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Crystallisation Kinetics of Metal Organic Frameworks From in situ Time-Resolved X-ray Diffraction

Published online by Cambridge University Press:  14 November 2013

Racha El Osta ,
Mark Feyand ,
Norbert Stock ,
Franck Millange  and
Richard I. Walton
Racha El Osta
Affiliation:
Institut Lavoisier Versailles, Université de Versailles, UMR 8180, 78035 Versailles, France
Mark Feyand
Affiliation:
Institut für Anorganische Chemie, Christian-Albrechts-Universität, Max-Eyth-Straße 2, D-24118 Kiel, Germany
Norbert Stock
Affiliation:
Institut für Anorganische Chemie, Christian-Albrechts-Universität, Max-Eyth-Straße 2, D-24118 Kiel, Germany
Franck Millange*
Affiliation:
Institut Lavoisier Versailles, Université de Versailles, UMR 8180, 78035 Versailles, France
Richard I. Walton*
Affiliation:
Department of Chemistry, University of Warwick, Coventry, CV4 7AL, UK
*
*Author for correspondence, email: r.i.walton@warwick.ac.uk or franck.millange@uvsq.fr
*Author for correspondence, email: r.i.walton@warwick.ac.uk or franck.millange@uvsq.fr
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Abstract

A time-resolved powder diffraction study of the crystallisation of porous metal organic framework materials with the CPO-27 structure ([M2(dhtp)(H2O)2]·8H2O where, dhtp=2,5-dioxoterephthalate) using the energy dispersive X-ray diffraction method is described. Crystallisation under solvothermal conditions is performed between 70 - 110 °C from clear solutions of metal salts (M=Co2+ or Ni2+) and 2,5-dihydroxyterephthalic acid in a mixture of THF-water in sealed reaction vessels, using both conventional and microwave heating. Integration of Bragg peak areas with time provides accurate crystallisation curves, which are modelled using the method of Gualtieri to determine rate constants for nucleation and for growth and then, by Arrhenius analysis, activation energies. Crystallisation is determined to be one-dimensional, consistent with the elongated morphology of the crystals produced in these reactions. With conventional heating the Co-containing CPO-27 crystallises more rapidly than the isostructural Ni-containing analogue and analysis of the kinetic parameters would suggest a complex multi-step crystallisation process. The effect of microwave heating is upon activation energies: the values for both nucleation and for crystal growth are lowered compared to reactions using conventional heating.

Keywords

Metal Organic FrameworksEnergy DispersiveTime ResolvedX-ray Diffraction
Type
Technical Articles
Information
Powder Diffraction , Volume 28 , Supplement S2 , September 2013 , pp. S256 - S275
Copyright
Copyright © International Centre for Diffraction Data 2013 

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