Towards acid MOFs – catalytic performance of sulfonic acid functionalized architectures

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: HSO sub(3)-MIL-101(Cr) synthesized following diffe...

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Bibliographic Details
Published in:Catalysis science & technology 2013-01, Vol.3 (9), p.2311-2318
Main Authors: Juan-Alcañiz, Jana, Gielisse, Robin, Lago, Ana B., Ramos-Fernandez, Enrique V., Serra-Crespo, Pablo, Devic, Thomas, Guillou, Nathalie, Serre, Christian, Kapteijn, Freek, Gascon, Jorge
Format: Article
Language:English
Subjects:
Acetic acid
Activation
Catalysis
Catalysts
Deactivation
Esterification
Esters
Sulfonic acid
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Summary: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: HSO sub(3)-MIL-101(Cr) synthesized following different approaches and a new structure based on HSO sub(3)-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 viaformation of butanol sulfonic esters has been observed. Due to the strong interaction between -SO sub(3) super(-) and the Cr open metal site where usually fluorine (F super(-)) is located in the structure, the HSO sub(3)-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.
ISSN:2044-4753
2044-4761
DOI:10.1039/c3cy00272a