A comprehensive study of the crystallization mechanism involved in the nonaqueous formation of tungstite.

We present a detailed study on the nonaqueous synthesis of tungstite nanostructures with the focus on crystallization processes and the evolution of particle morphology. Time-dependent transmission electron microscopy (TEM) revealed a complex, particle-based crystallization mechanism involving first the formation of spherical and single-crystalline primary particles of 2-8 nm, which are cross-linked to large and unordered agglomerates, followed by their organization into rod-like structures of 40 × 200-400 nm. These rods undergo an internal ordering process, during which crystallographically oriented stacks of platelets develop. In situ small angle X-ray scattering (SAXS) experiments confirm this pathway of particle formation. The scattering intensity is dominated by the fast formation of rod-like particles, which cause an inter-platelet peak in the SAXS pattern with ongoing internal ordering. With continuous reaction time, the platelet stacks start to fall apart forming shorter assemblies of just a few platelets or even single platelets.

Study of the chemical mechanism involved in the formation of tungstite in benzyl alcohol by the advanced QEXAFS technique.

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.

Extension of the benzyl alcohol route to metal sulfides: "nonhydrolytic" thio sol-gel synthesis of ZnS and SnS2.

Crystalline ZnS and SnS(2) particles were synthesized by a modified benzyl alcohol route using benzyl mercaptan as solvent.

Co-operative formation of monolithic tungsten oxide-polybenzylene hybrids via polymerization of benzyl alcohol and study of the catalytic activity of the tungsten oxide nanoparticles.

Hard and brittle monolithic tungsten oxide-polybenzylene nanohybrids can be obtained in one step by reacting tungsten iso-propoxide with benzyl alcohol. In a first step, crystalline tungsten oxide W(18)O(49) nanowires with a diameter of about 1.5 nm form via ether elimination reaction. Subsequently, the large residue of the benzyl alcohol is transformed to dibenzyl ether, which then polymerizes to polybenzylene, incorporating the nanoparticles into the forming polymer. The catalytic effect of the tungsten oxide nanowires on the quantitative formation of polybenzylene is proven by reacting them in different concentrations and at varying temperatures either with benzyl alcohol or with dibenzyl ether. Complete polymerization of benzyl alcohol is achieved within just 30 min by using a particle-to-monomer molar ratio of 1:115 at 160 degrees C. Lower reaction temperatures (100-130 degrees C) or higher ratios (1:340 and 1:680) prolong the reaction time to several hours. Further studies show that the tungsten oxide nanoparticles are able to completely polymerize various other alcohols with an aryl methanol group.