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Magnetometric Characterization of Intermediates in the Solid-State Electrochemistry of Redox-Active Metal-Organic Frameworks

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Switching Kr/Xe selectivity with temperature in a metal-organic framework.

Carlos A Fernandez¹, Jian Liu, Praveen K Thallapally

¹Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States.

Journal of the American Chemical Society

|May 18, 2012

Summary

Researchers studied krypton (Kr) and xenon (Xe) adsorption on fluorinated metal-organic frameworks. One material, FMOFCu, exhibited unusual Kr selectivity below 0°C due to its unique structure.

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Area of Science:

Materials Science
Adsorption Science
Chemical Engineering

Background:

Metal-organic frameworks (MOFs) are porous materials with tunable properties.
Selective gas adsorption is crucial for gas separation and purification.
Fluorinated MOFs offer unique adsorption characteristics.

Purpose of the Study:

To investigate the adsorption behavior of krypton (Kr) and xenon (Xe) on two distinct partially fluorinated MOFs (FMOFCu and FMOFZn).
To understand the structural factors influencing gas selectivity in these materials.
To evaluate the potential of FMOFCu for Kr/Xe separation.

Main Methods:

Gas adsorption isotherms were measured for Kr and Xe on FMOFCu and FMOFZn.
Structural analysis was performed to correlate framework topology with adsorption behavior.
Selectivity was calculated based on adsorption data at various temperatures and pressures.

Main Results:

FMOFCu exhibited an inversion in sorption selectivity for Kr at temperatures below 0 °C, unlike FMOFZn.
The unique 1D microtubular structure and bottleneck windows in FMOFCu were identified as the cause of this behavior.
An estimated Kr/Xe selectivity of 36 was achieved with FMOFCu at 0.1 bar and 203 K.

Conclusions:

The specific topology of FMOFCu, featuring 1D microtubes and narrow windows, leads to unique and inverted Kr/Xe selectivity.
Partially fluorinated MOFs can be designed for selective noble gas separation.
FMOFCu shows promise for applications in Kr/Xe separation technologies.