Sulfation of metal-organic frameworks: Opportunities for acid catalysis and proton conductivity

Maarten Goesten; Jana Juan-Alcañiz; Enrique V. Ramos-Fernandez; K. B. Sai Sankar Gupta; Eli Stavitski; Herman Van Bekkum; Jorge Gascon; Freek Kapteijn

doi:10.1016/j.jcat.2011.04.015

Sulfation of metal-organic frameworks: Opportunities for acid catalysis and proton conductivity

Maarten Goesten, Jana Juan-Alcañiz, Enrique V. Ramos-Fernandez, K. B. Sai Sankar Gupta, Eli Stavitski, Herman Van Bekkum, Jorge Gascon^*, Freek Kapteijn

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

261 Scopus citations

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 Brønsted 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 Brønsted acidity provide the structure S-MIL-53(Al) a high proton conductivity up to moderate temperatures.

Original language	English (US)
Pages (from-to)	177-187
Number of pages	11
Journal	Journal of Catalysis
Volume	281
Issue number	1
DOIs	https://doi.org/10.1016/j.jcat.2011.04.015
State	Published - Jul 1 2011
Externally published	Yes

Keywords

Esterification
Flexibility
MIL-101
MIL-53
Metal-organic frameworks
Proton conductivity

ASJC Scopus subject areas

Catalysis
Physical and Theoretical Chemistry

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10.1016/j.jcat.2011.04.015

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title = "Sulfation of metal-organic frameworks: Opportunities for acid catalysis and proton conductivity",

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 Br{\o}nsted 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{\textregistered} 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 Br{\o}nsted acidity provide the structure S-MIL-53(Al) a high proton conductivity up to moderate temperatures.",

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author = "Maarten Goesten and Jana Juan-Alca{\~n}iz and Ramos-Fernandez, {Enrique V.} and {Sai Sankar Gupta}, {K. B.} and Eli Stavitski and {Van Bekkum}, Herman and Jorge Gascon and Freek Kapteijn",

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AU - Goesten, Maarten

AU - Juan-Alcañiz, Jana

AU - Ramos-Fernandez, Enrique V.

AU - Sai Sankar Gupta, K. B.

AU - Stavitski, Eli

AU - Van Bekkum, Herman

AU - Gascon, Jorge

AU - Kapteijn, Freek

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N2 - 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 Brønsted 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 Brønsted acidity provide the structure S-MIL-53(Al) a high proton conductivity up to moderate temperatures.

AB - 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 Brønsted 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 Brønsted acidity provide the structure S-MIL-53(Al) a high proton conductivity up to moderate temperatures.

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Sulfation of metal-organic frameworks: Opportunities for acid catalysis and proton conductivity

Abstract

Keywords

ASJC Scopus subject areas

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