Boosting Photocatalytic H₂O₂ Synthesis Over HKUST-1 MOFs-Derived Hollow HKUST-1@CuFePBA@CuS Heterojunctions

Abstract

Recently, photocatalytic synthesis of H₂O₂ has received much attention. However, the photocatalytic activity of photocatalysts is generally limited due to multiple factors, such as insufficiency of photoelectrons, low adsorption capability of O₂ on the photocatalyst surface, and high thermodynamic barrier. To address these issues, herein we have designed an interesting kind of hollow HKUST-1@CuFePBA@CuS (HS@CuFe@CuS) heterojunction photocatalyst. HKUST-1 metal–organic frameworks (MOFs) with cubic morphology were first synthesized as the precursor. Next, Cu²⁺ ions were released from HKUST-1 for the growth of CuFe Prussian blue analogue (CuFePBA) nanosheets on the HKUST-1 surface and then CuS nanoparticles on the CuFePBA nanosheet surface, simultaneously creating a hollow structure in HKUST-1. It is demonstrated that the resultant photocatalysts exhibit remarkable photocatalytic activity for H₂O₂ synthesis. Particularly, the H₂O₂ yield rate reaches 927 μmol g⁻¹ h⁻¹ over the HS@CuFe@CuS-4, which is increased by 5.3, 10.3, and 5.2 times as compared with that over single HKUST-1, CuFePBA, and CuS, respectively. Experimental and theoretical studies outline several advantages of the hollow HS@CuFe@CuS heterostructures for boosting the photocatalytic H₂O₂ synthesis: 1) more photoelectrons available for O₂ photoreduction reactions due to the efficient photocarrier separation/transfer and unique hollow structure, 2) increased O₂ adsorption on the active sites, and 3) a decrease in the Gibbs free energies for O₂ photoreduction reactions. This study highlights a promising nanostructure design strategy of photocatalysts for boosting H₂O₂ synthesis.

Keywords

charge transfer mechanism / enhanced photocatalysis mechanism / HKUST-1@CuFePBA@CuS heterojunctions / hollow architectures / photocatalytic H₂O₂ synthesis

References

[1] J. J. Cai, Z. Zhang, A. B. Cui, Y. X. Wang, Y. Zhang, J. M. Wang, Q. Xie, Mater. Today Energy 2025, 49, 101845.

[2] G. Y. Chen, C. Y. Lin, F. C. Han, H. T. Zhang, S. J. Zhou, F. Yang, Y. Kong, E. H. Ang, Mater. Horiz. 2025, 12, 5492.

[3] U. Kumar, M. R. Pai, I. Sinha, J. Environ. Chem. Eng. 2025, 13, 117357.

[4] Z. X. Wu, P. H. Ding, V. Gueskine, R. Boyd, E. D. Glowacki, M. Odén, X. Crispin, M. Berggren, E. M. Björk, M. Vagin, Energy Environ. Mater. 2024, 7, e12551.

[5] Z. Y. Liao, J. J. Du, L. Wang, M. Yang, L. L. Zhao, X. Q. Zhan, H. L. Yang, W. Y. Yang, H. L. Hou, J. Alloys Compd. 2023, 976, 173322.

[6] L. Zhang, H. T. Wang, J. Peng, Q. J. Yi, D. Zhang, L. Lv, J. H. Qiu, W. X. Tang, Sep. Purif. Technol. 2025, 364, 132284.

[7] H. Gao, C. Yu, X. Zhou, D. Li, L. Li, S. Wang, A. Syed, Mater. Sci. Semicond. Process. 2025, 200, 109956.

[8] Y. Li, L. Y. Wang, D. Q. Fan, Z. L. Li, C. X. Zhao, X. F. Yang, Energy Environ. Mater. 2025, e70150.

[9] R. Q. Zhang, X. T. Yao, X. R. Meng, X. Y. Li, D. F. Zhang, J. C. Liu, P. Q. Cai, X. P. Pu, Sep. Purif. Technol. 2025, 354, 129479.

[10] R. Garg, S. Gonuguntla, S. Sk, M. S. Iqbal, A. O. Dada, U. Pal, M. Ahmadipour, Adv. Colloid Interf. Sci. 2024, 330, 103203.

[11] S. Mehmood, S. Sk, B. M. Abraham, M. Ahmadipour, U. Pal, J. Dutta, Adv. Funct. Mater. 2025, 35, 2418602.

[12] N. Chanda, S. Gonuguntl, S. K. Verma, A. K. Basak, Y. Soujanya, M. Ahmadipour, S. Bojja, U. Pal, Int. J. Hydrog. Energy 2023, 48, 37715.

[13] M. Ahmadipour, M. S. Iqbal, M. A. Saeed, A. A. Hamzah, A. Ramzan, A. Bhattacharya, U. Pal, M. Ahmadipour, A. L. Pang, M. Satgunam, Results Eng. 2025, 28, 107168.

[14] A. Zhang, Z. Q. Jiang, S. D. Zhang, P. H. Lan, N. H. Miao, W. H. Chen, N. Huang, X. N. Tian, Y. J. Liu, Z. Y. Cai, Appl. Catal. B Environ. 2023, 331, 122721.

[15] C. Zhou, H. Yu, M. Yang, X. T. Dong, Y. Yang, ACS Appl. Nano Mater. 2025, 8, 12828.

[16] A. Sabbah, I. Shown, M. Qorbani, F. Y. Fu, T. Y. Lin, H. L. Wu, P. W. Chung, C. Wu, S. R. M. Santiago, J. L. Shen, K. H. Chen, L. C. Chen, Nano Energy 2021, 93, 106809.

[17] U. Kumar, E. Picheau, H. R. Li, Z. H. Zhang, T. Kikuchi, I. Sinha, R. Z. Ma, ACS Appl. Energy Mater. 2025, 8, 3107.

[18] S. Wu, H. T. Yu, S. Chen, X. Quan, ACS Catal. 2020, 10, 14380.

[19] H. L. Hou, X. K. Zeng, X. W. Zhang, Angew. Chem. Int. Ed. 2020, 28, l7356.

[20] R. Q. Zhang, R. C. Liu, Z. H. Ding, J. H. Ma, T. Wang, D. F. Zhang, J. C. Liu, P. Q. Cai, X. P. Pu, J. Colloid Interface Sci. 2025, 682, 568.

[21] T. Xian, W. L. Jing, L. J. Di, L. K. Pan, Y. K. Zhang, C. Y. Sun, X. F. Sun, H. Q. Wang, H. Yang, Appl. Surf. Sci. 2025, 682, 161655.

[22] S. Wang, H. Liu, Y. Zhang, X. Yu, Y. Han, H. Gao, L. Fang, A. V. Jagadeesha, M. Ubaidullah, B. Pandit, J. Environ. Chem. Eng. 2023, 11, 111453.

[23] C. H. Chen, X. W. Zhu, H. Yu, M. Yang, X. T. Dong, Y. Yang, Solid State Sci. 2025, 168, 108025.

[24] J. L. Ren, Q. F. Ma, X. F. Sun, S. F. Wang, G. R. Liu, H. Yang, J. Colloid Interface Sci. 2025, 691, 137452.

[25] Q. F. Ma, J. L. Ren, X. F. Sun, S. F. Wang, X. J. Chen, G. R. Liu, H. Yang, Chem. Eng. J. 2025, 509, 161444.

[26] H. Heo, J. U. Jang, E. Jeong, H. J. Kim, Y. J. Kim, C. W. Park, J. S. So, D. Y. Koh, Energy Environ. Mater. 2025, 8, e12815.

[27] C. F. Wen, M. Zhou, P. F. Liu, Y. W. Liu, X. F. Wu, F. X. Mao, S. Dai, B. B. Xu, X. L. Wang, Z. Jiang, P. Hu, S. Yang, H. F. Wang, H. G. Yang, Angew. Chem. Int. Ed. 2022, 61, e202111700.

[28] F. Ahmadijokani, S. Ahmadipouya, M. H. Haris, M. Rezakazemi, A. Bokhari, H. Molavi, M. Ahmadipour, S. Y. Pung, J. J. Klemes, T. M. Aminabhavi, M. Arjmand, ACS Appl. Mater. Interfaces 2023, 15, 30106.

[29] A. Jamma, T. A. Lakshmi, M. Ahmadipour, Y. T. Prabhu, U. Pal, ChemCatChem 2025, 17, e202500389.

[30] S. Sk, C. S. Vennapoosa, A. Tiwari, B. M. Abraham, M. Ahmadipour, U. Pal, Int. J. Hydrog. Energy 2022, 47, 33955.

[31] A. Jamma, B. Jaksani, C. S. Vennapoosa, S. Gonuguntla, S. Sk, M. Ahmadipour, I. Mondal, U. Pa, Mater. Adv. 2024, 5, 2785.

[32] M. Kabir, M. Rahman, T. Islam, Q. Meng, H. L. Liu, M. H. Li, S. H. Wu, Chem. Eng. J. 2025, 513, 162753.

[33] T. Zhao, S. Q. Nie, M. L. Luo, P. C. Xiao, M. M. Zou, Y. Chen, J. Alloys Compd. 2024, 974, 172897.

[34] Y. Li, J. P. Qu, J. Y. Wang, P. F. Wang, Z. L. Liu, J. Shu, T. F. Yi, Chem. Eng. J. 2024, 503, 158266.

[35] Z. X. Li, X. Z. Wang, Y. W. Xu, X. R. Li, J. C. Zhang, Y. Liu, J. B. Luo, Y. Zhou, Fuel 2024, 371, 131838.

[36] Y. Yin, M. Y. Li, X. Liu, N. Xie, C. Y. Zheng, G. K. Liu, S. Y. Yin, X. T. Li, Y. B. Pei, J. F. Zhang, Y. Z. Qin, M. D. Guiver, J. Power Sources 2022, 537, 231542.

[37] R. P. Ojha, S. Pal, R. Prakash, Microchem. J. 2021, 171, 106854.

[38] H. Y. Zhu, Q. Y. Shen, Y. Y. Yuan, H. Gao, S. Zhou, F. L. Yang, L. M. Sun, X. J. Wang, J. J. Yi, X. G. Han, Inorg. Chem. 2024, 63, 4078.

[39] A. Khobotov-Bakishev, C. V. Baeckmann, B. Ortín-Rubio, L. Hernández-López, A. Cortés-Martínez, J. Martínez-Esaín, F. Gándara, J. Juanhuix, A. E. Platero-Prats, J. Faraudo, A. Carné-Sánchez, D. Maspoch, J. Am. Chem. Soc. 2022, 144, 15745.

[40] Y. Y. Zou, C. Liu, C. Q. Zhang, L. Yuan, J. X. Li, T. Bao, G. F. Wei, J. Zou, C. Z. Yu, Nat. Commun. 2023, 14, 5780.

[41] X. L. Liu, A. Wang, C. P. Wang, J. L. Li, Z. Y. Zhang, A. M. Al-Enizi, A. Nafady, F. Shui, Z. F. You, B. Y. Li, Y. B. Wen, S. Q. Ma, Nat. Commun. 2023, 14, 7022.

[42] Z. X. Yang, M. L. Song, Y. Chen, F. N. Chen, Spectrochim. Acta A Mol. Biomol. Spectrosc. 2024, 304, 123421.

[43] J. Shen, L. Qian, J. Huang, Y. Guo, Z. Zhang, Sep. Purif. Technol. 2021, 275, 119239.

[44] S. Wang, M. Li, H. Gao, Z. Yin, C. Chen, H. Yang, L. Fang, V. J. Angadi, Z. Yi, D. Li, Appl. Surf. Sci. 2023, 608, 154977.

[45] X. F. Sun, T. Xu, T. Xian, Z. Yi, G. R. Liu, J. F. Dai, H. Yang, Appl. Surf. Sci. 2023, 640, 158408.

[46] L. A. Alfonso Herrera, F. Mondaca, S. Conejeros, L. M. Torres-Martínez, J. M. Mora-Hernandez, New J. Chem. 2024, 48, 11377.

[47] W. T. Wu, Y. F. Wu, Z. Q. Zhang, R. P. Wei, L. J. Gao, X. M. Pan, J. Zhang, J. Yu, G. M. Xiao, Sep. Purif. Technol. 2024, 328, 125009.

[48] Y. X. Sun, K. Z. Lai, N. Li, Y. Q. Gao, L. Ge, Appl. Catal. B Environ. Energy 2024, 357, 124302.

[49] W. Y. Shi, X. F. Sun, M. H. Xu, S. F. Wang, G. R. Liu, H. Yang, J. Water Process Eng. 2024, 67, 106229.

[50] J. J. Li, C. X. Dang, Q. C. Zhu, L. Li, W. M. Zhang, Acta Mater. 2025, 287, 120781.

[51] J. Q. Zhang, X. F. Sun, W. J. Zhu, G. R. Liu, T. Xian, H. Yang, J. Environ. Chem. Eng. 2024, 12, 114405.

[52] P. Liu, K. X. Cai, K. L. Wang, T. X. Zhao, D. J. Tao, Green Energy Environ. 2024, 9, 1711.

[53] Z. Y. Zhang, L. Li, X. M. Chen, W. T. Ding, S. Han, J. B. Jiang, Chem. Eng. J. 2024, 496, 154370.

[54] X. Yu, S. Wang, Y. Zhang, X. Yu, H. Gao, H. Yang, L. Fang, H. Zhang, Small 2025, 21, 2410819.

[55] C. Wang, G. R. Liu, X. F. Sun, J. Y. Ma, T. Xian, H. Yang, Chin. Phys. B 2025, 34, 127503.

[56] X. Y. Sun, X. C. Li, P. A. Chen, Y. L. Zhu, M. K. Qiao, Chem. Eng. J. 2024, 499, 155857.

[57] Q. F. Ma, J. L. Ren, X. F. Sun, X. J. Chen, G. R. Liu, S. F. Wang, H. Yang, Appl. Surf. Sci. 2025, 679, 161275.

[58] X. D. Zhang, D. D. Gao, B. C. Zhu, B. Cheng, J. G. Yu, H. G. Yu, Nat. Commun. 2024, 15, 3212.

[59] J. L. Ren, Q. F. Ma, X. F. Sun, J. Y. Ma, G. R. Liu, H. Yang, Fuel 2025, 397, 135454.

[60] X. F. Sun, T. Xian, C. Y. Sun, J. Q. Zhang, G. R. Liu, H. Yang, J. Mater. Sci. Technol. 2025, 228, 256.

[61] W. W. Chi, J. L. Wu, Y. M. Dong, J. Wu, Y. F. Zhu, Angew. Chem. Int. Ed. 2025, 64, e202508690.

[62] Z. H. Sun, J. Wei, Y. Yuanfeng, A. Cao, J. L. Zhang, X. Y. Shen, ACS Sustain. Chem. Eng. 2025, 13, 14037.

[63] X. F. Sun, J. Q. Zhang, M. X. Luo, J. Y. Ma, T. Xian, G. R. Liu, H. Yang, Chem. Eng. J. 2024, 499, 156455.

[64] Y. Y. Dai, G. R. Liu, X. F. Sun, J. Y. Ma, T. Xian, H. Yang, Appl. Surf. Sci. 2025, 681, 161611.

[65] F. Y. Zhang, G. R. Liu, X. F. Sun, Y. Y. Dai, J. Y. Ma, T. Xian, H. Yang, Sep. Purif. Technol. 2025, 379, 134913.

[66] J. H. Zhang, Z. M. Ge, J. Wang, D. C. Zhong, T. B. Lu, Nat. Commun. 2025, 16, 2448.

[67] G. R. Liu, Y. Y. Dai, X. F. Sun, J. Y. Ma, T. Xian, H. Yang, Sep. Purif. Technol. 2025, 361, 131622.

[68] X. M. Yu, S. F. Wang, Y. Y. Zhang, H. J. Gao, X. J. Zhou, D. F. Li, H. Yang, L. M. Fang, H. J. Zhang, A. Syed, Ceram. Int. 2024, 50, 29528.

[69] J. Hafner, J. Comput. Chem. 2008, 29, 2044.

[70] J. H. Du, X. F. Sun, S. F. Wang, Z. Yi, G. R. Liu, H. Yang, Appl. Surf. Sci. 2026, 719, 165024.

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