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A pressure-amplifying framework material with negative gas adsorption transitions

Abstract

Adsorption-based phenomena are important in gas separations1,2, such as the treatment of greenhouse-gas3 and toxic-gas4 pollutants, and in water-adsorption-based heat pumps5 for solar cooling systems. The ability to tune the pore size, shape and functionality of crystalline porous coordination polymers—or metal–organic frameworks (MOFs)—has made them attractive materials for such adsorption-based applications3,6,7,8. The flexibility and guest-molecule-dependent response9,10 of MOFs give rise to unexpected and often desirable adsorption phenomena11,12,13,14. Common to all isothermal gas adsorption phenomena, however, is increased gas uptake with increased pressure. Here we report adsorption transitions in the isotherms of a MOF (DUT-49) that exhibits a negative gas adsorption; that is, spontaneous desorption of gas (methane and n-butane) occurs during pressure increase in a defined temperature and pressure range. A combination of in situ powder X-ray diffraction, gas adsorption experiments and simulations shows that this adsorption behaviour is controlled by a sudden hysteretic structural deformation and pore contraction of the MOF, which releases guest molecules. These findings may enable technologies using frameworks capable of negative gas adsorption for pressure amplification in micro- and macroscopic system engineering. Negative gas adsorption extends the series of counterintuitive phenomena such as negative thermal expansion15,16 and negative refractive indices17 and may be interpreted as an adsorptive analogue of force-amplifying negative compressibility transitions proposed for metamaterials18.

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Figure 1: Gas adsorption isotherms, pressure and kinetic profiles.
Figure 2: In situ PXRD during methane adsorption at 111 K.
Figure 3: Structure of DUT-49op and DUT-49cp.
Figure 4: Temperature-dependent methane adsorption and simulations.

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Acknowledgements

V.B. thanks the German Federal Ministry for education and research (project BMBF number 05K13OD3). S. Krause, V.B., I.S. and S. Kaskel thank the Helmholtz-Zentrum Berlin for financial support and allocation of synchrotron radiation beam time at the KMC-2 beamline. F.-X.C. thanks GENCI (grant number x2015087069) for access to High-Performance Computing resources. G.M. thanks Institut Universitaire de France for its support. We thank U. Koch for scanning electron microscope images, as well as L. Sarkisov and A. Fuchs for discussions.

Author information

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Authors

Contributions

S. Krause and U.S. synthesized and activated the material investigated; S. Krause, V.B., I.S. and S. Kaskel conducted and interpreted volumetric and gravimetric sorption experiments. S. Krause, V.B., D.W. and D.M.T. conducted the in situ PXRD investigations. S. Krause V.B., D.W. and S.Z. conducted the in situ EXAFS investigations. V.B. solved the crystal structure and performed structure modelling. S. Krause performed filming and animation of the structural transitions. F.-X.C. performed quantum mechanical calculations. G.M. and R.S.P. performed the grand canonical Monte Carlo simulations of adsorption. S. Krause, V.B., I.S., F.-X.C., G.M. and S. Kaskel wrote the manuscript.

Corresponding author

Correspondence to Stefan Kaskel.

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Competing interests

The authors declare no competing financial interests.

Additional information

The following crystal structures are available free of charge from the Cambridge Crystallographic Data Centre under reference numbers CCDC-1413081, CCDC-1413083, CCDC-1413082 and CCDC-1413084, respectively: DUT-49op in vacuum at 111 K; DUT-49cp432CH4 (where indicates the number of methane molecules per unit cell) at a relative pressure of 0.28 for methane at 111 K during adsorption; DUT-49op1,344CH4 at a relative pressure of 0.97 for methane at 111 K during adsorption; and DUT-49ip1,176CH4 at a relative pressure of 0.25 for methane at 111 K during desorption.

Supplementary information

Supplementary Information

This file contains Supplementary Methods and Data, Supplementary Schemes 1-2, Supplementary Tables 1-15, Supplementary Figures 1-44 and Supplementary References. (PDF 4061 kb)

Visualization of a framework material during NGA

This video clip shows macroscopic movement of a DUT-49 sample bed filmed in a glass capillary during adsorption of n-butane at 298 - 299 K. (WMV 9263 kb)

Visualization of the framework’s structural transition

This video clip illustrates in an animation the framework structural transition including visualization of ligand deformation and changes of pore size occurring upon contraction of DUT-49op to DUT-49cp. (WMV 93412 kb)

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Krause, S., Bon, V., Senkovska, I. et al. A pressure-amplifying framework material with negative gas adsorption transitions. Nature 532, 348–352 (2016). https://doi.org/10.1038/nature17430

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