TY - JOUR
T1 - Zeolites at high pressure
T2 - A review
AU - Gatta, G. D.
AU - Lee, Y.
PY - 2014/4
Y1 - 2014/4
N2 - This is a review of the elastic behaviour and pressure (P)-induced structural evolution of zeolites and presents a comparative analysis of the deformation mechanisms of the Si/Al-framework and the rearrangement of the extra-framework species in response to applied pressure. The interaction between P-transmitting fluids and zeolites, which can lead to phenomena such as P-induced over-hydration, is described. The comparative elastic analysis and the high-P structural data of zeolites reported so far allow us to make some generalizations: (1) The range of compressibility among this class of openframework silicates is large, with bulk moduli ranging between 15 and 70 GPa; (2) Microporosity does not necessarily imply high compressibility, as several zeolites are less compressible than other nonzeolitic rock-forming minerals; (3) Compressibilities of zeolites do not seem to be directly related to microporosity, at least if we model microporosity with the framework density; (4) The flexibility observed in zeolites under hydrostatic compression is mainly governed by tilting of rigid tetrahedra around O atoms that behave as hinges within the framework. Pressure-induced tilting commonly leads to continuous rearrangement of the framework without any phase transition. More rarely, tilting induces displacive phase transitions and isothermal P-induced reconstructive phase transitions (i.e. with change in framework topology), have not been reported in this class of materials; (5) Deformation mechanisms in response to applied pressure are generally dictated by the topological configuration of the framework rather than the Si/Al-distribution or the extra-framework content. The channel content governs the compressibility of the cavities, leading to different unit-cell-volume compressibilities in isotypic structures.
AB - This is a review of the elastic behaviour and pressure (P)-induced structural evolution of zeolites and presents a comparative analysis of the deformation mechanisms of the Si/Al-framework and the rearrangement of the extra-framework species in response to applied pressure. The interaction between P-transmitting fluids and zeolites, which can lead to phenomena such as P-induced over-hydration, is described. The comparative elastic analysis and the high-P structural data of zeolites reported so far allow us to make some generalizations: (1) The range of compressibility among this class of openframework silicates is large, with bulk moduli ranging between 15 and 70 GPa; (2) Microporosity does not necessarily imply high compressibility, as several zeolites are less compressible than other nonzeolitic rock-forming minerals; (3) Compressibilities of zeolites do not seem to be directly related to microporosity, at least if we model microporosity with the framework density; (4) The flexibility observed in zeolites under hydrostatic compression is mainly governed by tilting of rigid tetrahedra around O atoms that behave as hinges within the framework. Pressure-induced tilting commonly leads to continuous rearrangement of the framework without any phase transition. More rarely, tilting induces displacive phase transitions and isothermal P-induced reconstructive phase transitions (i.e. with change in framework topology), have not been reported in this class of materials; (5) Deformation mechanisms in response to applied pressure are generally dictated by the topological configuration of the framework rather than the Si/Al-distribution or the extra-framework content. The channel content governs the compressibility of the cavities, leading to different unit-cell-volume compressibilities in isotypic structures.
KW - Compressibility
KW - Elastic behaviour
KW - High pressure
KW - Open-framework structures
KW - Zeolites
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U2 - 10.1180/minmag.2014.078.2.04
DO - 10.1180/minmag.2014.078.2.04
M3 - Review article
AN - SCOPUS:84908455503
SN - 0026-461X
VL - 78
SP - 267
EP - 291
JO - Mineralogical Magazine
JF - Mineralogical Magazine
IS - 2
ER -