In situ dehydration behavior of zeolite-like pentagonite: A single-crystal X-ray study
- Mineralogical Crystallography, Institute of Geological Sciences, University of Bern, Freiestrasse 3, Bern CH-3012 (Switzerland)
The structural modifications upon heating of pentagonite, Ca(VO)(Si{sub 4}O{sub 10}){center_dot}4H{sub 2}O (space group Ccm2{sub 1}, a=10.3708(2), b=14.0643(2), c=8.97810(10) A, V=1309.53(3) A{sup 3}) were investigated by in situ temperature dependent single-crystal X-ray structure refinements. Diffraction data of a sample from Poona district (India) have been measured in steps of 25 up to 250 Degree-Sign C and in steps of 50 Degree-Sign C between 250 and 400 Degree-Sign C. Pentagonite has a porous framework structure made up by layers of silicate tetrahedra connected by V{sup 4+}O{sub 5} square pyramids. Ca and H{sub 2}O molecules are extraframework occupants. Room temperature diffraction data allowed refinement of H positions. The hydrogen-bond system links the extraframework occupants to the silicate layers and also interconnects the H{sub 2}O molecules located inside the channels. Ca is seven-fold coordinated forming four bonds to O of the tetrahedral framework and three bonds to extraframework H{sub 2}O. The H{sub 2}O molecule at O9 showing a high displacement parameter is not bonded to Ca. The dehydration in pentagonite proceeds in three steps. At 100 Degree-Sign C the H{sub 2}O molecule at O8 was released while O9 moved towards Ca. As a consequence the displacement parameter of H{sub 2}O at O9 halved compared to that at room temperature. The unit-cell volume decreased to 1287.33(3) A{sup 3} leading to a formula with 3H{sub 2}O per formula unit (pfu). Ca remained seven-fold coordinated. At 175 Degree-Sign C Ca(VO)(Si{sub 4}O{sub 10}){center_dot}3H{sub 2}O transformed into a new phase with 1H{sub 2}O molecule pfu characterized by doubling of the c axis and the monoclinic space group Pn. Severe bending of specific T--O--T angles led to contraction of the porous three-dimensional framework. In addition, H{sub 2}O at O9 was expelled while H{sub 2}O at O7 approached a position in the center of the channel. The normalized volume decreased to 1069.44(9) A{sup 3}. The Ca coordination reduced from seven- to six-fold. At 225 Degree-Sign C a new anhydrous phase with space group Pna2{sub 1} but without doubling of c had formed. Release of H{sub 2}O at O7 caused additional contraction of T--O--T angles and volume reduction (V=1036.31(9) A{sup 3}). Ca adopted five-fold coordination. During heating excursion up to 400 Degree-Sign C this anhydrous phase remained preserved. Between room temperature and 225 Degree-Sign C the unit-cell volume decreased by 21% due to dehydration. The dehydration steps compare well with the thermo-gravimetric data reported in the literature. - Graphical abstract: Pentagonite structure at room temperature and at 225 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer We investigate the relationship between the removal of H{sub 2}O molecules and structural modifications of the framework of pentagonite. Black-Right-Pointing-Pointer Pentagonite undergoes phase transitions upon heating. Black-Right-Pointing-Pointer We analyze similarities and differences between pentagonite and related structures.
- OSTI ID:
- 22131219
- Journal Information:
- Journal of Solid State Chemistry, Vol. 197; Other Information: Copyright (c) 2012 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
- Country of Publication:
- United States
- Language:
- English
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