SYNTHESIS AND INVESTIGATION OF ALUMINUM-SUBSTITUTED SPINELS BASED ON ZNMN2O4: STRUCTURE, PROPERTIES, AND APPLICATION PROSPECTS
DOI:
https://doi.org/10.32782/naturaljournal.10.2024.9Keywords:
spinels, sol-gel method, aluminum substitution, bandgap, crystal structureAbstract
Spinels are important functional materials that are actively researched due to their promising properties in various fields such as catalysis, sensors, and batteries. Aluminum-substituted spinels based on ZnMn2O4 may exhibit enhanced properties compared to other materials in this class, thanks to their stability, broad tunability of the bandgap, and high porosity. The relevance of this work is underscored by the necessity to search for new materials with controllable properties for use in high-tech industries, particularly in energy applications, to adapt catalysts to modified substrates. This article presents the results of the synthesis and comprehensive study of the properties of aluminum-substituted spinels with the composition Zn(1-x)AlxMn2O4 (x = 0,05, 0,10, 0,15, 0,20, 0,25, 0,30) synthesized using the sol-gel method. For structural characterization and phase composition determination, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), diffuse reflectance spectroscopy (DRS), and scanning electron microscopy (SEM) methods were employed. The size of the diffracting crystallites was estimated using the Scherrer equation. X-ray phase analysis confirmed the single-phase nature of all samples regardless of the substitution level, indicating the stability of the obtained structures. Structural refinement was conducted using the Rietveld method, demonstrating a high correspondence between experimental diffractograms and theoretical models. The main parameters of the unit cell and the X-ray density were established, and changes in the metal-oxide distances in the coordination polyhedra were analyzed. FTIR spectroscopy revealed the presence of three absorption bands in the range of 1000 to 385 cm-¹ for both reference and substituted samples, with a gradual shift to the long-wavelength region. Bandgap, calculated using the Kubelka-Munk function and Tauc’s graphical method, changes from 2.76 eV to 2.90 eV with initial increases in substitution, then decreases to 2.53 eV with further increases in aluminum concentration. SEM studies confirmed the high porosity and developed surface area of the synthesized samples, which is a crucial characteristic for potential applications of these materials in various fields, including catalysis and sensors.
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