A Neutron/X-Ray Diffraction, IR, and 1H/29Si NMR Spectroscopic Investigation of Armenite: Behavior of Extra Framework Ca Cations and H2O Molecules in Microporous Silicates
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Data di Pubblicazione:
2012
Citazione:
A Neutron/X-Ray Diffraction, IR, and 1H/29Si NMR Spectroscopic Investigation of Armenite: Behavior of Extra Framework Ca Cations and H2O Molecules in Microporous Silicates / C.A. Geiger, G.D. Gatta, X. Xue, G.J. Mcintyre. ((Intervento presentato al 1. convegno European Mineralogical Conference tenutosi a Frankfurt, Germany nel 2012.
Abstract:
The crystal chemistry of armenite, ideally BaCa2Al6Si9O30 2H2O, from Wasenalp, Valais, Switzerland was studied.
Armenite typically forms in relatively low-temperature hydrothermal veins and fissures and has small pores
containing Ca cations and H2O molecules as extra-framework species. Single-crystal neutron and X-ray diffraction
measurements were made on armenite from the above locality for the first time. IR powder spectroscopic measurements
were made from room temperature (RT) down to 10 K. 1H and 29Si NMR measurements were made at
RT. Attention was given to investigating the behavior of the extra-framework species and hydrogen bonding. The
diffraction results show new features not observed before in published diffraction studies on armenite crystals from
other localities. The neutron results also give the first static description of the protons, allowing bond distances and
angles relating to the H2O molecules and H-bonds to be determined. The diffraction results indicate Al/Si order
in the framework. Four crystallographically independent Ca and H2O molecule sites were refined, whereby both
sites appear to have partial occupancies such that locally a Ca atom can have only a single H2O molecule bonded
to it through an ion-dipole interaction. The Ca cation is further bonded to six O atoms of the framework forming
a quasi cluster around it. The IR spectrum of armenite is characterized in the OH-stretching region at RT by two
broad bands at roughly 3470 and 3410 cm1 and by a single H2O bending mode at 1654 cm1. At 10 K four
intense OH bands are located at 3479, 3454, 3401 and 3384 cm1 and two H2O bending modes at 1650 and 1606
cm1. The 29Si MAS NMR spectra show four resonances at -81.9, -83.2, -94.9 and -101.8 ppm that are assigned to
crystallographically different Si sites in an ordered structure, although their relative intensities deviate somewhat
from those predicted for complete Al/Si order. The 1H MAS spectra contain a single main resonance near 5.3 ppm
and a smaller one near 2.7 ppm, which can be assigned to H2O molecules bonded to Ca and a second H2O type located
in a partially occupied site, respectively. Bonding for the extra-framework “Ca-oxygen-anion-H2O-molecule
quasi-clusters” and also the nature of H-bonding in the microporous zeolites scolecite, wairakite and epistilbite
are analyzed. The average OH stretching wavenumbers shown by the IR spectra of armenite and scolecite are,
for example, not far removed from that observed in liquid H2O, but greater than that of ice. What remains poorly
understood in microporous silicates is how the ion-dipole interaction in quasi clusters affects H-bonding strength
between the H2O molecules and the aluminosilicate framework.
Tipologia IRIS:
14 - Intervento a convegno non pubblicato
Elenco autori:
C.A. Geiger, G.D. Gatta, X. Xue, G.J. Mcintyre
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