JAST
2012 March;3(1):95-103.
Published online 2012 January 17.
doi:http://dx.doi.org/10.5355/JAST.2012.95
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| Copyright ⓒ 2010 Journal of Analytical Science & Technology |
| Synthesis and characterization of perchlorate enclathrated aluminogermanate sodalite and its potassium and silver derivatives |
| Ashok Vishram Borhade*, Arun Gabaji Dholi, Dipak Ramrao Tope, Sanjay Gauram Wakchaure |
| Research Centre and Department of Chemistry, HPT Arts and RYK Science College, Nasik 422005, India |
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Corresponding Author:
Ashok Borhade ,Tel: O9421831839, Email: ashokborhade2007@yahoo.co.in |
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ABSTRACT |
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| Perchlorate enclathrated sodalite with aluminogermanate host framework has been obtained from low temperature hydrothermal synthesis at 373K. In addition mixed sodium, potassium and silver perchlorate sodalite is obtained by aqueous cation exchange method. The crystal structure of Na8[AlGeO4]6(ClO4)2, Na3.2K4.8[AlGeO4]6(ClO4)2 and Na3.9Ag4.1[AlGeO4]6(ClO4)2 sodalites were refined from X-ray powder data in the space group P 3n: a = 9.249 Å, V = 791.35 Å, Rwp = 0.2230, Rp = 0.1609 and Al-O-Ge angle is 140.930o and a = 9.257 Å, V = 793.28 Å, Rwp = 0.1596, Rp = 0.1180 and Al-O-Ge angle is 141.080o, a = 9.195 Å, V = 775.95 Å, Rwp = 0.2211, Rp = 0.1662 and Al-O-Ge angle is 139.034o ,respectively. The 27Al MAS NMR study confirms alternating Ge and Al ordering of sodalite framework, while 23Na give insights into the structure and dynamics of the cage fillings. The recorded Infrared and Raman spectra show absorption band typical for the sodalite structure. Thermogravimetric analysis has provided information on the extent of perchlorate entrapment, stability within the sodalite cage and decomposition properties. SEM study shows the retention of cubical morphology of the sodalite derivatives.
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| Keywords: Hydrothermal method, Aluminogermanate sodalite, Cation exchange, IR shift, Rietveld refinement, MAS NMR |
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FIGURES |
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Fig.1
IR absorption spectra of a) Na8[AlGeO4]6(ClO4)2, b) Na3.2K4.8[AlGeO4]6(ClO4)2, and c) Na3.9Ag4.1[AlGeO4]6(ClO4)2 sodalites. Sample is mixed with KBr and pallet is prepared. IR-transmission spectra of the aluminogermanate sodalites are obtained at room temperature. |
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Fig.2
Raman absorption spectra of a)Na8[AlGeO4]6(ClO4)2, b) Na3.2K4.8[AlGeO4]6(ClO4)2, c) Na3.9Ag4.1[AlGeO4]6(ClO4)2. Raman spectra of the perchlorate enclathrated sodalites taken at room temperature. The range is 200 cm-1to 800 cm-1 |
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Fig.3
Profile fit to powder X-ray data for a) Na8[AlGeO4]6(ClO4)2, b) Na3.2K4.8[AlGeO4]6(ClO4)2, and c) Na3.9Ag4.1[AlGeO4]6(ClO4)2. Full line is the difference and thick mark shows the reflection positions and difference curve below. |
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Fig.4
Schematic diagram of sodalite cage structure. The perchlorate ion is at the center of the cage. The solid lines represent the aluminogermanate cage. |
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Fig.5
27Al MAS NMR spectra of a) Na8[AlGeO4]6(ClO4)2, b) Na3.2K4.8[AlGeO4]6(ClO4)2, and c) Na3.9Ag4.1[AlGeO4]6(ClO4)2. The 27Al MAS NMR spectra of aluminogermanate sodalites significant shift due to potassium and silver cations.
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Fig.6
23Na MAS NMR spectra of a) Na8[AlGeO4]6(ClO4)2, b) Na3.2K4.8[AlGeO4]6(ClO4)2, and c) Na3.9Ag4.1[AlGeO4]6(ClO4)2. The 23Na MAS NMR spectra of aluminogermanate sodalites showing clear quadrupolar interaction due to non symmetrical environment in all three sodalites. Resonance shift is due to ion exchanged. |
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Fig.7
TGA and DTA of a) Na8[AlGeO4]6(ClO4)2, b) Na3.2K4.8[AlGeO4]6(ClO4)2, and c) Na3.9Ag4.1[AlGeO4]6(ClO4)2 sodalites. Thermal stability of perchlorate encapsulated in aluminogermanate sodalite cage and its decomposition temperature are higher than perchlorate salts is visible in thermogram. |
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Fig.8
SEM images of a) Na8[AlGeO4]6(ClO4)2, b) Na3.2K4.8[AlGeO4]6(ClO4)2, and c) Na3.9Ag4.1[AlGeO4]6(ClO4)2 sodalites. Cubical habits of sodalite and smooth surface are seen from aluminogermanate sodalite. After ion exchanged with potassium and silver the morphology is retained. |
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TABLES |
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Table.1
Mid IR spectral frequencies (cm-1) and Raman frequencies (cm-1) for the framework region and anion modes for perchlorate sodalites. |
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Table.2
Crystallographic data and experimental conditions for the structure refinement of perchlorate
aluminogermanate sodalite. |
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Table.3
Fractional coordinates and equivalent displacement
parameters of aluminogermanate perchlorate sodalites. |
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Table.4
Selected derived bond distances and bond angles for aluminogermanate perchlorate sodalites perchlorate sodalites. |
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Table.5
23Na and 27Al NMR data of sodium, potassium and silver aluminogermanate perchlorate sodalites. |
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