Griffith, Christopher S., Luca, Vittorio, Hanna, John V., Pike, Kevin J., Smith, Mark E. and Thorogood, Gordon S. (2009) Microcrystalline hexagonal tungsten bronze. 1. Basis of ion exchange selectivity for cesium and strontium. Inorganic Chemistry, Vol.48 (No.13). pp. 5648-5662. doi:10.1021/ic801294x ISSN 0020-1669.

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Abstract

The structural basis of selectivity for cesium and strontium of microcrystalline hexagonal tungsten bronze (HTB) phase NaxWO3+x/2 center dot zH(2)O has been studied using X-ray and neutron diffraction techniques, 1D and 2D Na-23 magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy, and radiochemical ion exchange investigations. For the HTB system, this study has shown that scattering techniques alone provide an incomplete description of the disorder and rapid exchange of water (with tunnel cations) occurring in this system. However, 1D and 2D Na-23 MAS NMR has identified three sodium species within the HTB tunnels-species A, which is located at the center of the hexagonal window and is devoid of coordinated water, and species B and C, which are the di- and monohydrated variants, respectively, of species A. Although species B accords with the traditional crystallographic model of the HTB phase, this work is the first to propose and identify the anhydrous species A and monohydrate species C. The population (total) of species B and C decreases in comparison to that of species A with increasing exchange of either cesium or strontium; that is, species B and C appear more exchangeable than species A. Moreover, a significant proportion of tunnel water is redistributed by these cations. Multiple ion exchange investigations with radiotracers Cs-137 and Sr-85 have shown that for strontium there is a definite advantage in ensuring that any easily exchanged sodium is removed from the HTB tunnels prior to exchange. The decrease in selectivity (wrt cesium) is most probably due to the slightly smaller effective size of Sr2+; namely, it is less of a good fit for the hexagonal window, ion exchange site. The selectivity of the HTB framework for cesium has been shown unequivocally to be defined by the structure of the hexagonal window, ion exchange site. Compromising the geometry of this window even in the slightest way by either (1) varying the cell volume through changes to hydration or sodium content or (2) introducing disorder in the a-b plane through isomorphous substitution of molybdenum is sufficient to reduce the selectivity. Indeed, it is our hypothesis that this applies for all cations which are strongly bound by the HTB framework.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Divisions:	Administration > University Executive Office Faculty of Science, Engineering and Medicine > Science > Physics
Journal or Publication Title:	Inorganic Chemistry
Publisher:	American Chemical Society
ISSN:	0020-1669
Official Date:	6 July 2009
Dates:	Date Event 6 July 2009 Published
Volume:	Vol.48
Number:	No.13
Number of Pages:	15
Page Range:	pp. 5648-5662
DOI:	10.1021/ic801294x
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Restricted or Subscription Access

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