Aluminium(III) fluoride originating from decomposition of hydrazinium fluoroaluminate(III) under oxidative conditions: Syntheses, X-ray photoelectron spectroscopy and some catalytic reactions

Skapin, T., Mazej, Z., Makarowicz, A., Jesih, A., Nickkho-Amiry, M., Schroeder, S.L.M., Weiher, N., Žemva, B. and Winfield, J.M. (2011) Aluminium(III) fluoride originating from decomposition of hydrazinium fluoroaluminate(III) under oxidative conditions: Syntheses, X-ray photoelectron spectroscopy and some catalytic reactions. Journal of Fluorine Chemistry, 132(10), pp. 703-712. (doi: 10.1016/j.jfluchem.2011.04.013)

Abstract

Decomposition of hydrazinium pentafluoroaluminate under oxidative (F-2) conditions leads to aluminium(III) fluoride whose properties are highly dependent on the conditions used for synthesis. In the presence of anhydrous HF, which probably acts as a heat exchange agent, samples have high BET areas, whereas BET areas of samples prepared under gas-solid conditions are small. XPS data are consistent with the presence of Lewis acid centres but, more importantly, emphasise the importance of surface hydroxyl groups, particularly in high surface area compounds. Catalytic behaviour towards isomerisation of 1,1,2-trichlorotrifluoroethane and subsequent dismutations at moderate temperatures and towards room temperature dehydrochlorination of tert-butyl chloride has been demonstrated for some high BET samples: both reactions indicate that surface Lewis sites exist. Catalytic ability is inhibited by surface hydroxyl groups but is improved by prior fluorination of the surface with CCl2F2. Catalysis is inhibited also by the presence of ammonium fluoroaluminate, a by-product of the decomposition process. The [NH4](+) salt level can be reduced by washing with anhydrous HF.

• Item Type: Articles
• Status: Published
• Refereed: Yes
• Glasgow Author(s) Enlighten ID: Winfield, Professor John
• Authors: Skapin, T., Mazej, Z., Makarowicz, A., Jesih, A., Nickkho-Amiry, M., Schroeder, S.L.M., Weiher, N., Žemva, B., and Winfield, J.M.
• College/School: College of Science and Engineering > School of Chemistry
• Journal Name: Journal of Fluorine Chemistry
• ISSN: 0022-1139
• Published Online: 30 April 2011