Towards general network architecture design criteria for negative gas adsorption transitions in ultraporous frameworks

Switchable metal-organic frameworks (MOFs) have been proposed for various energy-related storage and separation applications, but the mechanistic understanding of adsorption-induced switching transitions is still at an early stage. Here we report critical design criteria for negative gas adsorption...

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Vydáno v:Nature communications Ročník 10; číslo 1; s. 3632 - 12
Hlavní autoři: Krause, Simon, Evans, Jack D., Bon, Volodymyr, Senkovska, Irena, Iacomi, Paul, Kolbe, Felicitas, Ehrling, Sebastian, Troschke, Erik, Getzschmann, Jürgen, Többens, Daniel M., Franz, Alexandra, Wallacher, Dirk, Yot, Pascal G., Maurin, Guillaume, Brunner, Eike, Llewellyn, Philip L., Coudert, François-Xavier, Kaskel, Stefan
Médium: Journal Article
Jazyk:angličtina
Vydáno: London Nature Publishing Group UK 12.08.2019
Nature Publishing Group
Nature Portfolio
Témata:
119/118
140/131
639/301/299/1013
639/638/263/915
639/638/298/921
Adsorption
Amplification
Argon
CD4 antigen
Chemical Sciences
Computer applications
Computer simulation
Contraction
Design criteria
Energy storage
Enthalpy
Humanities and Social Sciences
Magnetic resonance spectroscopy
Metal-organic frameworks
Methane
Micromechanics
Monte Carlo simulation
multidisciplinary
Neutron diffraction
Neutrons
NMR
NMR spectroscopy
Nuclear magnetic resonance
Pore size
Porosity
Pressure
Science
Science (multidisciplinary)
Stiffening
Switching theory
ISSN:2041-1723, 2041-1723
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Popis
Shrnutí:Switchable metal-organic frameworks (MOFs) have been proposed for various energy-related storage and separation applications, but the mechanistic understanding of adsorption-induced switching transitions is still at an early stage. Here we report critical design criteria for negative gas adsorption (NGA), a counterintuitive feature of pressure amplifying materials, hitherto uniquely observed in a highly porous framework compound (DUT-49). These criteria are derived by analysing the physical effects of micromechanics, pore size, interpenetration, adsorption enthalpies, and the pore filling mechanism using advanced in situ X-ray and neutron diffraction, NMR spectroscopy, and calorimetric techniques parallelised to adsorption for a series of six isoreticular networks. Aided by computational modelling, we identify DUT-50 as a new pressure amplifying material featuring distinct NGA transitions upon methane and argon adsorption. In situ neutron diffraction analysis of the methane (CD 4 ) adsorption sites at 111 K supported by grand canonical Monte Carlo simulations reveals a sudden population of the largest mesopore to be the critical filling step initiating structural contraction and NGA. In contrast, interpenetration leads to framework stiffening and specific pore volume reduction, both factors effectively suppressing NGA transitions. Porous framework material DUT-49 was recently demonstrated to exhibit a unique counterintuitive negative gas adsorption (NGA) behaviour. Here the authors identify framework DUT-50 as an additional pressure amplifying material that features distinct NGA transitions, and suggest structural design criteria to access other such materials.
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ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-019-11565-3