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.more »
Affinity of small-molecule solutes to hydrophobic, hydrophilic, and chemically patterned interfaces in aqueous solution
Performance of membranes for water purification is highly influenced by the interactions of solvated species with membrane surfaces, including surface adsorption of solutes upon fouling. Current efforts toward fouling-resistant membranes often pursue surface hydrophilization, frequently motivated by macroscopic measures of hydrophilicity, because hydrophobicity is thought to increase solute–surface affinity. While this heuristic has driven diverse membrane functionalization strategies, here we build on advances in the theory of hydrophobicity to critically examine the relevance of macroscopic characterizations of solute–surface affinity. Specifically, we use molecular simulations to quantify the affinities to model hydroxyl- and methyl-functionalized surfaces of small, chemically diverse, charge-neutral solutes represented in produced water. We show that surface affinities correlate poorly with two conventional measures of solute hydrophobicity, gas-phase water solubility and oil–water partitioning. Moreover, we find that all solutes show attraction to the hydrophobic surface and most to the hydrophilic one, in contrast to macroscopically based hydrophobicity heuristics. We explain these results by decomposing affinities into direct solute interaction energies (which dominate on hydroxyl surfaces) and water restructuring penalties (which dominate on methyl surfaces). Finally, we use an inverse design algorithm to show how heterogeneous surfaces, with multiple functional groups, can be patterned to manipulate solute affinity and selectivity. more »
- Publication Date:
- NSF-PAR ID:
- 10207734
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 118
- Issue:
- 1
- Page Range or eLocation-ID:
- Article No. e2020205118
- ISSN:
- 0027-8424
- Publisher:
- Proceedings of the National Academy of Sciences
- Sponsoring Org:
- National Science Foundation
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