Tuning molecular adsorption in SBA-15-type periodic mesoporous organosilicas by systematic variation of their surface polarity

Abstract

Surface polarity plays a key role in controlling molecular adsorption at solid–liquid interfaces, with major implications for reactions and separations. In this study, the chemical composition of periodic mesoporous organosilicas (PMOs) was varied by co-condensing Si(OEt)₄ with organodisilanes, to create a homologous series of materials with similar surface areas, pore volumes, and hydroxyl contents. Their relative surface polarities, obtained by measuring the fluorescence of a solvatochromic dye, cover a wide range. In this series of PMO materials, EPR spectra of tethered nitroxide radicals show monotonically decreasing mobility as larger fractions of the radicals interact strongly with increasingly non-polar surfaces. The surface properties of the materials also correlate with their affinities for organic molecules dissolved in various solvents. The most polar PMO has negligible affinity for phenol, p-cresol, or furfural when these molecules are dissolved in water. However, stronger solute–surface interactions and favor adsorption as the surface polarity decreases. The trend is reversed for furfural in benzene, where weaker solvent–surface interactions result in higher adsorption on polar surfaces. In DMSO, furfural adsorption is suppressed due to the similar strengths of solute-surface and solvent–surface interactions. Thus, the polarity of the surface relative to the solvent is critical for molecular adsorption. These findings show how adsorption/desorption can be precisely and systematically tuned by appropriate choice of both solvent and surface, and contribute to a predictive strategy for the design of catalytic and separations processes.