Synchrotron X-ray absorption spectroscopy study of the local atomic structures and cation ordering in perovskite- and spinel-type zinc stannate synthesized by co-precipitation method

Abstract

Zinc stannate nanocrystalline powders with two different crystal structures were synthesized from two different initial Zn2+/Sn4+ ratios by a simple co-precipitation method. X-ray diffraction (XRD), X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) techniques were used to investigate crystal structure, oxidation, and cation ordering of the after-calcined powders. XRD patterns clearly showed that the ZnSnO3 perovskite phase was obtained using an equal initial Zn2+/Sn4+ ratio of 1:1, while a double Zn2+ excess sample (2:1) produced the pure Zn2SnO4 spinel phase. The chemical shifts in Zn K- and Sn L3-edge XANES spectra supported that only Zn2+ and Sn4+ ions existed in these stannate samples. Moreover, the theoretical simulation of the Zn K-edge EXAFS experimental data also indicated a change in the cation ordering from orthorhombic, for perovskite ZnSnO3, to cubic for spinel Zn2SnO4. This is the first time that the local atomic structural characterization of zinc stannate powders derived from EXAFS analysis has been presented.