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Item Cobalt-doped LaFeO3 for photo-Fenton degradation of organic pollutants and visible-light-assisted water splitting(Springer, 2024) James, A.; Rodney, J.D.; Manojbabu, A.; Joshi, S.; Rao, L.; Badekai Ramachandra, B.R.; Udayashankar, N.K.The increasing demand for clean energy sources and the growing concerns about environmental pollution have led to a significant interest in developing efficient photocatalytic and photoelectrochemical systems. Here, we report the visible-light-induced photo-Fenton catalytic degradation of Methylene Blue (MB) dye over LaFeO3 and LaCo xFe1−xO3 (x = 0.01, 0.05, 0.1) catalysts synthesized via the facile combustion method. The LaCo0.01Fe0.99O3 has significantly enhanced the photo-Fenton catalytic efficiency of LaFeO3 from 67.75 to 93.85% for MB dye removal after 180 min of light irradiation. The rate constants calculated via the pseudo-first-order kinetics mechanism are found to be 0.00532/min for LaFeO3 and 0.01476/min for LaCo0.01Fe0.99O3, respectively. In addition, the most effective LaCo0.01Fe0.99O3 catalyst has demonstrated remarkable degradation performance towards Tetracycline (TC) and Methyl Orange (MO) dye with an efficacy of 93.81% and 69.67%, respectively, indicating its versatility. Further, the pristine and doped LaFeO3 were structurally optimized using DFT, and the computed band gaps were following the experimental data. Interestingly, the same catalyst can be employed as a light-induced electrocatalyst in addition to water treatment by taking advantage of its dual functionality. The LaCo0.01Fe0.99O3 catalyst achieved a benchmark current density of 10 mA/cm2 for H2 evolution at an overpotential of 297 mV vs. RHE which further improved to 190 mV vs. RHE under illumination. This work provides valuable insights on partial Co incorporation at the B-site of LaFeO3 for the development of visible-light-induced photocatalytic and electrocatalytic systems, which is hoped to contribute to the advancement of sustainable energy production and environmental remediation. © 2024, The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.Item 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(Elsevier B.V., 2024) James, A.; Naik, S.; Rodney, J.D.; Joshi, S.; Udayakumar, U.; Kim, B.C.; Udayashankar, N.K.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. © 2024 Elsevier B.V.