Confined geometry effects on reorientational dynamics of molecular liquids in porous silica glasses

Abstract

This work investigates the relative role of the pure geometrical confinement and the strength of the surface effect on the dynamics of liquids in porous silica glasses prepared by the sol-gel process. The deuteron NMR spin-lattice relaxation times T1 of several molecular liquids in porous silica glasses are reported as function of pore size in the range from 18 to 143 Å over the temperature range from 260 to 310 K. Molecular liquids studied include strongly interacting polar liquids such as pyridine-d5, aniline-d5, and nitrobenzene-d5, whereas the saturated cyclic hydrocarbon liquids of cyclohexane-d12 and cis-decalin-d18 represent the weakly interacting liquids. In a first approximation, toluene-d1 and dioxane-d18 are chosen as examples of liquids with intermediate interactions with the silica surface. The experimental relaxation data are analyzed by using the two-state, fast-exchange model which is found to be valid for the strongly interacting liquids and liquids with intermediate interactions. In terms of this model, the viscosity of the surface layer for pyridine-d5 is about 30 times higher than that for bulk liquid pyridine. The importance of the two-dimensional approach to describe motional dynamics of liquids confined to pores smaller than 30 Å is illustrated in the case of weakly interacting liquid of cyclohexane-d12. Additional information on the relative role of surface interactions and the pure topological effects on the dynamics of liquids in confined geometries was obtained by using surface-modified glasses in which the surface hydroxyl groups were replaced by OSi(CH3)2OC2H5 groups. Indeed, the effects of surface modifications on the 2H T−11 are most pronounced for strongly interacting liquids whereas they are absent for cyclohexane. In agreement with the concept of two-dimensional behavior of liquids in small pores, one finds that the low-frequency relaxation times, namely, the spin–spin relaxation time T2, and the spin-lattice relaxation time in the rotating coordinate frame, T1ρ, remain unchanged by surface modification. In fact, this is a consequence of logarithmic enhancement of the spectral density at low frequencies so that the effect of pure geometrical confinement on the T−12 and T−11ρ relaxation rates is much larger than any relaxation rate changes arising from surface modification. Several selected NMR T1 experiments on pyridine-d5 confined to anopore and zeolites are also presented.