Abstract
The high-pressure behaviour and the crystal-fluid interaction of a natural offretite have been investigated by in situ single-crystal synchrotron X-ray diffraction, using a diamond anvil cell. Five different P-transmitting fluids have been employed: the non penetrating daphne oil 7575 and the potentially penetrating methanol:ethanol:H2O = 16:3:1 mixture, ethanol:water = 1:1 mixture, distilled H2O and liquid Ne. The daphne oil 7575 experiment allowed to describe the intrinsic compressional behaviour of offretite, without any pressure-induced crystal-fluid interaction, with an isothermal bulk modulus KV0 = 59(2) GPa (βV0 = 0.0170(9) GPa−1) for the range Pamb-1.83(5) GPa. All the experiments in potentially penetrating P-transmitting fluids showed the P-induced sorption of extra molecules within the large 12 mRs channel of offretite, obtained on the basis of X-ray structure refinements. For the aqueous mixtures, the magnitude of the adsorption appears to be governed by the H2O content of the P-transmitting fluid. Ne atoms are also able to penetrate into the 12 mRs channel in response to the applied pressure, interacting with the extraframework population via weak Van der Waals attraction. A comparative analysis of the P-mediated crystal-fluid interaction phenomena between offretite and the structurally similar erionite is provided.
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