3 years ago

Disordered but primitive gallosilicate hydro-sodalite: Structure and thermal behaviour of a framework with novel cation distribution

Disordered but primitive gallosilicate hydro-sodalite: Structure and thermal behaviour of a framework with novel cation distribution
The structure of a new gallosilicate sodalite |Na6.16(1)(H2O)8|[Ga1.04(1)Si0.96(1)O4]6 described in space group P 4 ¯ 3 n with lattice parameter a = 885.208(7) pm is reported. For such a sodalite with a deviation from a 1:1 ratio in the framework cations a body-centred structure in space group I 4 ¯ 3 m could be expected. The structure shows structural stress resulting from this unusual substitution by a high strain visible in reflections which are forbidden by symmetry in I 4 ¯ 3 m . Distinct amounts of Ga and Si are redistributed on the opposite crystallographic position. The second coordination sphere of Si was examined by 29Si MAS NMR, the absence of OH in the sodalites cages was checked by FTIR- and Raman spectroscopy. The intensity distribution of MAS NMR signal is modelled using a new technique to calculate the framework metal second neighbour coordination. The confirmed distribution leads to a low thermal stability of the cubic sodalite indicated by a new intermediated phase which could be regarded as a triclinic distorted cancrinite with three-time increased c lattice parameter. This intermediate phase decomposes at around 1000 K to a beryllonite-type sodium gallosilicate.

Publisher URL: www.sciencedirect.com/science

DOI: S1387181117305553

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