jiang, Z. Han, N. Liu, Y. Li, L. Ma. Nat. Commun. 2024, 15, 3896. doi: 10.1038/s41467-024-48160-0
30	X. Yang, L. Tian, X. Zhao, H. Tang, Q. Liu, G. Li. Appl. Catal. B Environ. 2019, 244, 240. doi: 10.1016/j.apcatb.2018.11.056
31	T. Zhang, Y. Hou, V. Dzhagan, Z. Liao, G. Chai, M. Löffler, D. Olianas, A. Milani, S. Xu, M. Tommasini, D.R.T. Zahn, Z. Zheng, E. Zschech, R. Jordan, X. Feng. Nat. Commun. 2018, 9, 1140. doi: 10.1038/s41467-018-03444-0
32	Y. Lu, Z. Li, J. Liang, X. Xu, G. Zhang, H. Min. Desalination 2024, 592, 118196. doi: 10.1016/j.desal.2024.118196
33	Z. Shen, X. Wang, D. Fan, X. Xu, Y. Lu. J. Mater. Sci. 2023, 58, 13154. doi: 10.1007/s10853-023-08849-x
34	J. Liu, W. Zan, K. Li, Y. Yang, F. Bu, Y. Xu. J. Am. Chem. Soc. 2017, 139, 11666. doi: 10.1021/jacs.7b05025
35	K. Wu, Q. Ye, L. Wang, F. Meng, H. Dai. Appl. Clay Sci. 2022, 229, 106660. doi: 10.1016/j.clay.2022.106660
36	S. Cao, B. Zhong, C. Bie, B. Cheng, F. Xu. Acta Phys. Chim. Sin. 2024, 40, 2307016. doi: 10.3866/PKU.WHXB202307016
37	L. Zhang, J. Zhang, J. Yu. H. García. Nat. Rev. Chem. 2025, 9, 328. doi: 10.1038/s41570-025-00698-3
38	J. Zhu, S. Wageh, A.A. Al-Ghamdi. Chin. J. Catal. 2023, 49, 5. doi: 10.1016/S1872-2067(23)64438-9
39	C. Wang, C. You, K. Rong, C. Shen, F. Yang, S. Li. Acta Phys. Chim. Sin. 2024, 40, 2307045. doi: 10.3866/PKU.WHXB202307045
40	S. Li, C. You, K. Rong, C. Zhuang, X. Chen, B. Zhang. Adv. Powder Mater. 2024, 3, 100183. doi: 10.1016/j.apmate.2024.100183
41	M. Cai, Y. Liu, K. Dong, X. Chen, S. Li. Chin. J. Catal. 2023, 52, 239. doi: 10.1016/S1872-2067(23)64496-1
42	D. Kong, X. Han, J. Xie, Q. Ruan, C.D. Windle, S. Gadipelli, K. Shen, Z. Bai, Z. Guo, J. Tang. ACS Catal. 2019, 9, 7697. doi: 10.1021/acscatal.9b02195
43	J.-H. Tsai, T.-Y. Lee, H.-L. Chiang. Nanomaterials 2023, 13, 1015. doi: 10.3390/nano13061015
44	Z. Li, T. Deng, S. Ma, Z. Zhang, G. Wu, J. Wang, Q. Li, H. Xia, S.-W. Yang, X. Liu. J. Am. Chem. Soc. 2023, 145, 8364. doi: 10.1021/jacs.2c11893

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