Tweaking the electron push-pull effect of vinylene-linked thienothiophene covalent organic frameworks for enhanced selective photocatalysis

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

Abstract

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

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.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65102-9

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

Figures/Tables 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

References

[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.