Ref HAL: hal-00975020_v1
DOI: 10.1021/jp412181f
WoS: WOS:000331861700032
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Résumé:

Microporous AlPO4-54·xH2O, which exhibits the largest pores among zeolites and aluminophosphates with a diameter of 12.7 Å, was investigated at high pressure by X-ray powder diffraction and Raman spectroscopy in diamond anvil cells. The material was found to begin to amorphize near 2 GPa using either a nonpenetrating pressure transmitting medium (PTM) silicone oil or no PTM. When H2O is used as a PTM, amorphization begins at a lower pressure of 0.9 GPa. In this case, superhydration effects are observed and higher relative unit cell volumes are observed prior to the beginning of pressure-induced amorphization (PIA) as compared to the experiment in silicone oil due to insertion of the H2O molecules in the pores. In all cases, in these experiments at room temperature, amorphization was irreversible. Ex situ experiments were used to investigate the local structure of pressure-amorphized AlPO4-54·xH2O by nuclear magnetic resonance and by X-ray absorption spectroscopy, which show that, upon increasing pressure, two water molecules enter in the coordination sphere of IVAl, thereby increasing the coordination number from 4 to 6, which destabilizes the structure. The present results show that the insertion of and/or reaction with guest species can be used to strongly modify the stability of microporous materials with respect to PIA.