Effects of nanosilica hydro-compaction and dispersion media on bound water, other solvents and solutes

Abstract

Interfacial phenomena linked to the behavior of bound water, organic solvents (co-sorbates, dispersion media), hydrogen, methane, acids/bases, and salts bound to various silicas, polymers, and carbon materials were analyzed vs. temperature and concentrations using ¹H NMR spectroscopy, differential scanning calorimetry (DSC) and other methods. The material characteristics were studied using microscopy, infrared spectroscopy (IR), small angle X-ray scattering (SAXS), and nitrogen adsorption. Confined space effects (CSE) result in enhanced freezing point depression (FPD) and stronger diminution of solvent activity and colligative properties of liquid mixtures in narrower pores. Short hydrophobic functionalities (≡Si-CH₃, =Si(CH₃)₂) at a silica surface and the presence of nanopores result in differentiation of bound water into weakly (WAW, δ_H=0.2–2.0 ppm) and strongly (SAW, δ_H=4–6 ppm) associated waters of smaller solvent activity in smaller clusters located in narrower pores and unfrozen below a bulk freezing point. These effects are enhanced in hydrophobic dispersion media. Hydrophobic liquids could displace bound water into narrower pores inaccessible for their molecules larger than water and/or into broader pores to reduce contact area between immiscible liquids. The observed phenomena depend on sorbent/sorbate kinds and play an important role on practical applications of various sorbents.