Geminal Coordinatively Unsaturated Sites on MOF-808 for the Selective Uptake of Phenolics from a Real Bio-Oil Mixture

The capping formate anions of the metal-organic framework (MOF) zirconium benzene-1,3,5-tricarboxylate (MOF-808) were removed by a solvent exchange procedure, resulting in a formate-free MOF-808 sample containing "geminal" defects consisting of six coordinatively unsaturated sites (CUSs) on each of the Zr₆ nodes. Adsorption experiments with this material showed that the uptake of 4-methylguaiacol from a bio-oil mixture was proportional to the number of defects and amounted to one mole adsorbed per mole of zirconium. The selective uptake behavior of MOF-808 towards phenolic compounds was further evident from competitive adsorption experiments between furfuryl alcohol and 4-methylguaiacol as well as from the excellent (20 wt % for phenolic compounds and <7 wt % for other compounds) uptake performance for real bio-oil mixtures containing a large concentration and diversity of molecules.