Dual-defect LaFeO3 photo-Fenton removes β-E2 from dairy wastewater
Abstract
Herein, LaFeO3 photocatalysts (HX-LFO and SX-LFO) were synthesized using hydrothermal and sol–gel methods, respectively, for removing β-E2 from dairy cattle breeding wastewater. A combination of flocculation pretreatment and photocatalytic Fenton oxidation was used to achieve efficient β-E2 degradation. Results revealed that HX-LFO had high defect concentrations and achieved better photocatalytic Fenton oxidation efficiency for β-E2 than SX-LFO. The H0.7-LFO/H2O2/visible (Vis) system completely degraded 2 mg/L of β-E2 within 2 h and achieved a total organic carbon (TOC) mineralization rate of 99.7%. The intermediate products, degradation pathways, and ecological toxicity of β-E2 degradation were analyzed. The H0.7-LFO/H2O2/Vis system exhibited stable degradation performance when humic acid and multiple anions coexisted in the reaction solution. The developed system increased the β-E2 degradation rate to 83.38%–100%. Characterizations and density functional theory calculations revealed that the La-defect formation energy in La/O dual-defect LaFeO3 was lower than that in LaFeO3 containing only La defects. Moreover, O defects facilitated the formation of La defects that lowered the energy barrier for free-radical desorption, making it easier for free radicals to form and diffuse into the reaction solution. La/O dual-defect LaFeO3 exhibited lower binding energy for β-E2, accelerating charge transfer within itself and from itself to β-E2.
Data availability
The data that support the findings of this study are available from the corresponding author upon reasonable request.
Code availability
No code was used in this study.
References
Zhao, X., Grimes, K. L., Colosi, L. M. & Lung, W. S. Attenuation, transport, and management of estrogens: A review. Chemosphere 230, 462–478 (2019).
Pratush, A. et al. Biotransformation strategies for steroid estrogen and androgen pollution. Appl. Microbiol. Biotechnol. 104, 2385–2409 (2020).
Zhang, Y. et al. Pollution characteristics and risk prediction of endocrine disruptors in lakes of Wuhan. Toxics 10, 93 (2022).
Li, S. & Sun, K. Suppression mechanism of model humic constituents on laccase-enabled 17β-estradiol oxidation and oligomerization. Chemosphere 290, 133356 (2022).
Zhao, C. X. et al. Formation and mechanisms of nano-metal oxide-biochar composites for pollutants removal: A review. Sci. Total Environ. 767, 145305 (2021).
Maridevaru, M. C., Naceruddin, A. H., Aljafari, B. & Anandan, S. Synthesis of Ce0.1La0.9MnO3 perovskite for degradation of endocrine-disrupting chemicals under visible photons. Catalysts 12, 1258 (2022).
Šojić Merkulov, D. et al. Sustainable removal of 17α-ethynylestradiol from aqueous environment using rare earth doped lanthanum manganite nanomaterials. Catal. Today 424, 113746 (2023).
Ayekoe, C. Y. P., Robert, D. & Lanciné, D. G. Combination of coagulation-flocculation and heterogeneous photocatalysis for improving the removal of humic substances in real treated water from Agbô River (Ivory-Coast). Catal. Today 281, 2–13 (2017).
Lin, Z. et al. Different photocatalytic levels of organics in papermaking wastewater by flocculation-photocatalysis and SBR-photocatalysis: Degradation and GC–MS experiments, adsorption and photocatalysis simulations. Chem. Eng. J. 412, 128715 (2021).
Kanhere, P. & Chen, Z. A review on visible light active perovskite-based photocatalysts. Molecules 19, 19995–20022 (2014).
Feng, M. et al. Green synthesis of CaxLa1-xMnO3 with modulation of mesoporous and vacancies for efficient low concentration phosphate adsorption. J. Environ. Manag. 351, 119837 (2024).
Zhong, X., Liu, J., Jie, H., Wu, W. & Jiang, F. Highly efficient copper doping LaFeO3 perovskite for bisphenol A removal by activating peroxymonosulfate. Catalysts 13, 575 (2023).
Yang, X. et al. Insights into the role of cation vacancy for significantly enhanced electrochemical nitrogen reduction. Appl. Catal. B 264, 118477 (2020).
Yang, X. et al. Defective MnxZr1–xO2 solid solution for the catalytic oxidation of toluene: Insights into the oxygen vacancy contribution. ACS Appl. Mater. Interfaces 11, 730–739 (2019).
Zheng, B. et al. Exsolution of iron oxide on LaFeO3 perovskite: A robust heterostructured support for constructing self-adjustable Pt-based room-temperature CO oxidation catalysts. ACS Appl. Mater. Interfaces 13, 27029–27040 (2021).
Zhu, Y. et al. Enhancing electrocatalytic activity of perovskite oxides by tuning cation deficiency for oxygen reduction and evolution reactions. Chem. Mat. 28, 1691–1697 (2016).
Guo, S. Q. et al. Insights for optimum cation defects in photocatalysis: A case study of hematite nanostructures. Appl. Catal. B 264, 118506 (2020).
He, J. et al. Subsurface A-site vacancy activates lattice oxygen in perovskite ferrites for methane anaerobic oxidation to syngas. Nat. Commun. 15, 5422 (2024).
Nakamura, K., Mashiko, H., Yoshimatsu, K. & Ohtomo, A. Impact of built-in potential across LaFeO3/SrTiO3 heterojunctions on photocatalytic activity. Appl. Phys. Lett. 108, 211605 (2016).
Arman, M. M. & Ahmed, M. A. Effects of vacancy co-doping on the structure, magnetic and dielectric properties of LaFeO3 perovskite nanoparticles. Appl. Phys. A 128, 554 (2022).
Li, M. et al. Different La/Fe oxide composites for efficient phosphate removal from wastewater: Properties and mechanisms. J. Environ. Chem. Eng. 10, 107329 (2022).
He, N. et al. Designing with A-site cation defects in LaFeO3: Removal of tetracycline hydrochloride in complex environments using photo-Fenton synergy. Chem. Eng. J. 484, 149613 (2024).
Yu, K. et al. Engineering cation defect-mediated Z-scheme photocatalysts for a highly efficient and stable photocatalytic hydrogen production. J. Mater. Chem. A 9, 7759–7766 (2021).
González, G. B. Investigating the defect structures in transparent conducting oxides using X-ray and neutron scattering techniques. Materials 5, 818–850 (2012).
Rani, S., Shekhar, M., Kumar, P. & Prasad, S. Study on quantitative rietveld analysis of XRD patterns of different sizes of bismuth ferrite. Appl. Phys. A 128, 1046 (2022).
Hou, Z. et al. Lattice-strain engineering for heterogenous electrocatalytic oxygen evolution reaction. Adv. Mater. 35, 2209876 (2023).
Porz, L. et al. Dislocation-based high-temperature plasticity of polycrystalline perovskite SrTiO3. J. Mater. Sci. 58, 2430–2438 (2023).
Jiang, J. et al. Carrier lifetime enhancement in halide perovskite via remote epitaxy. Nat. Commun. 10, 4145 (2019).
Thommes, M. et al. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem. 87, 1051–1069 (2015).
Gao, P. et al. The role of cation vacancies in electrode materials for enhanced electrochemical energy storage: Synthesis, advanced characterization, and fundamentals. Adv. Energy Mater. 10, 1903780 (2020).
Gionco, C. et al. Paramagnetic defects in polycrystalline zirconia: An EPR and DFT study. Chem. Mat. 25, 2243–2253 (2013).
Sorescu, M., Xu, T., Burnett, J. D. & Aitken, J. A. Investigation of LaFeO3 perovskite growth mechanism through mechanical ball milling of lanthanum and iron oxides. J. Mater. Sci. 46, 6709–6717 (2011).
Zitolo, A. et al. Identification of catalytic sites for oxygen reduction in iron- and nitrogen-doped graphene materials. Nat. Mater. 14, 937–942 (2015).
Kharton, V. V. et al. Oxygen nonstoichiometry, mixed conductivity, and mössbauer spectra of Ln0.5A0.5FeO3−δ (Ln = La−Sm, A = Sr, Ba): Effects of cation size. Chem. Mat. 20, 6457–6467 (2008).
Mahapatra, A. S. et al. Modulation of magnetic and dielectric property of LaFeO3 by simultaneous doping with Ca2+ and Co2+-ions. J. Alloy. Compd. 743, 274–282 (2018).
Al-Mamari, R. T. et al. Core and surface structure and magnetic properties of mechano-synthesized LaFeO3 nanoparticles and their Eu3+-doped and Eu3+/Cr3+-co-doped variants. Sci. Rep. 14, 14770 (2024).
Palstra, T. T. M., Mydosh, J. A., Nieuwenhuys, G. J., van der Kraan, A. M. & Buschow, K. H. J. Study of the critical behaviour of the magnetization and electrical resistivity in cubic La(Fe, Si)13 compounds. J. Magn. Magn. Mater. 36, 290–296 (1983).
Çoban Özkan, D., Türk, A. & Çelik, E. Synthesis and characterizations of sol-gel derived LaFeO3 perovskite powders. J. Mater. Sci. Mater. Electron. 31, 22789–22809 (2020).
Peng, K., Fu, L., Yang, H. & Ouyang, J. Perovskite LaFeO3/montmorillonite nanocomposites: Synthesis, interface characteristics and enhanced photocatalytic activity. Sci. Rep. 6, 19723 (2016).
Gong, S. et al. Highly active and humidity resistive perovskite LaFeO3 based catalysts for efficient ozone decomposition. Appl Catal. B 241, 578–587 (2019).
Gu, C.-H. et al. Upcycling waste sewage sludge into superior single-atom Fenton-like catalyst for sustainable water purification. Nat. Water 2, 649–662 (2024).
Li, M. et al. Green and efficient Al-doped LaFexAl1–xO3 perovskite oxide for enhanced phosphate adsorption with creation of oxygen vacancies. ACS Appl. Mater. Interfaces 15, 16942–16952 (2023).
Ahile, U. J., Wuana, R. A., Itodo, A. U., Sha’Ato, R. & Dantas, R. F. A review on the use of chelating agents as an alternative to promote photo-Fenton at neutral pH: Current trends, knowledge gap and future studies. Sci. Total Environ. 710, 134872 (2020).
Wu, Y. & Wang, H. Construction of CuMoO4/MnO2/tourmaline composite for efficient organic wastewater decontamination via photo-Fenton-like processes. J. Environ. Chem. Eng. 11, 111190 (2023).
Huang, X. et al. Enhanced heterogeneous photo-Fenton catalytic degradation of tetracycline over yCeO2/Fh composites: Performance, degradation pathways, Fe2+ regeneration and mechanism. Chem. Eng. J. 392, 123636 (2020).
Zhang, P. et al. Catalytic degradation of estrogen by persulfate activated with iron-doped graphitic biochar: Process variables effects and matrix effects. Chem. Eng. J. 378, 122141 (2019).
Ciślak, M., Kruszelnicka, I., Zembrzuska, J. & Ginter-Kramarczyk, D. Estrogen pollution of the European aquatic environment: A critical review. Water Res 229, 119413 (2023).
Yan, Y. et al. Designing defect enriched Bi2Ti2O7/C3N4 micro-photo-electrolysis reactor for photo-Fenton like catalytic reaction. Sep. Purif. Technol. 330, 125380 (2024).
Yang, Z., Xia, X., Shao, L., Wang, L. & Liu, Y. Efficient photocatalytic degradation of tetracycline under visible light by Z-scheme Ag3PO4/mixed-valence MIL-88A(Fe) heterojunctions: Mechanism insight, degradation pathways and DFT calculation. Chem. Eng. J. 410, 128454 (2021).
Yuan, T. et al. Efficient recovery of high-concentration phosphorus from livestock wastewater: Combined effects of magnesium-based metal-organic framework-derived metal oxide morphology and magnesium oxide different vacancy species. Sep. Purif. Technol. 374, 133784 (2025).
Lv, S. et al. Superoxide radical (·O2−)-driven peroxymonosulfate activation via cation-deficient lanthanum ferrite perovskite oxides: Electronic structure modulation for high-efficiency estrogen degradation in dairy wastewater. Adv. Compos. Hybrid Mater. 8, 397 (2025).
Li, H., Li, P., Lin, M. & Zhu, X. Effects of LaFeO3 morphology on oxygen species and chemical looping partial oxidation of methane. Chem. Mat. 37, 2931–2942 (2025).
Acknowledgements
This work was supported by the Key R & D and Technology Transfer Projects of Hulunbuir [SF2025004], the National Key Research and Development Program of China [2022YFD1901305], Yunnan Fundamental Research Projects [202101AT070002], Wangfeng Expert Primary-level Workstation, Yunnan Province, Intelligent aid to Xinjiang Innovation and Development Talent Plan (“Group Group” aid team) “Environmental functional materials Development and agricultural applications”.
Author information
Authors and Affiliations
Contributions
S.L., Conceptualization, Writing–original draft, Visualization; T.Y., Data curation, Writing–review and editing; X.Z., Formal analysis; P.Y., Investigation; K.F., Methodology; X.Y., Project administration; W.F., Software; Q.Z., Validation; Y.L., Supervision; F.W., Funding acquisition, Resources.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing interests.
Additional information
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary information
Rights and permissions
Open Access This article is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License, which permits any non-commercial use, sharing, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if you modified the licensed material. You do not have permission under this licence to share adapted material derived from this article or parts of it. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by-nc-nd/4.0/.
About this article
Cite this article
Lv, S., Yuan, T., Zhang, X. et al. Dual-defect LaFeO3 photo-Fenton removes β-E2 from dairy wastewater. npj Clean Water (2025). https://doi.org/10.1038/s41545-025-00535-6
Received:
Accepted:
Published:
DOI: https://doi.org/10.1038/s41545-025-00535-6