Laboratory for Multifunctional Materials, Department of Materials, ETH Zürich, Wolfgang-Pauli-Strasse 10, 8093 Zürich, Switzerland.
Chemistry. 2012 Feb 20;18(8):2305-12. doi: 10.1002/chem.201101514. Epub 2012 Jan 16.
Insight into the complex chemical mechanism for the formation of tungstite nanoparticles obtained by the reaction of tungsten hexachloride with benzyl alcohol is presented herein. The organic and inorganic species involved in the formation of the nanoparticles were studied by time-dependent gas chromatography and X-ray diffraction as well as by time-resolved in situ X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopy. Principal component analysis revealed two intermediates, which were identified as WCl(4) and WOCl(4) by using linear combination analysis. Quick-scanning extended X-ray absorption fine structure spectroscopy enabled the time-dependent evolution of the starting compound, the intermediates and the product to be monitored over the full reaction period. The reaction starts with fast chlorine substitution and partial reduction during the dissolution of the tungsten hexachloride in benzyl alcohol followed by the generation of intermediates with W=O double bonds and finally the construction of the W-O-W network of the tungstite structure.
本文揭示了六氯化钨与苄醇反应生成钨酸锌纳米粒子的复杂化学机理。通过气相色谱随时间变化分析、X 射线衍射、时间分辨原位 X 射线吸收近边结构和扩展 X 射线吸收精细结构光谱研究了纳米粒子形成过程中的有机和无机物种。主成分分析揭示了两个中间体，通过线性组合分析鉴定为 WCl4 和 WOCl4。快速扫描扩展 X 射线吸收精细结构光谱能够在整个反应期间监测起始化合物、中间体和产物的随时间变化的演化。反应始于六氯化钨在苄醇中的快速氯取代和部分还原，随后生成具有 W=O 双键的中间体，最后构建钨酸锌结构的 W-O-W 网络。
