Linking Defect-Controlled Grain Growth and Band-Edge Optical Response in Chymosin-Assisted Pechini-Derived CeO2−δ Nanoparticles

Abstract

We investigate how grain growth, strain relaxation, and vacancy chemistry shape the near-edge optical response of nanocrystalline Ce (Formula presented.) prepared by a chymosin-assisted Pechini route from nitrate–citrate precursors. Rietveld line-profile analysis shows that phase-pure Ce (Formula presented.) 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 (Formula presented.) and activation energy (Formula presented.) kJ (Formula presented.). Raman spectroscopy tracks the sharpening of the (Formula presented.) mode and the fading of defect-related bands, X-ray photoelectron spectroscopy reveals a nonmonotonic evolution of the surface (Formula presented.) fraction and separates lattice from adsorbed oxygen species, and electron paramagnetic resonance detects vacancy-bound (Formula presented.) polarons that weaken at high temperature. Diffuse-reflectance UV–Vis spectra show a modest blue shift of the apparent band gap from (Formula presented.) to 2.95 eV as crystallites coarsen, while the Urbach energy (Formula presented.) follows the (Formula presented.) 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 (Formula presented.) nanoparticles.