Pyridine Nitrogen-modified Covalent Organic Frameworks for Photocatalytic One-step 2e-H2O2 Production

doi:10.1007/s40242-025-5091-z

Abstract

Abstract: The precise regulation of photocatalytic oxygen reduction reaction (ORR) pathways, particularly the more energy-efficient one-step 2e^- route, is of fundamental importance for optimizing H₂O₂ production efficiency in rationally designed covalent organic frameworks (COFs). Here, a strengthened donor-acceptor (D-A) structured TPCN-COF[COF synthesized from 2,4,6-hydroxy-1,3,5-benzotricarboxaldehyde and 1,3,5-tris (4-aminophenyl) benzene] photocatalyst was developed through the strategic incorporation of pyridine nitrogen moieties into the COF skeleton. The strengthened D-A structure facilitates effective separation of photogenerated charge carriers while promoting rapid electron transfer kinetics. Concurrently, the introduced pyridine nitrogen units increase the surface polarity, thereby improving hydrophilicity and enabling more efficient proton delivery to active sites. Remarkably, the synergistic combination of enhanced charge separation and optimized proton transport in TPCN-COF effectively shifts the ORR mechanism from two-step 1e^- pathway to one-step 2e^- process. As a result, TPCN-COF achieves an exceptional H₂O₂ production rate of 1320.9 μmol∙g^-1∙h^-1 under visible light irradiation (λ ≥ 420 nm) in an air-equilibrated aqueous system, representing a nearly 3-fold enhancement compared to the unmodified TPCC-COF[COF synthesized from 2,4,6-hydroxy-1,3,5-benzotricarboxaldehyde and 5,5',5''-(benzene-1,3,5-triyl) tris (pyridin-2-ylamino)]. This work establishes an effective design strategy for constructing COFs photocatalysts with strong D-A structures, and elucidates the synergistic regulatory mechanism, by which both electronic structure and surface properties govern ORR pathway selectivity in COF-based systems.

Key words: Photocatalysis, Covalent organic framework (COF), H₂O₂ preparation, D-A structure, Reaction pathway

WU Jingyao, ZHAO Qiang, LV Yujing, WANG Shuo, WANG Pengzhao, LONG Jinlin, WANG Ying. Pyridine Nitrogen-modified Covalent Organic Frameworks for Photocatalytic One-step 2e^-H₂O₂ Production[J]. Chemical Research in Chinese Universities, 2025, 41(4): 822-830.

References

[1] Zhang J., Xue F., Wang Z., Angew. Chem. Int. Ed., 2025, e202425617.
[2] Qin L., Ma C., Zhang J., Zhou T., Adv. Funct. Mater., 2024, 34, 2401562.
[3] Xi Y., Zhang C., Tu W., Guo Y., Bao T., Zou Y., Liu C., Yu C., Angew. Chem. Int. Ed., 2025, e202505046.
[4] Wu S. K., Wang X., Yu H., Chin. J. Struct. Chem., 2024, 43, 100457.
[5] Wu Z. X., Ding P. H., Gueskine V., Boyd R., Głowacki E. D., Odén M., Crispin X., Berggren M., Björk E. M., Vagin M., Energy Environ. Mater., 2024, 7, e12551.
[6] Zeng W. G., Dong Y. C., Ye X. Y., Zhao Y., Zhang Z. Y, Zhang T., Zhang L., Chen J., Guan X. J., ACS Catal., 2025, 15, 6036.
[7] Liu M. H., Xu Y. C., Liu Y. X., Shang S. C., Gao W. Q., Wang X. Y., Hong J. X., Xu H. L., Hua C. Y., You Z. W., Zhou Z. X., Guo S. J., Liu Y. Q., Chen J. Y., Angew. Chem. Int. Ed., 2025, e202505491.
[8] Das P., Chakraborty G., Roeser J., Vogl S., Rabeah J., Thomas A., J. Am. Chem. Soc., 2023, 145, 2975.
[9] Das P., Roeser J., Thomas A., Angew. Chem. Int. Ed., 2023, 62, e202304349.
[10] Hou H. L., Zeng X. K., Zhang X. W., Angew. Chem. Int. Ed., 2020, 59, 17356.
[11] Qu S. Y., Wu H., Ng Y. H., Adv. Energy Mater., 2023, 13, 2301047.
[12] Xu M. Y., Shen R. C., Mo Y. Y., Liang G. J., Li S. J., Zhang P., Chen X. B., Li Y. J., Li X., Inf. Sci., 2025, e70001.
[13] Gopakumar A., Ren P., Chen J. H., Rodrigues B. V. M., Ching H. Y. V., Jaworski A., Van Doorslaer S., Rokicińska A., Kuśtrowski P., Barcaro G., Monti S., Slabon A., Das S., J. Am. Chem. Soc., 2022, 144, 2603.
[14] Luo Y., Zhang B. P., Liu C. C., Xia D. H., Ou X. W., Cai Y. P., Zhou Y., Jiang J., Han B., Angew. Chem. Int. Ed., 2023, 62, e202305355.
[15] Xiao J., Liu Q., Song M., Li X. R., Li Q., Shang J. K., Water Res., 2021, 198, 117125.
[16] Liu L. J., Gao M. Y., Yang H. F., Wang X. Y., Li X. B., Cooper A. I., J. Am. Chem. Soc., 2021, 143, 19287.
[17] Li W. T., Han B., Liu Y. H., Xu J. Y., He H. R., Wang G. G., Li J. S., Zhai Y. X., Zhu X. L., Zhu Y. F., Angew. Chem. Int. Ed., 2025, 64, e202421356.
[18] Tsukamoto D., Shiro A., Shiraishi Y., Sugano Y., Ichikawa S., Tanaka S., Hirai T., ACS Catal., 2012, 2, 599.
[19] Cao L. Z., Wang C., Wang H., Xu X. M., Tao X., Tan H. Q., Zhu G. S., Angew. Chem. Int. Ed., 2024, 63, e202402095.
[20] Zhu Y. C., Qin L. Y., Yang M. Y., Shi Z. C., Chen H. X., Wen N., Wang Y., Long J. L., Han S. T., Zhu M., Xi H. L., Small, 2025, 21, 2412118.
[21] Wang L., Han C. Z., Gao S. Y., Jiang J. X., Zhang Y., ACS Catal., 2025, 15, 5683.
[22] Liu R. Y., Chen Y. Z., Yu H. D., Položij M., Guo Y. Y., Sum T. C., Heine T., Jiang D. L., Nat. Catal., 2024, 7, 195.
[23] Wang J., Wang Z. L., Zhang J. F., Dai K., Chin. J. Struct. Chem., 2023, 42, 100202.
[24] Huang K. H., Bai J. X., Shen R. C., Li X. Z., Qin C. C., Zhang P., Li X., Adv. Funct. Mater., 2023, 33, 2307300.
[25] An Q., Wang H. E., Zhao G. F., Wang S. M., Xu L. F., Wang H., Fu Y., Guo H., Energy Environ. Mater., 2023, 6, e12345.
[26] Xue D. M., Zhang Y. J., Chen J. W., Yang H., Xie R. J., Qi S. C., Bu Y. Q., Liu F., Zhang H. H., Lalevée J., Chem. Eng. J., 2024, 502, 157874.
[27] Shen R. C., Liang G. J., Hao L., Zhang P., Li X., Adv. Mater., 2023, 35, 2303649.
[28] Liao Q. B., Li Z. Y., Sun Q. N., Xu H. C., Wang Y. D., Xu Y., Wu H. M., Zhang Z. Y., Xie Y. C., Li H. J., Wang D., Li G. S, Xi K., ACS Appl. Nano Mater., 2025, 8, 8095.
[29] Meng F. C., Li X. W., An Q. Z., Yang S., Zhang Z. X., Xu Q., Xue B., Jin X., Zhang F., Sci. China Mater., 2025, 68, 1138.
[30] Zhou S. J., Hu H., Hu H. K., Jiang Q. C., Xie H. R., Li C. L., Gao S. Y., Kong Y., Hu Y. J., Sci. China Mater., 2023, 66, 1837.
[31] Zhou S. J., Hu H., Hu H., Jiang Q. K., Xie H. R., Li C. L., Gao S. Y., Kong Y., Hu Y. J., Nat. Chem., 2018, 10, 1180.
[32] Liu F. Y., Zhou P., Hou Y. H., Tan H., Liang Y., Liang J. J., Zhang Q., Guo S. J., Tong M. P., Ni J. R., Nat. Commun., 2023, 14, 4344.
[33] Ouyang Z. H., Sheng G., Zhong Y., Wang J., Cai J. X., Deng S. G., Deng Q., Angew. Chem. Int. Ed., 2025, 64, e202418790.
[34] Zheng H. L., Huang Z. P., Wei P., Lin Y. H., Cao Y. H., Zhang X. Y., Zhou B. P., Peng C., ACS Sustain. Chem. Eng., 2025, 13, 4078.
[35] Chen Y. Z., Liu R. Y., Guo Y. Y., Wu G., Sum T. C., Yang S. W., Jiang D. L., Nat. Synth., 2024, 3, 998.
[36] Xu H. C., Wang Y. D., Xu Y., Wang Q. M., Zhuang M. Y., Liao Q. B., Xi K., Angew. Chem. Int. Ed., 2024, 63, e202408802.

Pyridine Nitrogen-modified Covalent Organic Frameworks for Photocatalytic One-step 2e^-H₂O₂ Production

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	LU Chongjiu, GONG Yunnan, ZHONG Dichang, LU Tongbu. Syntheses and Photocatalytic Application of Porous Supramolecular Frameworks [J]. Chemical Research in Chinese Universities, 2025, 41(4): 655-665.
[2]	ZHOU Yu, WANG Weikang, LI Jinhe, REN Wei, WANG Lele, LIU Qinqin. Transition Metal Sulfide Cocatalysts: Applications and Challenges in Photocatalytic Hydrogen Production [J]. Chemical Research in Chinese Universities, 2025, 41(4): 687-703.
[3]	LIU Chuang, GAO Tengyuan, WANG Guohong, CHENG Qiang WANG Kai. Efficient CO₂ Photoreduction into Solar Fuels over MoO_3-x/COF S-Scheme Photocatalyst [J]. Chemical Research in Chinese Universities, 2025, 41(4): 726-733.
[4]	YU Hong, ZHANG Xuening, CHEN Qian, ZHOU Pan-Ke, XU Fei, WANG Hongqiang, CHEN Xiong. Linkage Conversion in Pyrene-based Covalent Organic Frameworks for Promoted Photocatalytic Hydrogen Peroxide Generation in a Biphasic System [J]. Chemical Research in Chinese Universities, 2025, 41(4): 734-740.
[5]	WANG Yufan, ZHOU Guosheng, XU Yangrui, CHENG Yu, SONG Minshan, JIN Jie, LIU Xinlin, LU Ziyang. Hydrothermal Synthesis of Inorganic Imprinted Bi₄Ti₃O₁₂ Nanosheets for Efficient Selective Photocatalytic Degradation of Ciprofloxacin [J]. Chemical Research in Chinese Universities, 2025, 41(4): 741-750.
[6]	CHENG Shuilian, FANG Yuxuan, YANG Siyuan, GAO Qiongzhi, CAI Xin ZHANG Shengsen. Synergistic Dual-cocatalyst Modified TiO₂/g-C₃N₄ Heterojunctions for Efficient Photocatalytic Overall Water Splitting [J]. Chemical Research in Chinese Universities, 2025, 41(4): 751-759.
[7]	LU Junyu, LU Yunshu, Pitcheri ROSAIAH, LIN Shu, Zada AMIR, QI Kezhen. ZnCo₂O₄-ZnO S-Scheme Heterojunction for Photocatalytic Degradation of Cefalexin and Antimicrobial Properties [J]. Chemical Research in Chinese Universities, 2025, 41(4): 799-811.
[8]	LI Xiaofang, LI Fang, WU Yetong, YANG Heng, WANG Chunlei, CHAI Bo, GUO Xiaoliang, YAN Juntao. Oxygen Vacancy-rich BiOBr for Enhanced Photocatalytic NO Removal and Bacterial Inactivation [J]. Chemical Research in Chinese Universities, 2025, 41(4): 839-849.
[9]	GAO Juanfeng, LIN Xiao, JIANG Bowen, TANG Senpei, ZHANG Haiyan, CHEN Feitai, JIN Zhiliang, LI Youji, Noritatsu Tsubaki. Epitaxial Vertical Growth of Carbon Nitride-based Homojunction Composites for Enhanced Photocatalytic Degradation of Tetracycline Hydrochloride [J]. Chemical Research in Chinese Universities, 2025, 41(4): 868-879.
[10]	LI Dan. Frontiers in Catalytic Technologies for Carbon Neutrality: Advances and Prospects [J]. Chemical Research in Chinese Universities, 2025, 41(3): 472-483.
[11]	HU Miao, Jumanah ALHARBI, ZHANG Huabin, Hassan S. Al QAHTANI, FENG Chengyang. Advanced In situ Characterization Techniques for Photocatalysis [J]. Chemical Research in Chinese Universities, 2025, 41(2): 237-253.
[12]	YANG Xiaodan, GUO Ziqi, XU Yichen, LI Ziliang, ZHOU Yangtao, YANG Zhenming, ZHOU Zishuai, GAO Yong, ZHANG Jinsong. In situ Preparation and Visible-light-driven Photocatalytic Degradation Performance of Nano 3C-SiC@Multilayer Graphene Oxide Heterostructure [J]. Chemical Research in Chinese Universities, 2024, 40(3): 536-547.
[13]	WANG Xinyi, ZHAO Zhenwei, ZAHRA Kiran, LI Junjun, ZHANG Zhicheng. Sub-nanomaterials for Photo/Electro-catalytic CO₂ Reduction: Achievements, Challenges, and Opportunities [J]. Chemical Research in Chinese Universities, 2023, 39(4): 580-598.
[14]	Samavia RAFIQ, Zulfiqar Ali RAZA, Muhammad ASLAM, Muhammad Junaid BAKHTIYAR. Graphene Nanosheets Decorated with Copper Oxide Nanoparticles for the Photodegradation of Methylene Blue [J]. Chemical Research in Chinese Universities, 2022, 38(6): 1518-1525.
[15]	SONG Weiyu, LV Xintong, GAO Yang, WANG Lu. Photocatalytic HER Performance of TiO₂-supported Single Atom Catalyst Based on Electronic Regulation:A DFT Study [J]. Chemical Research in Chinese Universities, 2022, 38(4): 1025-1031.