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The effect of catalyst hydrophobicity on the kinetics of hydrogenation of aqueous phenol was investigated. The hydrophobicity of a Pd/SBA-15 catalyst was altered by synthesizing an organosilane with biphenylene framework linkers. Partitioning of phenol between the aqueous solution and the pores favors the hydrophobic catalyst by an order of magnitude at room temperature, relative to the hydrophilic catalyst. The rate of hydrogenation at 75 °C is higher in the hydrophobic catalyst, as is the selectivity for the partial hydrogenation product, cyclohexanone. Analysis of kinetic profiles measured using operando 13C NMR reveals that the hydrophobic catalyst has a larger apparent (i.e., composite) adsorption constant for phenol, which results in higher phenol surface coverage and, consequently, faster and more selective hydrogenation to cyclohexanone. 

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.