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Study of The Hydrothermal Synthesis of Gallium Phosphates Using in Situ Time-Resolved X-Ray Diffraction

Published online by Cambridge University Press:  16 February 2011

R.I. Walton ,
T. Loiseau ,
R.J. Francis ,
D. O'Hare  and
G. Férey
R.I. Walton
Affiliation:
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK, [email protected]
T. Loiseau
Affiliation:
Institut Lavoisier, UMR CNRS C173, Université de Versailles-Saint Quentin-en-Yvelines, 45, avenue des Etats-Unis, 78035 Versailles, Cedex, France
R.J. Francis
Affiliation:
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK, [email protected]
D. O'Hare
Affiliation:
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford, OX1 3QR, UK, [email protected]
G. Férey
Affiliation:
Institut Lavoisier, UMR CNRS C173, Université de Versailles-Saint Quentin-en-Yvelines, 45, avenue des Etats-Unis, 78035 Versailles, Cedex, France
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Abstract

The hydrothermal crystallisation (130-180 °C) of three-dimensional open-framework gallium and aluminium oxyfluoro-phosphates with the ULM-3 and ULM-4 structures have been studied in situ for the first time. The in situ energy-dispersive X-ray diffraction method has allowed the formation of the crystalline products to be observed under hydrothermal conditions The integrated areas of the strongest Bragg reflections has allowed quantitative kinetic data to be extracted. The effect of temperature, phosphorus source, templating agent have been investigated. The nature of phosphorus source in the reaction mixture has been found to affect dramatically the course of reaction for certain combinations of amine and temperature. Previously unobserved transient crystalline phases have been seen during the production of ULM-3 gallium phosphates when P2O5 or polyphosphoric acid are used. The formation of these intermediates affects the kinetics of product growth. In the case of the aluminium ULM-3 materials reaction always proceeds via a crystalline intermediate whatever phosphorus source is used. The ULM-4 framework materials are found to always crystallise directly with no evidence for any intermediates. Kinetic data for each system have been modelled using standard solid-state chemistry expressions, and these calculations indicate the reactions to be diffusion controlled.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 547: Symposium DD – Solid-State Chemistry of Inorganic Materials II , 1998 , 63
Copyright
Copyright © Materials Research Society 1999

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