Towards acid MOFs-catalytic performance of sulfonic acid functionalized architectures

Jana Juan-Alcañiz*, Robin Gielisse, Ana B. Lago, Enrique V. Ramos-Fernandez, Pablo Serra-Crespo, Thomas Devic, Nathalie Guillou, Christian Serre, Freek Kapteijn, Jorge Gascon

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

150 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)2311-2318
Number of pages8
JournalCatalysis Science and Technology
Issue number9
StatePublished - Sep 2013
Externally publishedYes

ASJC Scopus subject areas

  • Catalysis


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