Desorption of water from hydrophilic MCM-41 mesopores: positron annihilation, FTIR and MD simulation studies

The desorption mechanism of water from the hydrophilic mesopores of MCM-41 was studied using positron annihilation lifetime spectroscopy (PALS) and attenuated total reflection Fourier transform infrared spectroscopy supplemented with molecular dynamics (MD) simulation. PALS results indicated that water molecules do not undergo sequential evaporation in a simple layer-by-layer manner during desorption from MCM-41 mesopores. The results suggested that the water column inside the uniform cylindrical mesopore become stretched during desorption and induces cavitation (as seen in the case of ink-bottle type pores) inside it, keeping a dense water layer at the hydrophilic pore wall, as well as a water plug at both the open ends of the cylindrical pore, until the water was reduced to a certain volume fraction where the pore catastrophically empties. Before being emptied, the water molecules formed clusters inside the mesopores. The formation of molecular clusters below a certain level of hydration was corroborated by the MD simulation study. The results are discussed.