Electrostatically assembled metal-free COF/g-C3N4 S-scheme heterojunction for enhanced photocatalytic H2O2 production

doi:10.1016/S1872-2067(26)65153-4

Abstract

Abstract:

Photocatalytic hydrogen peroxide synthesis driven by solar energy represents a sustainable alternative to the energy-intensive anthraquinone process. However, practical efficiency is often compromised by the chemical leaching of metal species in conventional photocatalysts, which accelerates H₂O₂ decomposition during reaction. Herein, a metal-free S-scheme heterojunction is constructed via electrostatic self-assembly between a sulfonic acid-functionalized covalent organic framework (COF) and protonated g-C₃N₄. The optimized composite exhibits a markedly enhanced H₂O₂ production rate compared with pristine COF and g-C₃N₄. In-situ irradiated X-ray photoelectron spectroscopy and femtosecond transient absorption spectroscopy provide direct evidence of S-scheme charge-transfer behavior, wherein photogenerated electrons in the COF recombine with holes in g-C₃N₄, thereby preserving highly reductive electrons in the conduction band of g-C₃N₄ for efficient oxygen reduction. This work highlights metal-free S-scheme heterojunctions as an effective strategy for designing high-performance photocatalysts toward sustainable H₂O₂ synthesis.

Key words: S-scheme heterojunction, Hydrogen peroxide, Metal-free photocatalyst, Covalent organic framework, Carbon nitride

Wei Xia, Chenchen Jiang, Wenjun Zhu, Xinwen Zhang, Jianjun Zhang, Chuanbiao Bie. Electrostatically assembled metal-free COF/g-C₃N₄ S-scheme heterojunction for enhanced photocatalytic H₂O₂ production[J]. Chinese Journal of Catalysis, 2026, 89: 326-336.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65153-4

https://www.cjcatal.com/EN/Y2026/V89/I10/326

Figures/Tables 7

Fig. 1. Schematic illustration of the synthesis of Tp-DSA-COF/g-C3N4 composites.

Fig. 2. (a) XRD patterns of Tp-DSA-COF (COF), g-C3N4 (GCN), and the composite CG60. (b) FTIR spectra of COF, GCN, and CG60. (c) TEM image of CG60. (d) HAADF-STEM image of CG60. (e-h) Corresponding EDS elemental mapping images of C, N, O, and S in CG60.

Fig. 3. (a) UV-vis DRS spectra of COF, GCN and CG60. (b) UPS spectra of COF. (c) Surface potentials of HOPG, COF, and GCN measured by KPFM. (d) Schematic band alignment of COF and GCN.

Fig. 4. (a) Charge-density difference of the COF/GCN heterojunction obtained from DFT calculations; the yellow and blue regions indicate charge accumulation and charge depletion, respectively. (b) ISI-XPS spectra of S 2p under dark and light irradiation conditions. (c) Schematic illustration of the charge transfer mechanism in the S-scheme COF/GCN heterojunction.

Fig. 5. PL spectra (a), TRPL spectra (b), photocurrent density responses (c), and EIS Nyquist plots (d) of COF, GCN and CG60.

Fig. 6. Transient absorption spectra depicting the femtosecond-time-scale dynamics of GCN (a) and CG60 (b). Time-resolved picosecond-time-scale transient absorption signals of GCN (c) and CG60 (d). Decay kinetics and corresponding fitted curves of GCN at 520 nm (e) and CG60 at 500 nm (f).

Fig. 7. (a) Photocatalytic H2O2 production rates of COF, GCN and CGx. (b) Cycle stability of CG60. (c) Fitted Kf and Kd for COF, GCN and CG60. (d) Effect of p-BQ on the photocatalytic H2O2 production activity of CG60. In-situ DRIFTS spectra of CG60 in the dark (e) and under light irradiation (f).

References

[1]	R. Ciriminna, L. Albanese, F. Meneguzzo, M. Pagliaro, ChemSusChem, 2016, 9, 3374-3381.
[2]	J. García-Serna, T. Moreno, P. Biasi, M. J. Cocero, J.-P. Mikkola, T. O. Salmi, Green Chem., 2014, 16, 2320-2343.
[3]	J. Yang, X. Zeng, B. Zhu, S. Rahman, C. Bie, M. Yong, K. Sun, M. Tebyetekerwa, Z. Wang, L. Guo, X. Sun, Y. Kang, L. Thomsen, Z. Sun, Z. Zhang, X. Zhang, Adv. Mater., 2025, 37, 2505653.
[4]	M. Sayed, H. Li, C. Bie, Acta Phys.-Chim. Sin., 2025, 41, 100117.
[5]	J. M. Campos-Martin, G. Blanco-Brieva, J. L. G. Fierro, Angew. Chem. Int. Ed., 2006, 45, 6962-6984.
[6]	S. C. Perry, S. Mavrikis, L. Wang, C. Ponce de León, Curr. Opin. Electrochem., 2021, 30, 100792.
[7]	Y. Shiraishi, T. Takii, T. Hagi, S. Mori, Y. Kofuji, Y. Kitagawa, S. Tanaka, S. Ichikawa, T. Hirai, Nat. Mater., 2019, 18, 985-993.
[8]	Y. Kofuji, Y. Isobe, Y. Shiraishi, H. Sakamoto, S. Tanaka, S. Ichikawa, T. Hirai, J. Am. Chem. Soc., 2016, 138, 10019-10025.
[9]	Y. Shiraishi, S. Kanazawa, D. Tsukamoto, A. Shiro, Y. Sugano, T. Hirai, ACS Catal., 2013, 3, 2222-2227.
[10]	Z. Jiang, J. Zhang, B. Cheng, Y. Zhang, J. Yu, L. Zhang, Small, 2025, 21, 2409079.
[11]	S. Thakur, T. Kshetri, N. H. Kim, J. H. Lee, J. Catal., 2017, 345, 78-86.
[12]	M. Gu, Y. Yang, B. Cheng, L. Zhang, P. Xiao, T. Chen, Chin. J. Catal., 2024, 59, 185-194.
[13]	Y. Ma, S. Wang, Y. Zhang, B. Cheng, L. Zhang, J. Materiomics, 2025, 11, 100978.
[14]	F. Xu, W. Mei, P. Hu, L. Zheng, J. Zhang, H. Cao, H. García, J. Yu, Angew. Chem. Int. Ed., 2025, 64, e202513364.
[15]	X. Yin, D. Gao, J. Zhang, H. García, J. Yu, H. Yu, J. Am. Chem. Soc., 2025, 147, 34881-34890.
[16]	X. Guan, Y. Yuan, L. Tian, Z. Huang, X. Ye, T. Zhang, B. Zhu, Z. Zhou, Chem. Synth., 2025, 5, 70.
[17]	F. Xu, L. Zheng, J. Zhang, Y. He, H. Cao, X. Zheng, H. García, J. Yu, Nat. Catal., 2026, 9, 73-86.
[18]	D. Gao, H. Yu, H. García, J. Yu, Prog. Mater. Sci., 2026, 159, 101663.
[19]	F. Xu, F. Zhao, X. Deng, J. Zhang, J. Zhang, C. Ai, J. Yu, H. García, Nat. Commun., 2025, 16, 6882.
[20]	L. Zhang, J. Zhang, J. Yu, Chem, 2026, 12, 102719.
[21]	M. Cabrero-Antonino, A. Uscategui-Linares, R. Ramírez-Grau, P. García-Aznar, G. Sastre, J. Zhang, S. Goberna-Ferrón, J. Albero, J. Yu, H. García, F. Xu, A. Primo, Angew. Chem. Int. Ed., 2025, 64, e202503860.
[22]	X. Zhou, S. Yang, X. Wang, Z. Wu, Y. Huo, J. Zhang, J. Mater. Sci. Technol., 2025, 234, 60-70.
[23]	W. Yu, M. H. Richter, P. Buabthong, I. A. Moreno-Hernandez, C. G. Read, E. Simonoff, B. S. Brunschwig, N. S. Lewis, Energy Environ. Sci., 2021, 14, 6007-6020.
[24]	X. Zhou, C. Ai, X. Wang, Z. Wu, J. Zhang, J. Materiomics, 2025, 11, 100974.
[25]	X. Li, Z. Wang, Acta Phys.-Chim. Sin., 2025, 41, 100080.
[26]	L. Zhao, K. Xu, C. Bie, Acta Phys.-Chim. Sin., 2026, 42, 100216.
[27]	B. Zhai, J. He, H. Li, X. Li, S. Nurmanov, O. Ruzimuradov, P. Niu, S. Chun, S. Wang, L. Li, Carbon Neutralization, 2024, 3, 888-903.
[28]	J. Qiu, C. Cheng, H. García, G. Liang, B. Zhu, L. Zhang, J. Yu, Angew. Chem. Int. Ed., 2025, 64, e202515898.
[29]	W. Yu, Chin. J. Catal., 2025, 73, 8-11.
[30]	F. Kolahdouzan, N. Goodarzi, M. Setayeshmehr, D. S. Mousavi, A. Z. Moshfegh, Chin. J. Catal., 2025, 70, 230-259.
[31]	Z. Wang, C. Bie, J. Mater. Sci. Technol., 2026, 243, 206-208.
[32]	X. Wu, M. Sayed, G. Wang, W. Yu, B. Zhu, Adv. Mater., 2026, 38, e11322.
[33]	G. Tang, J. Zhang, C. Bie, X. Zheng, C. Jiang, J. Yu, Adv. Mater., 2025, 37, e14576.
[34]	L. Zhang, J. Zhang, J. Yu, H. García, Nat. Rev. Chem., 2025, 9, 328-342.
[35]	M. Sayed, K. Qi, X. Wu, L. Zhang, H. García, J. Yu, Chem. Soc. Rev., 2025, 54, 4874-4921.
[36]	M. Li, X. Li, J. B. Ghasemi, Chin. J. Catal., 2025, 73, 12-15.
[37]	B. Liu, J. Zhang, H. Li, B. Cheng, C. Bie, Acta Phys.-Chim. Sin., 2025, 41, 100121.
[38]	S. Wang, Q. Liu, W. Zhang, J. Liu, X. Ji, P. Cai, R. Chen, S. Liu, W. Ma, D. Zhang, X. Pu, Carbon Neutralization, 2025, 4, e70054.
[39]	L. Wang, J. Zhao, J. Mater. Sci. Technol., 2026, 241, 18-20.
[40]	H. Li, J. Zhang, B. Zhu, B. He, C. Bie, J. Yu, L. Zhang, Adv. Funct. Mater., 2026, 36, e21318.
[41]	Z. Meng, J. Zhang, H. Long, H. García, L. Zhang, B. Zhu, J. Yu, Angew. Chem. Int. Ed., 2025, 64, e202505456.
[42]	R. He, D. Xu, M. Sayed, J. Materiomics, 2025, 11, 100989.
[43]	Y. Zhao, Y. Zhang, L. Wang, C. Ai, J. Zhang, J. Mater. Sci. Technol., 2025, 229, 213-222.
[44]	Y. Liu, M. Li, T. Liu, Z. Wu, L. Zhang, J. Mater. Sci. Technol., 2025, 233, 201-209.
[45]	J. Yang, C. Bie, Chem. Synth., 2025, 5, 12.
[46]	K. Meng, J. Zhang, B. Zhu, C. Jiang, H. García, J. Yu, Adv. Mater., 2025, 37, 2505088.
[47]	F. Fu, Y. Li, Chin. J. Catal., 2025, 78, 4-6.
[48]	M. Wei, C. Cheng, B. He, B. Cheng, K. Qi, C. Bie, Acta Phys.-Chim. Sin., 2025, 41, 100158.
[49]	L. Lv, Y. Liu, X. Li, Y. Huang, T. Li, H. Jian, Y. Fan, H. Song, H. Feng, Y. Wang, Carbon Neutralization, 2025, 4, e70021.
[50]	X. Li, H. Wu, S. Yin, C. Yu, Y. Shao, D. Zhou, P. She, Chem. Synth., 2025, 5, 29.
[51]	Y. Yang, X. Zhou, M. Gu, B. Cheng, Z. Wu, J. Zhang, Acta Phys.-Chim. Sin., 2025, 41, 100064.
[52]	Y. Zhang, Y. Wang, Y. Liu, S. Zhang, Y. Zhao, J. Zhang, J. Materiomics, 2025, 11, 100985.
[53]	M. Liu, J. Wen, R. Xiao, R. Tan, Y. Qin, J. Li, Y. Bai, M. Xi, W. Yang, Q. Fang, L. Hu, W. Gu, C. Zhu, Nano Lett., 2023, 23, 5358-5366.
[54]	Y. Wang, H. Sun, Z. Yang, Y. Zhu, Y. Xia, Carbon Neutralization, 2024, 3, 737-767.
[55]	S. Zhang, C. Bie, Rare Met., 2025, 44, 9289-9292.
[56]	Y. Chen, Y. Qiu, T. Chen, H. Wang, ACS Nano, 2025, 19, 6588-6600.
[57]	M. Solakidou, A. Giannakas, Y. Georgiou, N. Boukos, M. Louloudi, Y. Deligiannakis, Appl. Catal. B, 2019, 254, 194-205.
[58]	X. Ning, J. Li, B. Yang, W. Zhen, Z. Li, B. Tian, G. Lu, Appl. Catal. B, 2017, 212, 129-139.
[59]	J. Lin, W. Tian, Z. Guan, H. Zhang, X. Duan, H. Wang, H. Sun, Y. Fang, Y. Huang, S. Wang, Adv. Funct. Mater., 2022, 32, 2201743.
[60]	M. Yoon, Y. Oh, S. Hong, J. S. Lee, R. Boppella, S. H. Kim, F. Marques Mota, S. O. Kim, D. H. Kim, Appl. Catal. B, 2017, 206, 263-270.
[61]	L. Wang, J. Zhang, Y. Zhang, H. Yu, Y. Qu, J. Yu, Small, 2022, 18, 2104561.
[62]	H. W. Richter, W. H. Waddell, J. Am. Chem. Soc., 1982, 104, 4630-4634.
[63]	M. I. Zaki, A. Katrib, A. I. Muftah, T. C. Jagadale, M. Ikram, S. B. Ogale, Appl. Catal. A, 2013, 452, 214-221.
[64]	S.-S. Lin, M. D. Gurol, Environ. Sci. Technol., 1998, 32, 1417-1423.
[65]	T. Huang, H. Jiang, J. C. Douglin, Y. Chen, S. Yin, J. Zhang, X. Deng, H. Wu, Y. Yin, D. R. Dekel, M. D. Guiver, Z. Jiang, Angew. Chem. Int. Ed., 2023, 62, e202209306.
[66]	W.-J. Ong, L.-L. Tan, Y. H. Ng, S.-T. Yong, S.-P. Chai, Chem. Rev., 2016, 116, 7159-7329.
[67]	J. Xu, L. Zhang, R. Shi, Y. Zhu, J. Mater. Chem. A, 2013, 1, 14766-14772.
[68]	W. Li, Q. Wang, F. Cui, G. Jiang, RSC Adv., 2022, 12, 17984-17989.
[69]	L. Li, X. Lv, Y. Xue, H. Shao, G. Zheng, Q. Han, Angew. Chem. Int. Ed., 2024, 63, e202320218.
[70]	W. Zou, G. Jiang, W. Zhang, L. Zhang, Z. Cui, H. Song, Z. Liang, L. Du, Adv. Funct. Mater., 2023, 33, 2213642.
[71]	C. Bie, J. Yang, X. Zeng, Z. Wang, X. Sun, Z. Yang, J. Yu, X. Zhang, Small, 2025, 21, 2411184.
[72]	Y.-W. Su, C. Pan, T.-Y. Sun, Y.-Q. Zou, Chem. Synth., 2025, 5, 10.
[73]	J. Tauc, R. Grigorovici, A. Vancu, Phys. Status Solidi B, 1966, 15, 627-637.
[74]	X. Shi, C. Dai, X. Wang, J. Hu, J. Zhang, L. Zheng, L. Mao, H. Zheng, M. Zhu, Nat. Commun., 2022, 13, 1287.
[75]	C. Yuan, H. Yin, J. Li, Y. Zhang, H. Chen, D. Xiao, Q. Wang, Y. Zhang, Q.-K. Xue, Nat. Commun., 2025, 16, 6607.
[76]	J. Hao, Q. Zhang, P. Chen, X. Zheng, Y. Wu, D. Ma, D. Wei, H. Liu, G. Liu, W. Lv, Environ. Sci.: Nano, 2019, 6, 3374-3387.
[77]	Y. Jiang, S. Li, S. Wang, Y. Zhang, C. Long, J. Xie, X. Fan, W. Zhao, P. Xu, Y. Fan, C. Cui, Z. Tang, J. Am. Chem. Soc., 2023, 145, 2698-2707.
[78]	C. Jiang, C. Yuan, K. Xu, X. Zhou, C. Bie, J. Mater. Sci. Technol., 2025, 231, 36-44.
[79]	C. Bie, C. Jiang, J. Yang, X. Sun, X. Zeng, J. Zhang, B. Zhu, J. Mater. Sci. Technol., 2025, 229, 48-57.
[80]	X. Lei, Q. Tang, Y. Zheng, P. Kidkhunthod, X. Zhou, B. Ji, Y. Tang, Nat. Sustain., 2023, 6, 816-826.
[81]	W. Zhou, H. Su, W. Cheng, Y. Li, J. Jiang, M. Liu, F. Yu, W. Wang, S. Wei, Q. Liu, Nat. Commun., 2022, 13, 6414.
[82]	J. Zhang, H. Zeng, B. He, Y. Liu, J. Xu, T. Niu, C. Pan, Y. Zhang, Y. Lou, Y. Wang, Y. Dong, Y. Zhu, Appl. Catal. B, 2024, 358, 124448.

Electrostatically assembled metal-free COF/g-C₃N₄ S-scheme heterojunction for enhanced photocatalytic H₂O₂ production

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