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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de Vos, R. M. & Verweij, H. High-selectivity, high-flux silica membranes for gas separation. Science 279, 1710–1711 (1998)
Nenoff, T. M. Hydrogen purification: MOF membranes put to the test. Nature Chem. 7, 377–378 (2015)
McDonald, T. M. et al. Cooperative insertion of CO2 in diamine-appended metal-organic frameworks. Nature 519, 303–308 (2015)
Barea, E., Montoro, C. & Navarro, J. A. R. Toxic gas removal—metal-organic frameworks for the capture and degradation of toxic gases and vapours. Chem. Soc. Rev. 43, 5419–5430 (2014)
Furukawa, H. et al. Water adsorption in porous metal–organic frameworks and related materials. J. Am. Chem. Soc. 136, 4369–4381 (2014)
Kitagawa, S., Kitaura, R. & Noro, S.-i. Functional porous coordination polymers. Angew. Chem. Int. Ed. 43, 2334–2375 (2004)
Furukawa, H., Cordova, K. E., O’Keeffe, M. & Yaghi, O. M. The chemistry and applications of metal-organic frameworks. Science 341, https://doi.org/10.1126/science.1230444 (2013)
Nugent, P. et al. Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation. Nature 495, 80–84 (2013)
Horike, S., Shimomura, S. & Kitagawa, S. Soft porous crystals. Nature Chem. 1, 695–704 (2009)
Schneemann, A. et al. Flexible metal-organic frameworks. Chem. Soc. Rev. 43, 6062–6096 (2014)
Matsuda, R. Materials chemistry: selectivity from flexibility. Nature 509, 434–435 (2014)
Sato, H. et al. Self-accelerating CO sorption in a soft nanoporous crystal. Science 343, 167–170 (2014)
Takashima, Y. et al. Molecular decoding using luminescence from an entangled porous framework. Nature Commun. 2, 168 (2011)
Yang, S. et al. A partially interpenetrated metal–organic framework for selective hysteretic sorption of carbon dioxide. Nature Mater. 11, 710–716 (2012)
Martinek, C. & Hummel, F. A. Linear thermal expansion of three tungstates. J. Am. Ceram. Soc. 51, 227–228 (1968)
Takenaka, K. Negative thermal expansion materials: technological key for control of thermal expansion. Sci. Technol. Adv. Mater. 13, 013001 (2012)
Shelby, R. A., Smith, D. R. & Schultz, S. Experimental verification of a negative index of refraction. Science 292, 77–79 (2001)
Nicolaou, Z. G. & Motter, A. E. Mechanical metamaterials with negative compressibility transitions. Nature Mater. 11, 608–613 (2012)
Fairen-Jimenez, D. et al. Opening the gate: framework flexibility in ZIF-8 explored by experiments and simulations. J. Am. Chem. Soc. 133, 8900–8902 (2011)
Kondo, A. et al. Novel expansion/shrinkage modulation of 2D layered MOF triggered by clathrate formation with CO2 molecules. Nano Lett. 6, 2581–2584 (2006)
Serre, C. et al. An explanation for the very large breathing effect of a metal–organic framework during CO2 adsorption. Adv. Mater. 19, 2246–2251 (2007)
Férey, G. & Serre, C. Large breathing effects in three-dimensional porous hybrid matter: facts, analyses, rules and consequences. Chem. Soc. Rev. 38, 1380–1399 (2009)
Salles, F. et al. Multistep N2 breathing in the metal—organic framework Co(1,4-benzenedipyrazolate). J. Am. Chem. Soc. 132, 13782–13788 (2010)
Thommes, M. et al. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem. 87, 1051–1069 (2015)
Stoeck, U., Krause, S., Bon, V., Senkovska, I. & Kaskel, S. A highly porous metal-organic framework, constructed from a cuboctahedral super-molecular building block, with exceptionally high methane uptake. Chem. Commun. 48, 10841–10843 (2012)
Traa, Y. & Weitkamp, J. in Handbook of Porous Solids (eds, Schüth, F., Sing, K. S. W. & Weitkamp, J. ) 1015–1057 (Wiley, 2008)
Bon, V. et al. In situ monitoring of structural changes during the adsorption on flexible porous coordination polymers by X-ray powder diffraction: instrumentation and experimental results. Micropor. Mesopor. Mater. 188, 190–195 (2014)
Tan, J. C. & Cheetham, A. K. Mechanical properties of hybrid inorganic–organic framework materials: establishing fundamental structure–property relationships. Chem. Soc. Rev. 40, 1059–1080 (2011)
Neimark, A. V., Coudert, F.-X., Boutin, A. & Fuchs, A. H. Stress-based model for the breathing of metal–organic frameworks. J. Phys. Chem. Lett. 1, 445–449 (2010)
Riekert, L. Instability of sorption complexes in synthetic faujasites. J. Phys. Chem. 73, 4384–4386 (1969)
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.
The authors declare no competing financial interests.
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-49cp⊃432CH4 (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-49op⊃1,344CH4 at a relative pressure of 0.97 for methane at 111 K during adsorption; and DUT-49ip⊃1,176CH4 at a relative pressure of 0.25 for methane at 111 K during desorption.
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)
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)
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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