Please use this identifier to cite or link to this item: http://repositorio.unicamp.br/jspui/handle/REPOSIP/79691
Type: Artigo de periódico
Title: Structural changes induced by dehydration in the crystalline layered silicate Na-RUB-18: a computational/experimental combined study
Author: Iozzi, MF
Bisio, C
Regi-Macedo, T
Airoldi, C
Cossi, M
Marchese, L
Abstract: Na-RUB-18 layered silicate (Na(8)Si(32)O(64)(OH)(8) center dot 32H(2)O) is prepared following the procedure reported in the literature (ref. 1: K. Kosuge and A. Tsunashima, J. Chem. Soc., Chem. Commun., 1995, 2427) and its significant structural modifications induced by progressive removal of hydration water molecules are studied for the first time by a combined experimental (TGA and variable temperature XRD and FTIR) and theoretical approach. A novel structure of a partially de-hydrated Na-RUB-18 obtained upon heating at 75 degrees C under inert gas flow, which leads to a reversible phase transformation in agreement with XRD and FTIR results, is found. TGA indicates that at this stage, two of the four hydration water molecules per Na ion are lost. Theoretical results based on DFT calculations suggest that the apical water molecules of the solvated octahedrally coordinated sodium ion, forming weak H-bonds with the silicate oxygen atoms, are removed at this stage. As a consequence of the dehydration, the silicate layers get closer, and, similarly to that observed for zeolites, the sodium ions move towards lattice oxygen atoms, to restore their coordination shell. A combination of IR spectroscopy and computational models is used to describe the vibrational properties of silanol/silanolate (SiOH/SiO)(-1) bridges, which are responsible for the proton conduction of Na-RUB-18. The method described can be of general utility to refine structures which are not fully accessible to standard X-ray structure analysis.
Country: Inglaterra
Editor: Royal Soc Chemistry
Rights: aberto
Identifier DOI: 10.1039/b822013c
Date Issue: 2009
Appears in Collections:Unicamp - Artigos e Outros Documentos

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