Ice-Water Equilibrium in Nanoscale Confinement.

We show that 2D ^{2}H NMR spectra enable valuable insights into the nature of an ice-water equilibrium in nanoscale confinement, which extends over a broad temperature range. In particular, 2D ^{2}H NMR line-shape analysis allows us to determine the timescale on which the coexisting ice and water phases exchange molecules. For D_{2}O in a silica nanopore with a diameter of 5.4 nm, we find that the residence time of a water molecule in either phase is characterized by an NMR exchange time of τ_{X}=5.7 ms at 220 K. Thus, the ice-water equilibrium is highly dynamic, which is an important aspect for an understanding of deeply cooled confined and, possibly, bulk waters.

2H NMR studies on the dynamics of supercooled water in a metal-organic framework.

We use 2H nuclear magnetic resonance (NMR) to study water (D2O) reorientation and diffusion in the metal-organic framework MFU-4l, which features a regular three-dimensional network of nearly spherical pores with diameters of 1.2 and 1.9 nm. We observe that the rotational correlation times follow Vogel-Fulcher-Tammann and Arrhenius (Ea = 0.48 eV) relations above ∼225 K and below ∼170 K, respectively, whereas the temperature dependence continuously evolves from one to the other behavior in the broad crossover zone in between. In the common temperature range, the present NMR results are fully consistent with previous broadband dielectric spectroscopy (BDS) data on water (H2O) in a very similar framework. Several of our observations, e.g., rotational-translational coupling, indicate that a bulk-like structural (α) relaxation is observed above the crossover region. When cooling through the crossover zone, a quasi-isotropic reorientation mechanism is retained, while 2H spin-lattice relaxation evolves from exponential to nonexponential, implying that the water dynamics probed at low temperatures does no longer fully restore ergodicity on the time scale of this experiment. We discuss that the latter effect may result from bulk-like and/or confinement-imposed spatially heterogeneous water properties. Comparison with previous NMR and BDS results for water in other confinements reveals that, for confinement sizes around 2 nm, water reorientation depends more on the pore diameter than on the pore chemistry, while water diffusion is strongly affected by the connectivity and topology of the pores.

Dynamical Susceptibilities of Confined Water from Room Temperature to the Glass Transition.

We confine water to narrow silica pores, where crystallization is suppressed, and determine the dynamical susceptibilities of the liquid from room temperature down to the glass transition by combining broadband dielectric spectroscopy (BDS) with 1H and 2H nuclear magnetic resonance (NMR), in particular, by establishing NMR field-cycling relaxometry. For the correlation times, derivative analysis reveals Vogel-Fulcher-Tammann and Arrhenius regimes at T ≥ 215 K and T ≤ 160 K, respectively, which are separated by a broad crossover region. The continuous transition in the temperature dependence is accompanied by a gradual change from asymmetric high-temperature shapes of the dynamical susceptibilities to symmetric low-temperature ones and by a steady decrease of the dielectric relaxation strength. In the Arrhenius regime (Ea = 0.48 eV) at T ≤ 160 K, 2D 2H NMR spectra reveal quasi-isotropic water reorientation. We rationalize these results in terms of a crossover to an interface-affected, noncooperative relaxation involving both rotational and translational motions.

The Nature of the Low-Temperature Crossover of Water in Hard Confinement.

The dynamics of water confined in mesoporous MIP (2-3 nm pores in size) with silica gel (secondary silica; further, the abbreviation SG will be used) and MAP (10-35 nm pores in size) without SG borosilicate glasses have been studied by broadband dielectric spectroscopy (BDS), nuclear magnetic resonance (NMR), and differential scanning calorimetry (DSC). MIP samples contain secondary silica inside the pores and provide a confinement size of about 2-3 nm, whereas MAP samples are free of secondary silica and provide a confinement size of about 10-35 nm. It is shown by BDS and NMR techniques that water exhibits a dynamic crossover of around 180 K when it is confined in MIP samples. By contrast, water confined in larger pores (MAP) does not exhibit any changes in its relaxation behavior. It is also shown that the crossover temperature depends on the hydration level (the higher the hydration level, the lower the crossover temperature). Below the crossover temperature, we find that water reorientation is isotropic (NMR) and that the temperature-dependent dielectric relaxation strength (BDS) follows the tendency expected for a solid-like material. In contrast, water reorientation is related to long-range diffusion above the crossover temperature, and the dielectric relaxation strength follows the tendency expected for a liquid-like material. Furthermore, the calorimetric results are compatible with crossing a glass transition near 180 K. Finally, the results are discussed within the Gibbs-Thomson model. In this framework, the crossover could be related to ice crystals melting.