Faculty Publications
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Item Bi-functional LaMxFe1-xO3 (M = Cu, Co, Ni) for photo-fenton degradation of methylene blue and photoelectrochemical water splitting(Elsevier Ltd, 2023) James, A.; Rodney, J.D.; Rao, L.; Badekai Ramachandra, B.R.; Udayashankar, N.K.Due to growing concern over environmental remediation and the energy crisis, perovskite nanoparticles have gained wide interest in converting solar energy to sustainable fuel and also in degrading organic effluents. Herein, we report the synthesis and bi-functional activity of one-pot-glycine combustion derived LaMxFe1-xO3 (M = Cu, Co, Ni; x = 0, 0.01) for photo-Fenton degradation of Methylene Blue (MB) and photoelectrochemical water splitting. When used as a photocatalyst, with partial substitution of Cu even at a lower concentration, LaCu0.01Fe0.99O3 has exhibited excellent degradation efficiency of 96.4% in 90 min, which is 2.5 times better than the LaFeO3. On the other hand, Co and Ni modified LaFeO3 photocatalysts have demonstrated prominent activities with degradation efficiency of 93.8% and 74.8% respectively within 180 min of visible light irradiation. The retention and reusability analysis showed that LaCu0.01Fe0.99O3 is stable against photo corrosion and remains unchanged after 5 consecutive cycles of MB dye degradation. In addition, LaCu0.01Fe0.99O3 is complimented as a single catalyst for dual functions such as photocatalysis and electrocatalysis, both of which are assisted by visible light. Under illumination, the overpotential (η) improved from 507.6 mV vs RHE (dark) to 498.1 mV vs RHE (light) for O2 evolution and 220.5 mV vs RHE (dark) to 182.8 mV vs RHE (light) for H2 generation respectively. The light response of the catalyst and improvement in activity is validated by the significant enhancement in current density under exposure at both half cycle of chronoamperometry. © 2023 Hydrogen Energy Publications LLCItem 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.Item Kinetic Comparison of Photocatalysis with the Photo-Fenton Process on the Removal of Tetracycline Using Bismuth-Modified Lanthanum Orthoferrite Nanostructures(American Chemical Society, 2024) James, A.; Rodney, J.D.; Udayashankar, N.K.In this study, we investigate visible-light-driven photocatalytic and photo-Fenton degradation of tetracycline (TC) using bismuth-impregnated lanthanum orthoferrite (BixLa1-xFeO3 (x = 0, 0.01, 0.05, 0.07)) nanostructures. Bi doping significantly improves the removal of TC, with Bi0.05La0.95FeO3 (LFO-Bi5) exhibiting optimal degradation. In both photocatalysis (PC) and photo-Fenton catalysis (PFC), the reaction follows pseudo-first-order kinetics, with LFO-Bi5 showing rate constants of 0.0065/min for PC and 0.02716/min for PFC, surpassing LaFeO3 by 2.76 and 3.43 times, respectively. The long-term presence of photoexcited carriers in LFO-Bi5 is confirmed through transient PL, TRPL, and EIS studies. The superior degradation capabilities are attributed to radicals in photocatalysis and OH• radicals in photo-Fenton catalysis. The PFC exhibited faster kinetics due to the rapid production of OH• radicals via the Fe-redox cycle and direct dissociation of H2O2 at oxygen vacancies. LFO-Bi5 demonstrates excellent photostability and reusability for up to six consecutive cycles. The degradation pathway and toxicological properties of the intermediates are analyzed, highlighting the potential of LFO-Bi5 catalysts in antibiotic-contaminated water treatment. © 2024 American Chemical Society.Item Cu- and Bi-codoped LaFeO3-Decorated MXene Nanosheets for Photo-Fenton Catalysis and Hydrogen Evolution(American Chemical Society, 2025) James, A.; Ray, S.; Rodney, J.D.; Carva, K.; Udayashankar, N.K.; Kim, B.C.The increasing release of contaminants into the environment and the demand for sustainable energy solutions have prompted the exploration of advanced oxidation methods such as photo-Fenton and photoelectrochemical water splitting. Herein, hierarchical heterostructures of Cu- and Bi-codoped LaFeO3(Bi0.05La0.95Cu0.1Fe0.9O3) (LFOBC)-decorated Ti3C2(MXene) nanosheets were developed by a low-cost one-pot combustion approach. The optimized LFOBC/Mx-7 (Bi0.05La0.95Cu0.1Fe0.9O3/Ti3C2-7) composite demonstrated superior photo-Fenton degradation of tetracycline (TC), achieving 1.69 times higher efficiency than LFOBC and 10.65 times more efficiency than pristine LaFeO3(LFO). This enhanced performance is attributed to strong interfacial coupling, which suppressed photoexcited carrier recombination, as confirmed by PL, TRPL, EIS, and photocurrent studies. Experimental and theoretical work function analyses revealed band bending and the formation of an Ohmic junction at the interface. Furthermore, a degradation mechanism and a reaction pathway were proposed, and the reduction in toxicity levels was identified. The LFOBC/Mx-7 catalyst also exhibited promising results for H2evolution with an overpotential of 156 mV vs RHE under visible-light illumination, which was 2.37 times less than that of LFOBC. These results, therefore, showcase the LFOBC/Mx composite as a multifunctional photocatalyst for both pollutant degradation and sustainable energy generation. © 2025 American Chemical Society