A comparative study on bulk and nanoconfined water by time-resolved optical Kerr effect spectroscopy

TL;DR

This study uses time-resolved optical Kerr effect spectroscopy to compare the vibrational and dynamical properties of water in porous silica with bulk water, revealing how hydration level influences hydrogen bonding and relaxation times.

Contribution

It provides a detailed spectral and dynamical analysis of water in nanoconfined pores, distinguishing between hydration layers and bulk-like water, which was not previously characterized in this way.

Findings

Water above 10% hydration behaves like bulk water.

Hydrogen bond features diminish at low hydration levels.

Inner water has relaxation times similar to bulk water.

Abstract

The low frequency vibrational spectra of hydrated porous silica are specifically sensitive to the hydrogen bond interactions and provides a wealth of information on the structural and dynamical properties of the water contained in the pores of the matrix. We investigate systematically this spectral region of Vycor porous silica (pore size about 4 nm) for a series of samples at different levels of hydration, from the dry matrix to completely filled pores. The spectra are obtained as the Fourier transforms of time-resolved heterodyne detected optical Kerr effect (HD- OKE) measurements. The comparison of these spectra with that of bulk water allows us to extract and analyze separately the spectral contributions of the first and second hydration layers, as well as that of bulk-like inner water. We conclude that the extra water entering the pores above 10 % water/silica weight ratio behaves very similarly to bulk water. At lower levels of hydration, corresponding to two complete superficial water layers or less, the H-bond bending and stretching bands, characteristic of the tetrahedral coordination of water in the bulk phase, progressively disappear: clearly in these conditions the H-bond connectivity is very different from that of liquid water. A similar behavior is observed for the structural relaxation times, measured from the decay of the time-dependent HD-OKE signal. The value for the inner water is very similar to that of the bulk liquid; that of the first two water layers is definitely longer by about a factor 4. These findings should be carefully taken into account when employing pore confinement to extend towards lower temperatures the accessible temperature range of supercooled water.