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<p>This is the first report on synthesis of Gadolinium (Gd) substituted oxygen-deficient BaFeO<sub>3-x</sub> perovskite using solution combustion method, which act as an extremely efficient photocatalyst in degradation of methylene blue (MB) dye. The structural analysis via XRD reveals the polymorphism and reversible phase transition (cubic ⇌ hexagonal) via octahedral tilting and site-selective Gd-substitution (2.5 – 10%), previously unreported thus far, for this material composition. The structural stability of BaFeO<sub>3-x</sub> is also discussed via Goldschmidt’s tolerance factor. A unique approach of Boltzmann regression analysis is used along with Tauc plot from optical absorption spectra and observed the narrowing and broadening of bandgaps controlled by site-selective Gd-substitution. The increased dislocations and reduced Urbach energy on B-site Gd-substitution, represent the high defect density and large number of charge carriers. This has presumably induced the photocatalytic activity in Gd<sub>0.1</sub>BaFe<sub>0.9</sub>O<sub>3-x</sub> against MB. A 99% dye degradation with only 20&#xa0;mg of catalyst for concentrations as high as 10&#xa0;ppm of dye within 60&#xa0;min, representing exceptional performance. The article also introduces a novel approach for photocatalytic dye-degradation study using adsorption-degradation statistics for monomers and rarely studied dimers of MB dye as a function of time, and dye/catalyst concentrations. The unique approach of comparative kinetic studies assisted with pseudo-ordered reaction models, provide half-life time (t<sub>1/2</sub>) as one of the critical parameters, under several conditions, for scaling up this technology for practical wastewater treatment applications.</p> Graphical Abstract <p></p>

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Photo-degradation of methylene blue using the stable rare-earth metal substituted oxygen-deficient BaFeO3-x perovskites

  • 期刊论文

  • 发表日期：

    2025年11月23日

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  • Palash Shendre,
  • Nivedita Singh,
  • Elangovan Elamurugu

摘要

This is the first report on synthesis of Gadolinium (Gd) substituted oxygen-deficient BaFeO3-x perovskite using solution combustion method, which act as an extremely efficient photocatalyst in degradation of methylene blue (MB) dye. The structural analysis via XRD reveals the polymorphism and reversible phase transition (cubic ⇌ hexagonal) via octahedral tilting and site-selective Gd-substitution (2.5 – 10%), previously unreported thus far, for this material composition. The structural stability of BaFeO3-x is also discussed via Goldschmidt’s tolerance factor. A unique approach of Boltzmann regression analysis is used along with Tauc plot from optical absorption spectra and observed the narrowing and broadening of bandgaps controlled by site-selective Gd-substitution. The increased dislocations and reduced Urbach energy on B-site Gd-substitution, represent the high defect density and large number of charge carriers. This has presumably induced the photocatalytic activity in Gd0.1BaFe0.9O3-x against MB. A 99% dye degradation with only 20 mg of catalyst for concentrations as high as 10 ppm of dye within 60 min, representing exceptional performance. The article also introduces a novel approach for photocatalytic dye-degradation study using adsorption-degradation statistics for monomers and rarely studied dimers of MB dye as a function of time, and dye/catalyst concentrations. The unique approach of comparative kinetic studies assisted with pseudo-ordered reaction models, provide half-life time (t1/2) as one of the critical parameters, under several conditions, for scaling up this technology for practical wastewater treatment applications.

Graphical Abstract