Chemical reduction of metal-organic framework materials as a method to enhance gas uptake and binding

Karen L. Mulfort; Joseph T Hupp

doi:10.1021/ja0740364

Chemical reduction of metal-organic framework materials as a method to enhance gas uptake and binding

Karen L. Mulfort, Joseph T Hupp^*

^*Corresponding author for this work

Chemistry

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

572 Scopus citations

Abstract

A mixed-ligand metal-organic framework (MOF) of the formula Zn₂(NDC)₂(diPyNI) (NDC = 2,6-dicarboxylate, diPyNI = N,N′-di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide) has been chemically reduced in the solid state by lithium metal in dimethylformamide (DMF). Striking hysteresis in the N₂ adsorption isotherm suggests dynamic framework behavior of the reduced material that is not observed in the neutral MOF. The reduced framework also exhibits significantly enhanced H₂ uptake and isosteric heat of adsorption over the entire loading range. Notably,the striking increase in H₂ uptake cannot be solely attributed to H₂-Li⁺ interactions and is most likely augmented by increased ligand polarizability and framework displacement effects.

Original language	English (US)
Pages (from-to)	9604-9605
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	129
Issue number	31
DOIs	https://doi.org/10.1021/ja0740364
State	Published - Aug 8 2007

ASJC Scopus subject areas

General Chemistry

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title = "Chemical reduction of metal-organic framework materials as a method to enhance gas uptake and binding",

abstract = "A mixed-ligand metal-organic framework (MOF) of the formula Zn2(NDC)2(diPyNI) (NDC = 2,6-dicarboxylate, diPyNI = N,N′-di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide) has been chemically reduced in the solid state by lithium metal in dimethylformamide (DMF). Striking hysteresis in the N2 adsorption isotherm suggests dynamic framework behavior of the reduced material that is not observed in the neutral MOF. The reduced framework also exhibits significantly enhanced H2 uptake and isosteric heat of adsorption over the entire loading range. Notably,the striking increase in H2 uptake cannot be solely attributed to H2-Li+ interactions and is most likely augmented by increased ligand polarizability and framework displacement effects.",

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N2 - A mixed-ligand metal-organic framework (MOF) of the formula Zn2(NDC)2(diPyNI) (NDC = 2,6-dicarboxylate, diPyNI = N,N′-di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide) has been chemically reduced in the solid state by lithium metal in dimethylformamide (DMF). Striking hysteresis in the N2 adsorption isotherm suggests dynamic framework behavior of the reduced material that is not observed in the neutral MOF. The reduced framework also exhibits significantly enhanced H2 uptake and isosteric heat of adsorption over the entire loading range. Notably,the striking increase in H2 uptake cannot be solely attributed to H2-Li+ interactions and is most likely augmented by increased ligand polarizability and framework displacement effects.

AB - A mixed-ligand metal-organic framework (MOF) of the formula Zn2(NDC)2(diPyNI) (NDC = 2,6-dicarboxylate, diPyNI = N,N′-di-(4-pyridyl)-1,4,5,8-naphthalenetetracarboxydiimide) has been chemically reduced in the solid state by lithium metal in dimethylformamide (DMF). Striking hysteresis in the N2 adsorption isotherm suggests dynamic framework behavior of the reduced material that is not observed in the neutral MOF. The reduced framework also exhibits significantly enhanced H2 uptake and isosteric heat of adsorption over the entire loading range. Notably,the striking increase in H2 uptake cannot be solely attributed to H2-Li+ interactions and is most likely augmented by increased ligand polarizability and framework displacement effects.

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Chemical reduction of metal-organic framework materials as a method to enhance gas uptake and binding

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