Synergistic Photo-Electro-Fenton Oxidation of Antibiotics Using a Ferrocene-Functionalized MXene (Ti₃C₂T_x) Electrode

Abstract

The persistence of antibiotics such as tetracycline in aquatic systems poses severe environmental and health risks by potential antimicrobial resistance. To address this, a hybrid photo-electro-Fenton oxidation system based on MXene-derived electrodes was developed for efficient tetracycline degradation. The integration of photo, electro, and Fenton processes synergistically enhances hydroxyl radical (•OH) generation and charge-carrier separation, ensuring superior removal efficiency. The cathode was synthesized via a Schiff base formation method, which facilitates functionalization of Ti₃C₂T_x MXene with ferrocene, as confirmed by X-ray diffraction, X-ray photoelectron spectroscopy, and UV–visible spectrometry. The Ti₃C₂–TiO₂ photoanode was fabricated by electrochemical oxidation of Ti₃C₂T_x. The photocatalytic properties of anatase TiO₂, when combined with Ti₃C₂T_x, create a Schottky junction that significantly improves charge separation, thereby enhancing the photo-electrocatalytic activity of the system. The hybrid photo-electro-Fenton (PEF) system demonstrates a substantial enhancement in tetracycline removal efficiency (∼90%) compared to unmodified Ti₃C₂T_x-based electrodes (∼46%). Furthermore, the Ti₃C₂–TiO₂ Schottky photoanode showed enhanced removal efficiency over a commercial P25-based photoanode for photocatalytic degradation. Through this hybrid PEF oxidation system, the removal efficiencies achieved above 90% in neutral and acidic pH, indicating significant efficacy for the advanced oxidation process. The transformation products formed during the PEF process were analyzed with liquid chromatography coupled with high-resolution mass spectrometry, showing breakdown of tetracycline and decreasing ecotoxicity with increasing treatment time. Moreover, the MXene-derived electrode system demonstrates stability and consistent degradation performance over numerous cycles, making it a promising material for environmental remediation applications.

Keywords

catalysts / clean water / materials science / two-dimensional materials / waste water treatment

References

[1] M. Khmaissa, H. Zouari-Mechichi, G. Sciara, E. Record, T. Mechichi, J. Hazard. Mater. Adv. 2024, 13, 100410.

[2] E. Felis, J. Kalka, A. Sochacki, K. Kowalska, S. Bajkacz, M. Harnisz, E. Korzeniewska, Eur. J. Pharmacol. 2020, 866, 172813.

[3] M. Trinchera, S. De Gaetano, E. Sole, A. Midiri, S. Silvestro, G. Mancuso, T. Catalano, C. Biondo, Antibiotics 2025, 14, 606.

[4] D. G. J. Larsson, C.-F. Flach, Nat. Rev. Microbiol. 2022, 20, 257.

[5] J. Lee, F. Ju, K. Beck, H. Bürgmann, ISME J. 2023, 17, 1993.

[6] Y. Chen, H. Kang, M. Cheng, G. Zhang, G. Wang, H. Liu, W. Xiao, Y. Liu, H. Jiang, Adv. Funct. Mater. 2024, 34, 2309223.

[7] K. Wang, C. Han, Z. Shao, J. Qiu, S. Wang, S. Liu, Adv. Funct. Mater. 2021, 31, 2102089.

[8] S. Zhu, W. Zheng, W. Duan, C. Feng, Chem 2023, 9, 1340.

[9] D. Chen, Y. Cheng, N. Zhou, P. Chen, Y. Wang, K. Li, S. Huo, P. Cheng, P. Peng, R. Zhang, L. Wang, H. Liu, Y. Liu, R. Ruan, J. Clean. Prod. 2020, 268, 121725.

[10] H. Zhou, H. Wang, C. Yue, L. He, H. Li, H. Zhang, S. Yang, T. Ma, Appl. Catal. B Environ. Energy 2024, 344, 123605.

[11] L. Prieto-Rodriguez, S. Miralles-Cuevas, I. Oller, P. Fernández-Ibáñez, A. Agüera, J. Blanco, S. Malato, Appl. Catal. B Environ. 2012, 128, 119.

[12] K. M. Lee, C. W. Lai, K. S. Ngai, J. C. Juan, Water Res. 2016, 88, 428.

[13] S. M. Thalluri, L. Bai, C. Lv, Z. Huang, X. Hu, L. Liu, Adv. Sci. 2020, 7, 1902102.

[14] Y. Xu, A. Li, T. Yao, C. Ma, X. Zhang, J. H. Shah, H. Han, ChemSusChem 2017, 10, 4277.

[15] A. Fischbacher, C. von Sonntag, T. C. Schmidt, Chemosphere 2017, 182, 738.

[16] G. Lyngsie, L. Krumina, A. Tunlid, P. Persson, Sci. Rep. 2018, 8, 10834.

[17] J. He, X. Yang, B. Men, D. Wang, J. Environ. Sci. 2016, 39, 97.

[18] J. Xiao, S. Guo, D. Wang, Q. An, Chem. Eur. J. 2024, 30, e202304337.

[19] S. Giannakis, S. Liu, A. Carratalà, S. Rtimi, M. Bensimon, C. Pulgarin, Appl. Catal. B Environ. 2017, 204, 156.

[20] H. Zeng, X. Zhao, F. Zhao, Y. Park, M. Sillanpää, Chem. Eng. J. 2020, 382, 122972.

[21] G. Kothandam, G. Singh, X. Guan, J. M. Lee, K. Ramadass, S. Joseph, M. Benzigar, A. Karakoti, J. Yi, P. Kumar, A. Vinu, Adv. Sci. 2023, 10, 2301045.

[22] A. VahidMohammadi, J. Rosen, Y. Gogotsi, Science 2021, 372, eabf1581.

[23] L. Lin, F. Zhang, X. Hou, L. Wang, W. Wu, L. Wang, Y. Li, H. Xie, Sep. Purif. Technol. 2024, 334, 125982.

[24] J. Shen, Y. Li, Y. Zhu, Y. Hu, C. Li, J. Environ. Chem. Eng. 2016, 4, 2469.

[25] S. H. Yoo, D. Jang, H.-I. Joh, S. Lee, J. Mater. Chem. A 2017, 5, 748.

[26] C. Li, S. Yu, H. Che, X. Zhang, J. Han, Y. Mao, Y. Wang, C. Liu, H. Dong, ACS Sustain. Chem. Eng. 2018, 6, 16437.

[27] H. Zhao, Y. Wang, Y. Wang, T. Cao, G. Zhao, Appl. Catal. B Environ. 2012, 125, 120.

[28] K. V. Plakas, S. D. Sklari, D. A. Yiankakis, G. T. Sideropoulos, V. T. Zaspalis, A. J. Karabelas, Water Res. 2016, 91, 183.

[29] N. A. Zubir, C. Yacou, J. Motuzas, X. Zhang, J. C. da Diniz Costa, Sci. Rep. 2014, 4, 4594.

[30] H. Ye, G. Zheng, X. Yang, D. Zhang, Y. Zhang, S. Yan, L. You, S. Hou, Z. Huang, J. Electroanal. Chem. 2021, 898, 115652.

[31] J. Cheng, X. Tu, L. Zhang, M. Han, R. Zhou, S. Luo, H. Zeng, T. Li, J. Zou, J. Environ. Chem. Eng. 2024, 12, 112902.

[32] D. Astruc, Eur. J. Inorg. Chem. 2017, 2017, 6.

[33] Y. Li, B. Zhang, X. Liu, Q. Zhao, H. Zhang, Y. Zhang, P. Ning, S. Tian, J. Hazard. Mater. 2018, 353, 26.

[34] T. Shang, S. Chen, Z. Wei, D. Huang, S. Yang, ChemistrySelect 2021, 6, 8114.

[35] I. Sánchez-Montes, J. Carneiro Doerenkamp, Y. Núñez-de la Rosa, P. Hammer, R. C. Rocha-Filho, J. M. Aquino, J. Photochem. Photobiol. A Chem. 2023, 435, 114276.

[36] L. Ma, Y. Liu, Y. Liu, S. Jiang, P. Li, Y. Hao, P. Shao, A. Yin, X. Feng, B. Wang, Angew. Chem. Int. Ed. 2019, 58, 4221.

[37] X. Lv, Y. Leng, R. Wang, Y. Wei, X. Ren, W. Guo, Environ. Sci. Pollut. Res. 2022, 29, 34464.

[38] Y. Nie, C. Hu, J. Qu, X. Hu, J. Hazard. Mater. 2008, 154, 146.

[39] F. Gao, W. Shi, Z. Wang, ACS EST Water 2022, 2, 2602.

[40] E. Raczuk, B. Dmochowska, J. Samaszko-Fiertek, J. Madaj, Molecules 2022, 27, 787.

[41] M. Chu, Y. Wang, J. Xin, L. Zhang, Y. Liu, G. Yang, H. Ma, Y. Wang, H. Pang, X. Wang, Chem. Eng. J. 2023, 469, 143866.

[42] J. Halim, I. Persson, P. Eklund, P. O. Å. Persson, J. Rosen, RSC Adv. 2018, 8, 36785.

[43] X. Chen, X. Wang, D. Fang, Fullerenes Nanotubes Carbon Nanostruct. 2020, 28, 1048.

[44] E. Desimoni, G. I. Casella, A. Morone, A. M. Salvi, Surf. Interface Anal. 1990, 15, 627.

[45] J. C. S. Chu, Y. Bu, M. C. Lin, Surf. Sci. 1993, 284, 281.

[46] J. Russat, Surf. Interface Anal. 1988, 11, 414.

[47] M. C. Biesinger, B. P. Payne, A. P. Grosvenor, L. W. M. Lau, A. R. Gerson, R. S. C. Smart, Appl. Surf. Sci. 2011, 257, 2717.

[48] S. Koutzaris, M. Xanthopoulou, A. Laskaridis, I. A. Katsoyiannis, Sustainability 2022, 14, 16306.

[49] K. M. Nair, V. Kumaravel, S. C. Pillai, Chemosphere 2021, 269, 129325.

[50] J. Li, J. Huang, G. Zeng, C. Zhang, H. Yu, Q. Wan, K. Yi, W. Zhang, H. Pang, S. Liu, S. Li, W. He, Chem. Eng. J. 2023, 463, 142512.

[51] E. L. Schymanski, T. Kondić, S. Neumann, P. A. Thiessen, J. Zhang, E. E. Bolton, J. Cheminform. 2021, 13, 19.

[52] M. Alhabeb, K. Maleski, B. Anasori, P. Lelyukh, L. Clark, S. Sin, Y. Gogotsi, Chem. Mater. 2017, 29, 7633.

[53] B. Ahmed, D. H. Anjum, M. N. Hedhili, Y. Gogotsi, H. N. Alshareef, Nanoscale 2016, 8, 7580.

[54] K. Dührkop, M. Fleischauer, M. Ludwig, A. A. Aksenov, A. V. Melnik, M. Meusel, P. C. Dorrestein, J. Rousu, S. Böcker, Nat. Methods 2019, 16, 299.

[55] K. Dührkop, H. Shen, M. Meusel, J. Rousu, S. Böcker, Proc. Natl Acad. Sci. USA 2015, 112, 12580.

[56] H. Horai, M. Arita, S. Kanaya, Y. Nihei, T. Ikeda, K. Suwa, Y. Ojima, K. Tanaka, S. Tanaka, K. Aoshima, Y. Oda, Y. Kakazu, M. Kusano, T. Tohge, F. Matsuda, Y. Sawada, M. Y. Hirai, H. Nakanishi, K. Ikeda, N. Akimoto, T. Maoka, H. Takahashi, T. Ara, N. Sakurai, H. Suzuki, D. Shibata, S. Neumann, T. Iida, K. Tanaka, K. Funatsu, F. Matsuura, T. Soga, R. Taguchi, K. Saito, T. Nishioka, J. Mass Spectrom. 2010, 45, 703.

[57] P. Peets, W.-C. Wang, M. MacLeod, M. Breitholtz, J. W. Martin, A. Kruve, Environ. Sci. Technol. 2022, 56, 15508.

Rights & permissions

2026 The Author(s). Energy & Environmental Materials published by John Wiley & Sons Australia, Ltd on behalf of Zhengzhou University.