Selective Sequestration of Aromatics from Aqueous Mixtures with Sugars by Hydrophobic Molecular Calixarene Cavities Grafted on Silica

The separation of aromatic contaminants from sugar-aromatic aqueous mixtures is required in second-generation biorefineries because aromatic compounds deactivate (bio)catalysts typically involved in upgrading lignocellulosic biomass to fuels and chemicals. This separation remains challenging, however, because of the degree of molecular recognition needed to sequester dilute aromatic impurities from concentrated sugar streams. Herein, we demonstrate that hydrophobic cavities of p-tert-butylcalix[4]arene macrocycles grafted on amorphous silica (calix/SiO₂) perform this separation selectively and efficiently by acting as selective molecular hosts that adsorb aromatic compounds (5-hydroxymethylfurfural, vanillin, and vanillic acid) while excluding monomeric sugar (glucose chosen as a prototypical model) in aqueous mixtures. By comparing calix/SiO₂ to a range of organically modified SiO₂ surfaces and other porous adsorbents, we demonstrate that the organization of hydrophobic functional groups within discrete nests consisting of calixarene cavities is crucial for facilitating the adsorption of aromatics. Density functional theory calculations of the host-guest complex indicate that adsorption is brought about by weak dispersive (van der Waals) interactions between tert-butyl upper-rim substituents in calixarene hosts and aromatic guests. Calix/SiO₂ can be repeatedly reused, demonstrating its viability as an adsorbent within a continuous biorefining process. These calix/SiO₂ adsorbents expand the palette of materials available for selective sugar-aromatic separations, which until now have been limited to pyrene-based sites of metal-organic framework NU-1000, and demonstrate that sites consisting of relatively simple hydrophobic tert-butyl substituents organized around a hemispherical molecular cavity provide a sufficient degree of molecular recognition for performing this separation selectively.