Conversion of levulinic acid to gamma-valerolactone over Zr-containing metal-organic frameworks: Evidencing the role of Lewis and Bronsted acid sites

[EN] Zr-containing UiO-66 and MOF-808 are evaluated for converting levulinic acid (LA) into gamma-valerolactone (GVL) through various routes: (i) Step-wise esterification of LA to n-butyl levulinate (nBuL) and Meerwein-PonndorfVerley (MPV) reduction to GVL; (ii) One-pot two-steps esterification with...

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Detalles Bibliográficos
Autores: Guarinos, J.M., Cirujano, F.G., Rapeyko, Anastasia|||0000-0002-8309-3702, Llabrés i Xamena, Francesc Xavier|||0000-0002-4238-5784
Tipo de recurso: artículo
Fecha de publicación:2021
País:España
Institución:Universitat Politècnica de València (UPV)
Repositorio:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Idioma:inglés
OAI Identifier:oai:riunet.upv.es:10251/188316
Acceso en línea:https://riunet.upv.es/handle/10251/188316
Access Level:acceso abierto
Palabra clave:Zirconium MOFs
MOF-808
UiO-66
Levulinic acid
Gamma-valerolactone
Descripción
Sumario:[EN] Zr-containing UiO-66 and MOF-808 are evaluated for converting levulinic acid (LA) into gamma-valerolactone (GVL) through various routes: (i) Step-wise esterification of LA to n-butyl levulinate (nBuL) and Meerwein-PonndorfVerley (MPV) reduction to GVL; (ii) One-pot two-steps esterification with n-butanol followed by MPV reduction with sec-butanol; and (iii) direct conversion of LA into GVL through a tandem reaction. Selection of this multistep complex reaction evidences the participation of the different acid sites (Lewis or Bronsted) of the material in each individual step: Bronsted-induced acid sites catalyze esterification reaction efficiently, while Lewis acid sites are the preferred sites for the MPV step. Sulfation of MOF-808 is used to enhance the Bronsted acidity of MOF-808, which improves the performance for esterification. However, the sulfate groups introduced are detrimental for the MPV step, since they reduce the intra-pore space available to form the required bulky transition state. These results evidence the need to find the best equilibrium between Bronsted and Lewis acid sites to optimize the outcome of this multistep reaction.