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.