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Study of the Chemical Mechanism Involved in the Formation of Tungstite in Benzyl Alcohol by the Advanced QEXAFS Technique
Author(s) -
OlligesStadler Inga,
Stötzel Jan,
Koziej Dorota,
Rossell Marta D.,
Grunwaldt JanDierk,
Nachtegaal Maarten,
Frahm Ronald,
Niederberger Markus
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201101514
Subject(s) - benzyl alcohol , chemistry , dissolution , absorption (acoustics) , reaction mechanism , absorption spectroscopy , chlorine , spectroscopy , alcohol , reaction intermediate , tungsten , crystallography , photochemistry , organic chemistry , materials science , catalysis , physics , quantum mechanics , composite material
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 WO double bonds and finally the construction of the WOW network of the tungstite structure.