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Carbon dioxide uptake in nitrite-sodalite: reaction kinetics and template ordering of the carbonate-nosean formation

  • Malik Šehović , Lars Robben EMAIL logo and Thorsten M. Gesing
Published/Copyright: January 2, 2015

Abstract

We report on the phase transformation and the reaction kinetics of aluminosilicate nitrite-sodalite |Na8(NO2)2|[AlSiO4]6 crystallizing in space group P4¯3n into carbonate-nosean |Na8(CO3)□|[AlSiO4]6 described in space group P23. Investigations were carried out in carbon dioxide atmosphere by in situ high-temperature X-ray diffraction measurements. The collected diffraction patterns were examined using the autocorrelation method and Rietveld and structure independent refinements. For this reaction an activation energy of EA=7.788(6) kJ/mol was observed. Whereas the framework remains almost unchanged during the phase transformation first a high number of newly formed template-domains are observed indicating only a short range order of CO32– occupied and empty cages. This can be deduced from the obtained average crystallite size ratios taken from structure independent Pawley fits of the reflections allowed in P4¯3n and constrained single-peak refinements of the remaining ones additionally allowed in P23. This initially high number of template domains is reduced with increasing reaction time developing faster at higher temperatures. An average formation of 2.2(1) ordered domains within one crystallite could be evaluated for the longest reaction time.


Corresponding author: Lars Robben, Institut für Anorganische Chemie, Chemische Kristallographie fester Stoffe, Universität Bremen, Leobener Strasse/NW2, D-28359 Bremen, Germany, E-mail:

Acknowledgments

We gratefully acknowledge the Deutsche Forschungsgemeinschaft (DFG) for the financial support in the Heisenberg program (GE1981/3-1 and GE1981/3-2). Additionally, we thank Dr. Claudia Weidenthaler (MPI für Kohlenforschung, Mühlheim an der Ruhr, Germany) for measurements regarding the feasibility of this study.

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Supplemental Material

The online version of this article (DOI: 10.1515/zkri-2014-1815) offers supplementary material, available to authorized users.


Received: 2014-11-1
Accepted: 2014-12-4
Published Online: 2015-1-2
Published in Print: 2015-4-1

©2015 by De Gruyter

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