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

Simon Krause, Jack D. Evans, Volodymyr Bon, Irena Senkovska, Paul Iacomi, Felicitas Kolbe, Sebastian Ehrling, Erik Troschke, Jürgen Getzschmann, Daniel M. Többens, Alexandra Franz, Dirk Wallacher, Pascal G. Yot, Guillaume Maurin, Eike Brunner, Philip L. Llewellyn, François-Xavier Coudert and Stefan Kaskel ()
Additional contact information
Simon Krause: Faculty of Chemistry and Food Chemistry, TU Dresden
Jack D. Evans: Faculty of Chemistry and Food Chemistry, TU Dresden
Volodymyr Bon: Faculty of Chemistry and Food Chemistry, TU Dresden
Irena Senkovska: Faculty of Chemistry and Food Chemistry, TU Dresden
Paul Iacomi: Aix-Marseille Univ., CNRS, MADIREL (UMR 7246)
Felicitas Kolbe: Faculty of Chemistry and Food Chemistry, TU Dresden
Sebastian Ehrling: Faculty of Chemistry and Food Chemistry, TU Dresden
Erik Troschke: Faculty of Chemistry and Food Chemistry, TU Dresden
Jürgen Getzschmann: Faculty of Chemistry and Food Chemistry, TU Dresden
Daniel M. Többens: Helmholtz-Zentrum Berlin für Materialien und Energie
Alexandra Franz: Helmholtz-Zentrum Berlin für Materialien und Energie
Dirk Wallacher: Helmholtz-Zentrum Berlin für Materialien und Energie
Pascal G. Yot: Institut Charles Gerhardt Montpellier UMR 5253 Univ. Montpellier CNRS UM ENSCM, Université de Montpellier, Place Eugène Bataillon
Guillaume Maurin: Institut Charles Gerhardt Montpellier UMR 5253 Univ. Montpellier CNRS UM ENSCM, Université de Montpellier, Place Eugène Bataillon
Eike Brunner: Faculty of Chemistry and Food Chemistry, TU Dresden
Philip L. Llewellyn: Aix-Marseille Univ., CNRS, MADIREL (UMR 7246)
François-Xavier Coudert: Chimie ParisTech, PSL University, CNRS, Institut de Recherche de Chimie, Paris
Stefan Kaskel: Faculty of Chemistry and Food Chemistry, TU Dresden

Nature Communications, 2019, vol. 10, issue 1, 1-12

Abstract: Abstract 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 (CD4) 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.

Date: 2019
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DOI: 10.1038/s41467-019-11565-3

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