Underlying Processes Driving the Evolution of Nanoporous Silica in Water and Electrolyte Solutions (original) (raw)
2020, The Journal of Physical Chemistry C
In this study, we related the alteration of mesoporous materials in aqueous solutions to the properties of confined water in the presence of ions, that is, its structure and its dynamics. To reach this goal, we have determined and quantified the evolution of the morphology of hexagonal mesoporous silica-based materials, that is, MCM-41 (mean pore size of 2.9 nm and dense pore wall) and SBA-15 (mean pore size of 6.8 nm and microporous pore wall), during their alteration in water and electrolyte solutions with ions presenting various kosmotropic properties ([XCl 2 ] = 1 M and X = Ba, Ca, Mg) at 50°C by in situ small and wide angle X-ray scattering. The experimental results and the calculated small-angle X-ray scattering spectra have demonstrated that the alteration behavior is strongly dependent on the type of silica and the water properties (water dynamics at a picosecond time scale and water structure) related to the confinement size, the nature of the cations, and their surface ion excesses. For MCM-41 silica, having reduced water dynamics, the alteration behavior is mainly driven by silica hydrolysisrecondensation/precipitation processes leading to a pore deformation and a possible precipitation of XCl 2 metastable phases partially clogging the pores. In case of SBA-15, its alteration behavior in aqueous solutions starts with an initial increase of the pore size and the formation of an alteration layer within its microporosity which grows following a diffusive process of the solution. Inside the microporosity, similar alteration processes to MCM-41 silica occur. These recondensation/precipitation processes may continue until a thermodynamically stable silica phase is formed. The results obtained within the scope of this work revealed the importance of the influence of the dynamics and the structure of water in chemical reactions taking place in confined media filled with water and ions.
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