Origin of NMR Spectral Features in MCM-41 at Low Hydrations

Abstract

Although extensive literature exists on NMR of water in MCM-41, the origin of a number of NMR spectral features in this material had not been understood. Specifically, the OH proton resonance observed in the dry material disappears completely as it is hydrated to 0.2 mono-layer hydration level. The purpose of this study was to gain insight into the physical basics for these spectral features and in the process broaden our understanding of behaviour/interactions of water molecules in porous material. First, measurements of MAS spectra as a function of temperature and hydration, at very low hydrations, made possible a definitive spectral peak assignment. Second, using 1D and 2D selective inversion recovery and magnetization exchange experiments, as well as MAS and non-MAS techniques, magnetization exchange between the water protons and surface OH group protons was quantified. The present results lead to the conclusion that chemical exchange is not responsible for producing the observed changes in proton spectra in MCM-41 as this material is hydrated up to the 0.2 mono-layer hydration level. This represents an important result as it is at odds with what is assumed in the literature in this connection and means that previous conclusions about hydration dynamics in this material need to be revisited. A dynamics model of water interaction with the surface OH hydration sites was introduced to explain the observed proton spectra. The model can successfully predict the observed chemical shifts and temperature dependent changes of proton spectra in the very low hydration MCM-41.