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.

Carbon nanothreads are among the most attractive new materials produced under high pressure conditions. Their synthesis can be achieved by compressing the crystals of aromatic molecules exploiting both the anisotropic stress produced by the unidirectional applied force and that intrinsic to the crystal arrangement. We explored here the transformation of pyridine into a nitrogen rich carbon nanothread crystal by varying the pressure and temperature conditions with the twofold purpose of disclosing the microscopic mechanism of transformation and optimizing the yield and quality of the produced crystalline nanothreads. The best conditions for the synthesis were identified in the 14–18 GPa range at temperatures between 400 and 500 K with a product yield greater than 30%. The comparison of experiments performed under different P–T conditions allowed us to understand the role of high temperature, which is necessary to weaken or even destroy the complex H-bond network characterizing the pyridine crystal and preventing the correct approach of the aromatic rings for nanothread formation. X-ray diffraction data confirm the excellent 2D hexagonal packing of the nanothreads over several tens of microns, whereas the sharp absorption lines observed in the IR spectrum strongly support a substantial order along the threads. Diffraction results suggest a polytwistane structure of the threads derived from a Diels–Alder [4 + 2] polymerization involving molecules arranged in a slipped parallel configuration along the pyridine crystal a and b axes. Electron microscopy evidences an arrangement of the nanothreads in bundles of tens of nanometers.

The siliceous zeolite TON with a 1-D pore system was studied at high pressure by X-ray diffraction, infrared spectroscopy, and DFT calculations. The behavior of this material was investigated using nonpenetrating pressure-transmitting media. Under these conditions, a phase transition from the Cmc2₁ to a Pbn2₁ structure occurs at close to 0.6 GPa with doubling of the primitive unit cell based on Rietveld refinements. The pores begin to collapse with a strong increase in their ellipticity. Upon decreasing the pressure below this value the initial structure was not recovered. DFT calculations indicate that the initial empty pore Cmc2₁ phase is dynamically unstable. Irreversible, progressive pressure-induced amorphization occurs upon further increases in pressure up to 21 GPa. These changes are confirmed in the mid- and far-infrared spectra by peak splitting at the Cmc2₁ to Pbn2₁ phase transition and strong peak broadening at high pressure due to amorphization.