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Sulfation of metal–organic frameworks: Opportunities for acid catalysis and proton conductivity
- Source :
- Journal of Catalysis. 281:177-187
- Publication Year :
- 2011
- Publisher :
- Elsevier BV, 2011.
-
Abstract
- A new post-functionalization method for metal–organic frameworks (MOFs) has been developed to introduce acidity for catalysis. Upon treatment with a mixture of triflic anhydride and sulfuric acid, chemically stable MOF structures MIL-101(Cr) and MIL-53(Al) can be sulfated, resulting in a Bronsted sulfoxy acid group attached to up to 50% of the aromatic terephthalate linkers of the structure. The sulfated samples have been extensively characterized by solid-state NMR, XANES, and FTIR spectroscopy. The functionalized acidic frameworks show catalytic activity similar to that of acidic polymers like Nafion® display in the esterification of n-butanol with acetic acid (TOF ∼ 1 min−1 @ 343 K). Water adsorbs strongly up to 4 molecules per sulfoxy acid group, and an additional 2 molecules are taken up at lower temperatures in the 1-D pore channels of S-MIL-53(Al). The high water content and Bronsted acidity provide the structure S-MIL-53(Al) a high proton conductivity up to moderate temperatures.
Details
- ISSN :
- 00219517
- Volume :
- 281
- Database :
- OpenAIRE
- Journal :
- Journal of Catalysis
- Accession number :
- edsair.doi...........8f0aa03ab331feb100e2ad8dbb632c68