调控亚乙烯基连接的噻吩并噻吩共价有机框架的电子推拉效应以增强选择性光催化

doi:10.1016/S1872-2067(26)65102-9

摘要/Abstract

摘要：

共价有机框架(COF)因其结构可精细调控、兼具有序多孔与π共轭等特征, 在光催化领域受到广泛关注. 通过策略性地选择有机构筑单元及连接键类型, 可有效调控COF的电子结构, 进而提升其光催化性能. 传统极性亚胺键COF在结构稳定性、π共轭延展性以及电荷传输方面仍存在明显局限. 相较之下, 亚乙烯基连接可赋予COF全共轭结构, 使其兼具更优越的结构稳定性、更宽的可见光吸收范围以及更高效的电荷转移能力. 此外, 引入具有电子推拉效应的构筑单元能够有效抑制光生电荷重组. 因此, 合理设计兼具亚乙烯基连接与电子推拉效应的COF, 是增强其选择性光催化性能的关键.

基于此, 本研究以异构噻吩并噻吩为电子供体, 苯并[c][1,2,5]噻二唑及苯并[c][1,2,5]噁二唑为电子受体, 通过亚乙烯基连接成功构筑了四种COF: MPBTD-T32T-COF、MPBTD-T23T-COF、MPBO-T32T-COF和MPBO-T23T-COF. 通过协同调控亚乙烯基连接的COF的电子推拉效应, 增强选择性光催化. 粉末X射线衍射结果表明, 四种COF均呈现高结晶性的AA堆叠模式, 其中噻吩并[3,2-b]噻吩单元赋予了材料更优异的平面性与结晶度. 傅里叶变换红外光谱、固体核磁共振碳谱及元素分析确证了四种COF的成功聚合, 氮气吸附-脱附实验则证实了材料内部丰富的微孔结构. 理论计算揭示了四种COF的最高占据分子轨道(HOMO)与最低未占据分子轨道(LUMO)分别局域于噻吩并噻吩供体与苯并[c][1,2,5]噻(噁)二唑受体单元, 证实了COF内存在显著的电子推拉效应. 光学性质研究显示, 四种材料均具备宽的可见光吸收范围, 且噻吩并[3,2-b]噻吩基COF较其异构体表现出更窄的光学带隙. 莫特-肖特基曲线证实四种COF均为n型半导体, 其电子结构完全满足氧气还原生成超氧自由基的热力学要求. 光电化学测试表明, MPBTD-T32T-COF在四种材料中展现出最高效的光生电荷分离与迁移能力. 在光催化选择性硫醚氧化反应中, 性能由高到低依次为: MPBTD-T32T-COF > MPBTD-T23T-COF > MPBO-T32T-COF > MPBO-T23T-COF. 得益于其优异的电荷传输动力学及最有利的氧气吸附能, MPBTD-T32T-COF表现出最佳的光催化性能. 循环实验证明该催化剂具有良好的循环稳定性, 循环使用四次后仍能保持对苯基甲基硫醚的高转化率. 控制实验与电子顺磁共振谱证实, 超氧自由基为反应的主要活性氧物种. 此外, 底物拓展实验表明MPBTD-T32T-COF具有良好的普适性, 可高效转化多种带有吸/供电子基团的芳香族及脂肪族硫醚衍生物.

综上, 本研究通过融合异构工程与电子推拉效应协同策略, 成功构建了一种基于亚乙烯基连接的COF光催化体系, 并将其应用于硫醚的高效选择性氧化. 研究系统阐释了其内在的构效关系, 所得结果有望为面向选择性有机转化的COF精准设计提供一种可行的分子设计思路.

关键词: 共价有机框架, 全共轭, 超氧自由基, 光催化氧化反应, 有机硫化物

Abstract:

Covalent organic frameworks (COFs) unveil exceptional potential for selective photocatalysis, owing to their molecularly tunable structures. Herein, four COFs are designed with vinylene-linked isomeric thienothiophenes. Thereby, the condensation of 4,7-bis(2,6-dimethylpyridin-4-yl)benzo[c] [1,2,5]thiadiazole (MPBTD) and 4,7-bis(2,6-dimethylpyridin-4-yl)benzo[c][1,2,5]oxadiazole (MPBO) with thieno[3,2-b]thiophene-2,5-dicarbaldehyde (T32T) and thieno[2,3-b]thiophene- 2,5-dicarbaldehyde (T23T) yields MPBTD-T32T-COF, MPBTD-T23T-COF, MPBO-T32T-COF, and MPBO-T23T-COF, respectively. Comprehensive characterizations and theoretical calculations confirm the well-defined crystalline porous structures and distinct optoelectronic properties of these four COFs. Notably, the electron-withdrawing units, benzo[c][1,2,5]thiadiazole and benzo[c][1,2,5]oxadiazole, tweak the electron push-pull effect of COFs, leading to distinct photocatalytic performances. In the selective photocatalytic oxidation of three sulfide substrates, the observed performance exhibits the following order: MPBTD-T32T-COF > MPBTD-T23T-COF > MPBO-T32T-COF > MPBO-T23T-COF. Mechanistic studies reveal that superoxide is the predominant reactive oxygen species powering the selective photocatalytic sulfoxidation over MPBTD-T32T-COF. Furthermore, MPBTD-T32T-COF demonstrates recyclability and broad substrate applicability for the selective photocatalytic sulfoxidation.

Key words: Covalent organic frameworks, Full conjugation, Superoxide, Photocatalytic oxidation, Organic sulfides

张可可, 张富林, 王月欣, 黄凤伟, 熊康慧, 顾向奎, 郎贤军. 调控亚乙烯基连接的噻吩并噻吩共价有机框架的电子推拉效应以增强选择性光催化[J]. 催化学报, 2026, 87: 206-216.

Keke Zhang, Fulin Zhang, Yuexin Wang, Fengwei Huang, Kanghui Xiong, Xiang-Kui Gu, Xianjun Lang. Tweaking the electron push-pull effect of vinylene-linked thienothiophene covalent organic frameworks for enhanced selective photocatalysis[J]. Chinese Journal of Catalysis, 2026, 87: 206-216.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65102-9

https://www.cjcatal.com/CN/Y2026/V87/I8/206

图/表 10

Fig. 1. (a) The structures of MPBTD-T32T-COF, MPBTD-T23T-COF, MPBO-T32T-COF, and MPBO-T23T-COF. Experimental and simulated PXRD patterns of MPBTD-T32T-COF (b), MPBTD-T23T-COF (c), MPBO-T32T-COF (d), and MPBO-T23T-COF (e).

Fig. 2. The solid-state 13C NMR spectra (a), N2 sorption isotherms (b), and pore-size distribution profiles (c) of MPBTD-T32T-COF, MPBTD-T23T-COF, MPBO-T32T-COF, and MPBO-T23T-COF.

Fig. 3. The SEM images of MPBTD-T32T-COF (a), MPBTD-T23T-COF (b), MPBO-T32T-COF (c), and MPBO-T23T-COF (d).

Fig. 4. The HOMO and LUMO distributions of MPBTD-T32T-COF (a), MPBTD-T23T-COF (b), MPBO-T32T-COF (c), and MPBO-T23T-COF (d).

Fig. 5. The solid-state UV-vis DRS (a), Tauc plots (b), and band structure diagrams (c) of MPBTD-T32T-COF, MPBTD-T23T-COF, MPBO-T32T-COF, and MPBO-T23T-COF.

Fig. 6. The Mott-Schottky plots of MPBTD-T32T-COF (a), MPBTD-T23T-COF (b), MPBO-T32T-COF (c), and MPBO-T23T-COF (d).

Fig. 7. Transient photocurrent densities (a), EIS Nyquist plots (b), time-resolved PL decay spectra (c), and O2 adsorption energies (d) of MPBTD-T32T-COF, MPBTD-T23T-COF, MPBO-T32T-COF, and MPBO-T23T-COF.

Fig. 8. Kinetic curves (a) and performance comparison (b) for the selective photocatalytic sulfoxidation over MPBTD-T32T-COF, MPBTD-T23T-COF, MPBO-T32T-COF, and MPBO-T23T-COF. Recycling (c) and control experiments (d) for the selective photocatalytic sulfoxidation over MPBTD-T32T-COF. Reaction conditions: COF (4 mg), O2 (0.1 MPa), sulfide (0.3 mmol), CH3OH (1 mL), blue LEDs, (b) 38 min, (c,d) 30 min.

Fig. 9. EPR spectra of e− (a) and DMPO-O2•− (b). (c) A plausible mechanism for the selective photocatalytic sulfoxidation over MPBTD-T32T-COF.

Table 1 Substrate applicability of the selective photocatalytic sulfoxidation over MPBTD-T32T-COF a.

Entry	t (min)	Conv. (%)	Sel. (%)
1	38	90	99
2	38	95	99
3	45	91	98
4	45	92	97
5	48	97	99
6	50	90	99
7	90	96	99
8	100	90	99
9	42	93	99
10	55	90	99
11	60	94	99
12	70	94	99
13	45	99	99
14	50	99	99

参考文献

[1]	F. Auras, L. Ascherl, V. Bon, S. M. Vornholt, S. Krause, M. Döblinger, D. Bessinger, S. Reuter, K. W. Chapman, S. Kaskel, R. H. Friend, T. Bein, Nat. Chem., 2024, 16, 1373-1380.
[2]	R. Sánchez-Naya, J. P. Cavalieri, J. Albalad, A. Cortés-Martínez, K. Wang, C. Fuertes-Espinosa, T. Parella, S. Fiori, E. Ribas, A. Mugarza, X. Ribas, J. Faraudo, O. M. Yaghi, I. Imaz, D. Maspoch, Science, 2025, 388, 1318-1323.
[3]	B. Mishra, A. Alam, A. Chakraborty, B. Kumbhakar, S. Ghosh, P. Pachfule, A. Thomas, Adv. Mater., 2025, 37, 2413118.
[4]	R. Liu, Y. Chen, H. Yu, M. Položij, Y. Guo, T. C. Sum, T. Heine, D. Jiang, Nat. Catal., 2024, 7, 195-206.
[5]	Y. Qian, H.-L. Jiang, Acc. Chem. Res., 2024, 57, 1214-1226.
[6]	M. H. Liu, Q., Xu G. F. Zeng, Angew. Chem. Int. Ed., 2024, 63, e202404886.
[7]	B. Hu, J. Xu, Z. Fan, C. Xu, S. Han, J. Zhang, L. Ma, B. Ding, Z. Zhuang, Q. Kang, X. Zhang, Adv. Energy Mater., 2023, 13, 2203540.
[8]	S. Yao, Y. Yang, Z. Liang, J. Chen, J. Ding, F. Li, J. Liu, L. Xi, M. Zhu, J. Liu, Adv. Funct. Mater., 2023, 33, 2212466.
[9]	Z.-Y. Mei, G. Zhao, C. Xia, S. Cai, Q. Jing, X. Sheng, H. Wang, X. Zou, L. Wang, H. Guo, B.-Y. Xia, Angew. Chem. Int. Ed., 2023, 62, e202303871.
[10]	S. S. A. Shah, M. S. Javed, T. Najam, M. A. Nazir, A. ur Rehman, A. Rauf, M. Sohail, F. Verpoort, S.-J. Bao, Mater. Today, 2023, 67, 229-255.
[11]	T. Zhang, G. Zhang, L. Chen, Acc. Chem. Res., 2022, 55, 795-808.
[12]	J.-P. Jeon, Y. J. Kim, S. H. Joo, H.-J. Noh, S. K. Kwak, J.-B. Baek, Angew. Chem. Int. Ed., 2023, 62, e202217416.
[13]	M. Yu, Y. Chen, M. Gao, G. Huang, Q. Chen, J. Bi, Small, 2023, 19, 2206407.
[14]	L. Qin, C. Ma, J. Zhang, T. Zhou, Adv. Funct. Mater., 2024, 34, 2401562.
[15]	Y. Wang, Z. Qiao, H. Li, R. Zhang, Z. Xiang, D. Cao, S. Wang, Angew. Chem. Int. Ed., 2024, 63, e202404726.
[16]	H.-Y. Qu, Y. Guo, ACS Mater. Lett., 2025, 7, 2580-2587.
[17]	H. Chen, H. S. Jena, X. Feng, K. Leus, P. Van Der Voort, Angew. Chem. Int. Ed., 2022, 61, e202204938.
[18]	D. Blätte, F. Ortmann, T. Bein, J. Am. Chem. Soc., 2024, 146, 32161-32205.
[19]	C. Qian, L. Feng, W. L. Teo, J. Liu, W. Zhou, D. Wang, Y. Zhao, Nat. Rev. Chem., 2022, 6, 881-898.
[20]	C. Y. He, S. S. Tao, R. Y. Liu, Y. F. Zhi, D. L. Jiang, Angew. Chem. Int. Ed., 2024, 63, e202403472.
[21]	X. B. Yang, Q. Xu, W. Wei, G. F. Zeng, Angew. Chem. Int. Ed., 2025, 64, e202504355.
[22]	S. Ma, Z. Li, J. Jia, Z. Zhang, H. Xia, H. Li, X. Chen, Y. Xu, X. Liu, Chin. J. Catal., 2021, 42, 2010-2019.
[23]	T. He, K. Geng, D. Jiang, Trends Chem., 2021, 3, 431-444.
[24]	J. Kang, S. Huang, K. Jiang, C. Lu, Z. Chen, J. Zhu, C. Yang, A. Ciesielski, F. Qiu, X. Zhuang, Adv. Funct. Mater., 2020, 30, 2000857.
[25]	Y. Xu, G. Ren, D. Zhang, L. Sun, Y. Zhao, Chin. J. Chem., 2023, 41, 3447-3472.
[26]	L. Dai, A. W. Dong, X. J. Meng, H. Y. Liu, Y. T. Li, P. F. Li, B. Wang, Angew. Chem. Int. Ed., 2023, 62, e202300224.
[27]	Z. Xie, X. Yang, P. Zhang, X. Ke, X. Yuan, L. Zhai, W. Wang, N. Qin, C.-X. Cui, L. Qu, X. Chen, Chin. J. Catal., 2023, 47, 171-180.
[28]	Y. C. Wang, X., Zhao G. C., Han J. J., Bi Y. J. Zhao, Adv. Funct. Mater., 2025, 35, 2508550.
[29]	X. Wang, H. Li, S. Zhou, J. Ning, H. Wei, X. Li, S. Wang, L. Hao, D. Cao, Adv. Funct. Mater., 2025, 35, 2424035.
[30]	H. Sun, H. Ji, D. Qiao, Y. Xu, X. Qu, Y. Qi, Z. Feng, X. Zhang, F. Zhang, R. Wang, B. Dong, Chem. Eng. J., 2025, 507, 160448.
[31]	F. Tao, W. Zhou, Z. Li, X. Jiang, L. Wang, Z. Yu, J. Zhang, H. Zhou, ACS Mater. Lett., 2024, 6, 1120-1129.
[32]	X. Chi, Z. Zhang, M. Li, Y. Jiao, X. Li, F. Meng, B. Xue, D. Wu, F. Zhang, Angew. Chem. Int. Ed., 2025, 64, e202418895.
[33]	G. Fu, D. Yang, S. Xu, S. Li, Y. Zhao, H. Yang, D. Wu, P. S. Petkov, Z.-A. Lan, X. Wang, T. Zhang, J. Am. Chem. Soc., 2024, 146, 1318-1325.
[34]	Y. Wang, W. Hao, H. Liu, R. Chen, Q. Pan, Z. Li, Y. Zhao, Nat. Commun., 2022, 13, 100.
[35]	T. Yang, F. Kong, Y. Chen, A. Kong, X. Cui, J. Shi, Angew. Chem. Int. Ed., 2025, 64, e202424110.
[36]	C. Qin, X. Wu, L. Tang, X. Chen, M. Li, Y. Mou, B. Su, S. Wang, C. Feng, J. Liu, X. Yuan, Y. Zhao, H. Wang, Nat. Commun., 2023, 14, 5238.
[37]	C. Chen, L. Wang, W. Xia, K. Qiu, C. Guo, Z. Gan, J. Zhou, Y. Sun, D. Liu, W. Li, T. Wang, Nat. Commun., 2024, 15, 6865.
[39]	W. Feng, T. Chen, Y. Li, T. Duan, X. Jiang, C. Zhong, Y. Zhang, J. Yu, G. Lu, X. Wan, B. Kan, Y. Chen, Angew. Chem. Int. Ed., 2024, 63, e202316698.
[40]	J. Wang, S. Qiao, M. Yang, Z. Guo, Small, 2025, 21, 2409292.
[42]	K. Zhang, F. Zhang, F. Huang, K. Xiong, B. Zeng, X. Lang, ACS Appl. Mater. Interfaces, 2024, 16, 52455-52465.
[43]	W. Zhang, M. Sun, J. Cheng, X. J. Wu, H. X. Xu, Adv. Mater., 2025, 37, 2500913.
[44]	H. Chen, D. Li, M. Lin, Q. Wang, Y. Zou, J. Ran, Y. Xing, X. Long, Adv. Mater., 2025, 37, 2500063.
[45]	T. Yang, D. Zhang, A. Kong, Y. Zou, L. Yuan, C. Liu, S. Luo, G. Wei, C. Yu, Angew. Chem. Int. Ed., 2024, 63, e202404077.
[46]	R. Guntermann, L. Frey, A. Biewald, A. Hartschuh, T. Clark, T. Bein, D. D. Medina, J. Am. Chem. Soc., 2024, 146, 15869-15878.
[47]	Z. Ding, J. Yang, Z. Wu, M. Adeli, X. Luo, X. Wang, X. Xie, X. Xu, C. Cheng, C. Zhao, Chem. Mater., 2025, 37, 1972-1982.
[48]	T. Q. Chen, Y. Y. Zhong, T. N. Duan, X. Tang, W. K. Zhao, J. Y. Wang, G. H. Lu, G. K. Long, J. B. Zhang, K. Han, X. J. Wan, B. Kan, Y. S. Chen, Angew. Chem. Int. Ed., 2025, 64, e202412983.
[49]	T. Lin, Y. Hai, Y. Luo, L. Feng, T. Jia, J. Wu, R. Ma, T. A. Dela Peña, Y. Li, Z. Xing, M. Li, M. Wang, B. Xiao, K. S. Wong, S. Liu, G. Li, Adv. Mater., 2024, 36, 2312311.
[50]	A. Kong, T. Yang, H. Yan, X. Chen, Y. Chen, F. Kang, Q. Zhang, R. Liu, J. Am. Chem. Soc., 2025, 147, 20855-20864.
[51]	W. B. Zhong, W. K. Han, S. Bi, X. K. Ma, C. Wang, Y. L. Wu, T. He, Z. D. Zhang, J. J. Guo, Y. L. Zhao, ACS Mater. Lett., 2025, 7, 811-819.
[52]	J. Zhang, W. Zhou, J. Zhao, L. Xu, X. Jiang, Z. Li, Y. Peng, G. Li, Small, 2025, 21, 2408324.
[53]	Y. Ju, H. Lin, G. Tan, P. Su, Z. Wang, C. Hu, R. Hou, T. Hao, F. Chen, Y. Tang, Nat. Commun., 2025, 16, 5658.
[54]	L. Wang, C. Han, S. Gao, J.-X. Jiang, Y. Zhang, ACS Catal., 2025, 15, 5683-5693.
[55]	W. Liu, J. Jiang, Z. Li, B. Gao, C. Liu, C. Liu, W. Hao, R. Fan, J. Liu, T. Yu, Z. Zou, Z. Li, Angew. Chem. Int. Ed., 2025, 64, e202507312.
[56]	K. Sun, Y. Huang, Q. Wang, W. Zhao, X. Zheng, J. Jiang, H.-L. Jiang, J. Am. Chem. Soc., 2024, 146, 3241-3249.
[57]	K. Cheng, S. Kong, J. Wang, Q. Wang, S. Yuan, P.-Z. Li, Y. Zhao, Angew. Chem. Int. Ed., 2025, 64, e202504772.
[58]	Y. Hou, P. Zhou, F. Liu, K. Tong, Y. Lu, Z. Li, J. Liang, M. Tong, Nat. Commun., 2024, 15, 7350.
[59]	F. Zhang, X. M. Lv, H. Z. Wang, J. Z. Cai, H. N. Wang, S. Bi, R. L. Wei, C. Yang, G. F. Zheng, Q. Han, Adv. Mater., 2025, 37, 2502220.
[60]	D. Xie, Y. Wang, X. Zhang, Z. Fu, D. Niu, Angew. Chem. Int. Ed., 2022, 61, e202204922.
[61]	T. Huang, J. Kou, H. Yuan, H. Guo, K. Yuan, H. Li, F. Wang, Z. Dong, Adv. Funct. Mater., 2025, 35, 2413943.
[62]	A. Garci, J. A. Weber, R. M. Young, M. Kazem-Rostami, M. Ovalle, Y. Beldjoudi, A. Atilgan, Y. J. Bae, W. Liu, L. O. Jones, C. L. Stern, G. C. Schatz, O. K. Farha, M. R. Wasielewski, J. F. Stoddart, Nat. Catal., 2022, 5, 524-533.
[63]	C.-J. Wu, X.-Y. Li, T.-R. Li, M.-Z. Shao, L.-J. Niu, X.-F. Lu, J.-L. Kan, Y. Geng, Y.-B. Dong, J. Am. Chem. Soc., 2022, 144, 18750-18755.
[64]	B. Zeng, F. Huang, Y. Wang, K. Xiong, X. Lang, Chin. J. Catal., 2024, 58, 226-236.
[65]	M. Li, X. Chi, Z. Zhang, S. Bi, F. Meng, Y. Jiao, K. Mou, Z. Wang, B. Xue, X. Li, F. Zhang, Angew. Chem. Int. Ed., 2024, 63, e202411474.
[66]	X. Dong, F. Zhang, Y. Wang, F. Huang, X. Lang, Appl. Catal. B, 2024, 345, 123660.
[67]	Z. Yang, X. Xu, Z. Li, C. Liu, J. Jiang, S. Zhang, J. Miao, W. Liu, W. Liu, Z. Zou, Z. Li, Angew. Chem. Int. Ed., 2025, 64, e202503901.
[68]	C. Chu, Y. Qin, C. Ni, N. Wu, J. Zou, Appl. Catal. B, 2024, 341, 123321.
[69]	S. Zhang, F. Zhang, B. Zeng, K. Zhang, Y. Wang, J. Shang, X. Lang, Appl. Catal. B, 2025, 369, 125147.