Mechanistic insights and DFT analysis of bimetal doped styrofoam-like LaFeO3 perovskites with in-built dual redox couples for enhanced Photo-Fenton degradation of Tetracycline

• Published in: Chemical engineering journal (Lausanne, Switzerland : 1996) Vol. 481; p. 148466
• Main Authors: James, Anupriya, Shivakumar, Rodney, John D, Joshi, Sindhur, Dalimba, Udayakumar, Kim, Byung Chul, Udayashankar, N.K.
• Format: Journal Article
• Language: English
• Published: Elsevier B.V 01.02.2024
• Subjects: LaFeO3; Perovskite; photo-Fenton; Photocatalysis; Tetracycline; LaFeO3; Perovskite; photo-Fenton; Photocatalysis; Tetracycline
• ISSN: 1385-8947; 1873-3212
• DOI: 10.1016/j.cej.2023.148466

[Display omitted] •LFOBC catalyst exhibited 94.6 % TC removal in 60 min.•Fe3+/Fe2+, Cu2+/Cu+ dual redox centers played a key role in TC removal.•Identified •OH radicals as the major active species in the photo-Fenton process.•Degradation pathway and mechanism are explored. The rising number of contaminants released into the environment and the inadequacies of traditional wastewater treatment techniques have led to the demand for enhanced oxidation technologies like photo-Fenton. In this study, bimetal co-doped lanthanum orthoferrite (BixLa1-xCuyFe1-yO3 (x = 0, 0.01, 0.05, 0.1; y = 0, 0.01, 0.05, 0.1, 0.15)) based photo-Fenton catalysts with the in-built redox couples Fe3+/Fe2+, Cu2+/Cu+ and oxygen vacancies have been successfully synthesised via a facile one-pot solution combustion route. Systematic studies show that the Bi0.05La0.95Cu0.1Fe0.9O3 (LFOBC) exhibits an optimal photo-Fenton degradation rate of 0.0497/min for Tetracycline (TC) removal, being ∼ 1.8 and ∼ 6.2 times greater than Bi0.05La0.95FeO3 (LFOB) and pristine LaFeO3 (LFO) respectively. DFT analysis confirmed the better adsorption and dissociation of H2O2 on a bimetal co-doped catalyst and identified the electron density difference in LFOBC, which can induce the H2O2 dissociation. A detailed investigation of various influencing reaction parameters is explored. The degradation pathway for the LFOBC catalyst with the toxicological characteristics of each intermediate is analysed. This study presents the Bi0.05La0.95Cu0.1Fe0.9O3 as a potential photocatalyst for enhanced photo-Fenton degradation with excellent efficiency observed for the degradation of various harmful pollutants for environmental remediation.