title: Isolation of Renewable Phenolics by Adsorption on Ultrastable Hydrophobic MIL-140 Metal-Organic Frameworks.
abstract: The isolation and separation of phenolic compounds from aqueous backgrounds is challenging and will gain in importance as we become more dependent on phenolics from lignocellulose-derived bio-oil to meet our needs for aromatic compounds. Herein, we show that highly stable and hydrophobic Zr metal-organic frameworks of the MIL-140 type are effective adsorbent materials for the separation of different phenolics and far outperform other classes of porous solids (silica, zeolites, carbons). The mechanism of the hydroquinone-catechol separation on MIL-140C was studied in detail by combining experimental results with computational techniques. Although the differences in adsorption enthalpy between catechol and hydroquinone are negligible, the selective uptake of catechol in MIL-140C is explained by its dense π-π stacking in the pores. The interplay of enthalpic and entropic effects allowed separation of a complex, five-compound phenol mixture through breakthrough over a MIL-140C column. Unlike many other metal-organic frameworks, MIL-140C is remarkably stable and maintained structure, porosity and performance after five adsorption-desorption cycles.
authors.affiliation: Center for Surface Chemistry and Catalysis, KU Leuven, Arenbergpark 23, 3001 Leuven (Belgium).
authors.forename: Ben
authors.initials: B
authors.lastname: Van de Voorde
authors.affiliation: Institut Charles Gerhardt, UMR CNRS 5253, UM ENSCM, Université de Montpellier, 34095 Montpellier Cedex 5 (France).
authors.forename: Daiane
authors.initials: D
authors.lastname: Damasceno Borges
authors.affiliation: Center for Surface Chemistry and Catalysis, KU Leuven, Arenbergpark 23, 3001 Leuven (Belgium).
authors.forename: Frederik
authors.initials: F
authors.lastname: Vermoortele
authors.affiliation: Center for Surface Chemistry and Catalysis, KU Leuven, Arenbergpark 23, 3001 Leuven (Belgium).
authors.forename: Robin
authors.initials: R
authors.lastname: Wouters
authors.affiliation: Department of Chemical Engineering, Vrije Universiteit Brussel, Pleinlaan 2, 1050 Elsene (Belgium).
authors.forename: Belgin
authors.initials: B
authors.lastname: Bozbiyik
authors.affiliation: Department of Chemical Engineering, Vrije Universiteit Brussel, Pleinlaan 2, 1050 Elsene (Belgium).
authors.forename: Joeri
authors.initials: J
authors.lastname: Denayer
authors.affiliation: Center for Surface Chemistry and Catalysis, KU Leuven, Arenbergpark 23, 3001 Leuven (Belgium).|Institut Lavoisier, UMR CNRS 8180, Université de Versailles St-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex (France).
authors.forename: Francis
authors.initials: F
authors.lastname: Taulelle
authors.affiliation: Institut Lavoisier, UMR CNRS 8180, Université de Versailles St-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex (France).
authors.forename: Charlotte
authors.initials: C
authors.lastname: Martineau
authors.affiliation: Institut Lavoisier, UMR CNRS 8180, Université de Versailles St-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles Cedex (France).
authors.forename: Christian
authors.initials: C
authors.lastname: Serre
authors.affiliation: Institut Charles Gerhardt, UMR CNRS 5253, UM ENSCM, Université de Montpellier, 34095 Montpellier Cedex 5 (France).
authors.forename: Guillaume
authors.initials: G
authors.lastname: Maurin
authors.affiliation: Center for Surface Chemistry and Catalysis, KU Leuven, Arenbergpark 23, 3001 Leuven (Belgium). Dirk.DeVos@biw.kuleuven.be.
authors.forename: Dirk
authors.initials: D
authors.lastname: De Vos
mesh_terms: D000327:Adsorption; D004355:Drug Stability; D057927:Hydrophobic and Hydrophilic Interactions; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D010636:Phenols / Q000737:chemistry* / Q000302:isolation & purification*; D014867:Water / Q000737:chemistry; D015034:Zinc Oxide / Q000737:chemistry; D015040:Zirconium / Q000737:chemistry
chemical_list: D009942:Organometallic Compounds; D010636:Phenols; D014867:Water; D015040:Zirconium; D015034:Zinc Oxide
keywords: host-guest systems; metal-organic frameworks; phenols; separation; zirconium