Veldhuis Sjoerd A, Vijselaar Wouter J C, Stawski Tomasz M, ten Elshof Johan E
Inorganic Materials Science Group, MESA+ Institute for Nanotechnology, University of Twente , P.O. Box 217, 7500 AE Enschede, The Netherlands.
Inorg Chem. 2014 Dec 15;53(24):13188-96. doi: 10.1021/ic502410v. Epub 2014 Nov 25.
Nanocrystalline barium titanate (8-10 nm crystallite size) was prepared at temperatures of 23-78 °C through reaction of a modified titanium alkoxide precursor in benzyl alcohol with barium hydroxide octahydrate. The room temperature formation of a perovskite phase from solution is associated with the use of benzyl alcohol as solvent medium. The formation mechanism was elucidated by studying the stability and interaction of each precursor with the solvent and with each other using various experimental characterization techniques. Density functional theory (DFT) computational models which agreed well with our experimental data could explain the formation of the solid phase. The stability of the Ti precursor was enhanced by steric hindrance exerted by phenylmethoxy ligands that originated from the benzyl alcohol solvent. Electron microscopy and X-ray diffraction indicated that the crystallite sizes were independent of the reaction temperature. Crystal growth was inhibited by the stabilizing phenylmethoxy groups present on the surface of the crystallites.
通过在苄醇中用改性钛醇盐前体与八水合氢氧化钡反应，在23至78°C的温度下制备了纳米晶钛酸钡（微晶尺寸为8 - 10nm）。从溶液中室温形成钙钛矿相与使用苄醇作为溶剂介质有关。通过使用各种实验表征技术研究每种前体与溶剂以及彼此之间的稳定性和相互作用，阐明了形成机理。与我们的实验数据吻合良好的密度泛函理论（DFT）计算模型可以解释固相的形成。源自苄醇溶剂的苯甲氧基配体施加的空间位阻增强了Ti前体的稳定性。电子显微镜和X射线衍射表明微晶尺寸与反应温度无关。微晶表面存在的稳定苯甲氧基基团抑制了晶体生长。
