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3073391 
Journal Article 
Conversion of levulinic acid into chemicals: Synthesis of biomass derived levulinate esters over Zr-containing MOFs 
Cirujano, FG; Corma, A; Llabres i Xamena, FX 
2015 
Yes 
Chemical Engineering Science
ISSN: 0009-2509 
124 
52-60 
English 
WOS:000349447000007 
Zr-containing metal-organic frameworks (MOFs) formed by either terephthalate (UiO-66) or 2-aminoterephthalate ligancls (UiO-66-NH2) are active and stable catalysts for the acid catalyzed esterification of levulinic acid with EtOH, n-BuOH and long-chain biomass derived alcohols, with activities comparable (in some cases superior) to other solid acid catalysts previously repotted. The effect of functional group substitution at the ligand benzene ring, alcohol chain length, particle size and contents of defects on the catalytic activity of the MOFs are studied in detail. In UiO-66-NH2, a dual acid-base activation mechanism is proposed, in which levulinic acid is activated on Zr sites and the alcohol at the amino groups of the ligand. Large variations of the catalytic activity from batch to batch suggest that the active sites are located at defect positions associated to ligand deficiency of the solid. Particle size seems to have a minor impact only in UiO-66-NH2, in which diffusion of levulinic acid is somehow hindered due to the amino groups present in the linkers. (C) 2014 Elsevier Ltd. All rights reserved 
MOF catalysis; Biomass into chemicals; Levulinic acid esterification; Dual acid-base activation