Freezing of water in hydrophilic nanopores (D=1.2 nm) is probed at the microscopic scale using x-ray diffraction, Raman spectroscopy, and molecular simulation. A freezing scenario, which has not been observed previously, is reported; while the pore surface induces orientational order of water in contact with it, water does not crystallize at temperatures as low as 173 K. Crystallization at the surface is suppressed as the number of hydrogen bonds formed is insufficient (even when including hydrogen bonds with the surface), while crystallization in the pore center is hindered as the curvature prevents the formation of a network of tetrahedrally coordinated molecules. This sheds light on the concept of an ubiquitous unfreezable water layer by showing that the latter has a rigid (i.e., glassy) liquidlike structure, but can exhibit orientational order.
Microporous AlPO 4 -54•xH 2 O, 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 H 2 O 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 H 2 O 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 AlPO 4 -54•xH 2 O 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 IV Al, 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.
Microporous AlPO4-54,
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 (XRD),
mid- and far-infrared (IR) spectroscopy in diamond anvil cells. The
material undergoes a phase transition beginning around 0.8 GPa. The
amount of AlPO4-8 gradually increases with pressure and
the phase transition is complete between 2 and 3 GPa. The closure
of the (POAl) angle destabilizes the structure of
AlPO4-54, which drives the transition to AlPO4-8. The pressure-induced phase transformation of AlPO4-54 to AlPO4-8 is associated with a symmetry reduction
from hexagonal to orthorhombic and with a change in the unidirectional
ring channel parallel to the c-axes from 18 to 14
AlO4 and PO4 tetrahedra. An abrupt decrease
along the b direction is linked to the formation of 4
new rings of 6 tetrahedra with significant structural reorganization.
The transition is followed by irreversible amorphization beginning
around 3.5 GPa due to the collapse of the pores. The amorphization
of AlPO4-8 was detected from the disappearance of the XRD
lines, abrupt shifts, and strong broadening of the mid-IR modes, and
by changes in the pressure dependence of the mid- and far-IR modes,
indicating a lower compressibility for the more dense amorphous form.
Far-IR spectra indicate that the new amorphous form retains the local
structure of AlPO4-8.
The insertion of H2O in AlPO4-54·xH2O at high pressure was investigated by single-crystal X-ray diffraction and Monte Carlo molecular simulation. H2O molecules are concentrated, in particular, near the pore walls. Upon insertion, the additional water is highly disordered. Insertion of H2O (superhydration) is found to impede pore collapse in the material, thereby strongly modifying its mechanical behavior. However, instead of stabilizing the structure with respect to amorphization, the results provide evidence for the early stages of chemical bond formation between H2O molecules and tetrahedrally coordinated aluminum, which is at the origin of the amorphization/reaction process.
AlPO4-17, known as the oxide with the highest negative
thermal expansion (NTE), was studied under high pressure by angle-dispersive
X-ray diffraction (XRD), mid- and far-infrared (IR) spectroscopy.
Upon increasing pressure, the closure of the (P–O–Al)
angle destabilizes the porous AlPO4-17 structure, which
drives the amorphization process. On the basis of the decrease in
intensity of the XRD lines and broadening of the IR modes, the material
was found to begin to amorphize near 1 GPa. XRD, mid- and far-IR analysis
evidenced pressure-induced framework softening and complete irreversible
amorphization near 2.5 GPa corresponding to the collapse of the pores.
The bulk modulus and its first pressure derivative (B
0 = 31.2(5) GPa and B′0 = −10.1(3)) at ambient temperature were determined by fitting
a third order Birch–Murnaghan equation of state (EOS) to the
pressure–volume data. The material is extremely compressible
and exhibits an elastic instability. Anomalous (negative) values of B′0 are very rare and have been observed
previously for cyanides and metal–organic frameworks. Such
an instability appears to be characteristic of materials, which exhibit
strong NTE behavior and indicates a link between NTE and anomalous
compressibility behavior. Mid-IR, far-IR, nuclear magnetic resonance,
and pair distribution function analysis of the new amorphous form
allow an amorphization mechanism to be proposed corresponding to a
collapse of the structure around its pores retaining the columns built
up of cancrinite cages and hexagonal prisms, based on alternating
AlO4 and PO4 tetrahedra. An increase in coordination
number of 10% of the Al atoms was observed. The pressure-induced amorphization
in the strong NTE material AlPO4-17 opens the door to the
development of new technological applications as crystal–amorphous
nanocomposites with zero or specifically selected thermal expansion
coefficients.
The RbSbGe 3 O 9 compound, grown by the high-temperature solution technique from the Rb 2 Mo 4 O 13 flux, crystallizes in the trigonal non-centrosymmetric space group P31c (n o. 159). The structure was solved and refined from single-crystal X-ray diffraction data recorded at ambient temperature, a = 12.1378(2), c = 9.9553(2) Å, V = 1270.18(5) Å 3 , R1 = 0.0241 and wR2 = 0.0452 for all data. The unit cell contains six formula units. The three-dimensional RbSbGe 3 O 9 network is built with three-membered units [Ge 3 O 9 ] 6of regular germanate tetrahedra involving three independent Ge atoms. The Ge 3 O 3 central rings located in the ab plan deviate only slightly from the planarity. Antimony Sb V is octahedrally coordinated by oxygen, and rubidium (Rb +), which is surrounded by six oxygen atoms, is located in the channels of the 3-D network. The structure of RbSbGe 3 O 9 containing both isolated SbO 6 octahedra and Ge 3 O 9 cyclic units is comparable but not isostructural to the benitoite type. The almost flat character of the Ge 3 O 3 rings is also attested by the vibrational study at room temperature via non-polarized infrared and Raman spectroscopy.
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