ArticleMaterials (Basel, Switzerland)2025
Linking Defect-Controlled Grain Growth and Band-Edge Optical Response in Chymosin-Assisted Pechini-Derived CeO
Article in Materials (Basel, Switzerland), 2025. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.
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Abstract
We investigate how grain growth, strain relaxation, and vacancy chemistry shape the near-edge optical response of nanocrystalline CeO2-δ prepared by a chymosin-assisted Pechini route from nitrate-citrate precursors. Rietveld line-profile analysis shows that phase-pure CeO2-δ forms after calcination between 400 and 1000 °C. Over this range, the average crystallite size increases from ≈3.4 to ≈57 nm, while the microstrain decreases from 0.79% to 0.05%, with size-strain scaling consistent with interface-controlled grain growth that follows a normal growth law with exponent m=2 and activation energy Q≈155 kJ mol-1. Raman spectroscopy tracks the sharpening of the F2g mode and the fading of defect-related bands, X-ray photoelectron spectroscopy reveals a nonmonotonic evolution of the surface Ce3+ fraction and separates lattice from adsorbed oxygen species, and electron paramagnetic resonance detects vacancy-bound Ce3+ polarons that weaken at high temperature. Diffuse-reflectance UV-Vis spectra show a modest blue shift of the apparent band gap from Eg≈2.78 to 2.95 eV as crystallites coarsen, while the Urbach energy Eu follows the Ce3+ content and sub-gap tailing. The structural, spectroscopic, and optical results together map out a quantitative connection between grain growth, vacancy populations, and near-edge optical properties in CeO2-δ nanoparticles.
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