Towards acid MOFs - Catalytic performance of sulfonic acid functionalized architectures

by J. Juan-Alcañiz, R. Gielisse, A.B. Lago, E.V. Ramos-Fernandez, P. Serra-Crespo, T. Devic, N. Guillou, C. Serre, F. Kapteijn, J. Gascon
Year: 2013 ISSN: DOI: 10.1039/C3CY00272A

Bibliography

J. Juan-Alcañiz, R. Gielisse, A.B. Lago, E.V. Ramos-Fernandez, P. Serra-Crespo, T. Devic, N. Guillou, C. Serre, F. Kapteijn, J. Gascon, Catal. Sci. & Tech. 3 (2013) 2311 - 2318, Towards acid MOFs - Catalytic performance of sulfonic acid functionalized architectures

Abstract

​In this work, the inclusion of free sulfonic acid groups in highly stable MOFs is explored. The synthesized catalysts have been applied in a model esterification reaction. Two metal organic frameworks bearing sulfonic acid moieties are investigated: HSO3-MIL-101(Cr) synthesized following different approaches and a new structure based on HSO3-bdc and Zr. The acidic properties, catalytic performance, deactivation and stability of the different structures are critically evaluated. In the case of MIL-101(Cr), deactivation of the sulfonic groups via formation of butanol sulfonic esters has been observed. Due to the strong interaction between –SO3− and the Cr open metal site where usually fluorine (F−) is located in the structure, the HSO3-MIL-101(Cr) catalysts are not stable under acidic regeneration conditions. When using Zr as a metal node, a new and stable sulfonic acid containing porous structure was synthesized. This structure showed high activity and full re-usability in the esterification of n-butanol with acetic acid. In this case, deactivation of the catalyst due to sulfonic ester formation could be reversed by reactivation under acidic conditions.

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