This paper reports the controlled synthesis of ZrO2 nanocrystals via a peroxide-assisted hydrothermal (HT) route at 120 °C, with processing times ranging from 12 to 72 h, and investigates the correlation between structural evolution, defect chemistry, and functional properties. X-ray diffraction (XRD) combined with Rietveld refinement confirmed the formation of a monophasic monoclinic structure with high structural reliability. Microstructural analysis revealed progressive crystallite growth and lattice ordering with increasing reaction time, accompanied by subtle distortions in local coordination environments. Micro-Raman spectroscopy indicated improved medium-range structural organization at longer synthesis durations, while transmission electron microscopy showed quasi-spherical and nanorod-like aggregates formed through oriented attachment, with particle sizes of 6–9 nm. Optical investigations using diffuse reflectance spectroscopy revealed band gap energies of 3.45–3.65 eV, attributed to defect-induced intermediate electronic states associated primarily with oxygen vacancies. A comprehensive photoluminescence (PL) analysis suggests that the observed emission arises from defect-mediated recombination pathways involving localized states within the band gap, modulated by the interplay between structural order and residual defects. The role of hydrogen peroxide is discussed in terms of regulating oxygen vacancy concentration, promoting structural stabilization while preserving functional defect states. The results demonstrate that precise control of HT processing time enables tuning of structural disorder, defect density, optical response, and the enhanced photocatalytic performance of ZrO2 toward RhB dye degradation, highlighting its potential for optoelectronic applications.
Sousa et al. (Mon,) studied this question.