Hydrothermal synthesis map of bismuth titanates

The hydrothermal synthesis of four bismuth titanate materials from common bismuth and titanium precursors under hydrothermal conditions is described. Reaction of NaBiO3·2H2O and anatase TiO2 in concentrated NaOH solution at 240 °C is shown to produce perovskite and sillenite phases Na0.5Bi0.5TiO3 and Bi12TiO20, depending on the ratio of metal precursors used. When KOH solution is used and a 1:1 ratio of the same precursors, a pyrochlore Bi1.43Ti2O6(OH)0.29(H2O)0.66 is formed. The use of a mixture of HNO3 and NaOH is shown to facilitate the formation of the Aurivillius-type bismuth titanate Bi4Ti3O12. The phases have been isolated separately as phase-pure powders and profile refinement of powder X-ray diffraction data allows comparisons with comparable materials reported in the literature. Analysis of Bi LIII-edge X-ray absorption near edge structure (XANES) spectra of the materials shows the oxidation state of bismuth is +3 in all of the hydrothermally derived products.

Graphical abstractUse of NaBiO3·2H2O and TiO2 as reagents under hydrothermal conditions allows the phase-pure preparation of four crystalline bismuth titanate materials. Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► NaBiO3 and TiO2 under hydrothermal conditions allow formation of bismuth titanates. ► Synthesis of four distint phases has been mapped. ► Bi LIII-edge XANES shows Bi is reduced to oxidation state +3 in all materials. ► A new hydrated bismuth titanate pyrochlore has been isolated