Crystallization and Dynamics of Water Confined in Model Mesoporous Silica Particles: Two Ice Nuclei and Two Fractions of Water.

The crystallization and dynamics of water confined in model mesoporous silica particles (pore diameters ranging from 2.1 to 5 nm; pore length ≈ 1 μm) are studied in homogeneous aqueous suspensions by dielectric spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance (NMR) techniques. We establish the phase diagram ( T vs 1/ d) of confined water covering a broad range of pore diameters. A linear dependence of the heterogeneous and the homogeneous nucleation temperatures on the inverse pore diameter is shown. The two lines converge at a pore diameter of ∼2.6 nm, below which formation of stable crystals is suppressed. By combining dielectric spectroscopy and different NMR techniques, we determine the dynamics of water within mesoporous silica over broad temperature and frequency ranges. Both techniques identify two dynamically distinguishable fractions of confined water coexisting within the pores. We attribute the two fractions to an interfacial water layer at the pore walls and confined water in the pore interior. Two alternative scenarios are proposed to rationalize the coexistence of two dynamically distinguishable water fractions. In the first scenario, two liquid fractions of water coexist under extreme confinement conditions for a range of temperatures; we discuss similarities with the two ultraviscous liquids (high-density liquid and low-density liquid) put forward for supercooled bulk water. In the second scenario, a liquid and a solid phase coexist; we conjecture that highly distorted and unstable crystal nuclei exist under extreme confinement that exhibit reorientation dynamics with time scales intermediate to the surrounding confined liquid and to bulk ice.