Understanding negative gas adsorption in highly porous networks for the design of pressure amplifying materials

Table of contents

1. 1. 1. ERC Advanced Grant:  “Amplipore”
      2. People
      3. Former Members
      4. Publications

ERC Advanced Grant:  “Amplipore”

ERC Advanced Grant:  “Amplipore” ERC Advanced Grant:  “Amplipore” ERC Advanced Grant:  “Amplipore” ERC Advanced Grant:  “Amplipore” ERC Advanced Grant:  “Amplipore”

(GA No.: 742743)
Duration: 9/2017-8/2022

Negative gas adsorption (NGA) is a new and counterintuitive phenomenon, for the first time reported in 2016: Normal solid materials with significant outer or inner surface area always take up gas when the pressure in the surrounding reservoir is increased (adsorption). NGA networks instead react at a certain point in the opposite direction: They release gas upon external gas pressure increase, leading to an overall pressure amplification in a closed system (Fig. 1). Comparable phenomena have never been reported before.

What is so exciting about NGA? We have a unique material in hand, that counteracts to an external force by force amplification. This phenomenon shows a characteristic negative step in the adsorption isotherm (Fig. 2).

So far NGA has solely been observed in a handful of coordination polymers, featuring a colossal compression associated with a mesopore-to-micropore transformation (Fig. 3). Gas pressure amplifying materials could lead to important innovations in gas releasing rescue systems, pneumatic control systems (production, transportation), micropumps, microfluidic devices, pneumatic actuators, and artificial lungs.

A fundamental understanding of the physical mechanisms, structures, and thermodynamic boundary conditions is an essential prerequisite for any industrial application of this counterintuitive phenomenon.

People

• Prof. Dr. rer. nat. habil. Stefan Kaskel

• Dr. rer. nat. Volodymyr Bon

• Dr. rer. nat. Kartik Maity
• Dr. phil. Arpan Hazra
• Dr. rer. nat. Hiroki Miura
• Dr. rer. nat. Andreas Schneemann
• Dr. rer. nat. Ines Hönicke
• B. Felsner
• L. Gilmanova
• Tian Luo

Former Members

• F. Walenszus
• J. Evans
• Thomas Otto
• Niklas Unglaube
• Nikita Busov
• Sattwick Haldar
• Hui-Chun Lee
• Bikash Garai
• Steffen Hausdorf

Publications

• "Chemically Stable Carbazole-Based Imine Covalent Organic Frameworks with Acidochromic Response for Humidity Control Applications", L. Gilmanova, V. Bon, L. Shupletsov, D. Pohl, M. Rauche, E. Brunner, S. Kaskel, J. Amer. Chem. Soc. 2021, 143 (44), 18368–18373.

• "Integration of Fluorescent Functionality into Pressure-Amplifying Metal–Organic Frameworks", F. Walenszus, J. D. Evans, V. Bon, F. Schwotzer, I. Senkovska, S. Kaskel, Chem. Mater. 2021, 33, 7964−7971.

• "Unraveling the Guest-Induced Switchability in the Metal-Organic Framework DUT-13 (Zn)", B. Felsner, V. Bon, J. D. Evans, F. Schwotzer, R. Grünker, I. Senkovska, S. Kaskel, Chem. Eur. J. 2021, 37, 9708-9715.

• "Charting the Complete Thermodynamic Landscape of Gas Adsorption for a Responsive Metal–Organic Framework", R. Goeminne, S. Krause, S. Kaskel, T. Verstraelen, J. D. Evans, J. Am. Chem. Soc. 2021, 143 (11), 4143–4147

• "Massive pressure amplification by stimulated contraction of mesoporous frameworks", V. Bon, S. Krause, I. Senkovska, N. Grimm, D. Wallacher, D. M. Többens, S. Kaskel, Angew. Chem., Int. Ed. 2021, 60 (11), 735-11739.

• "Elucidating the Structural Evolution of a Highly Porous Responsive Metal–Organic Framework (DUT-49(M)) upon Guest Desorption by Time-Resolved in Situ Powder X-ray Diffraction", B. Garai, V. Bon, F. Walenszus, A. Khadiev, D. V. Novikov, S. Kaskel, Cryst. Growth Des. 2021, 21 (1), 270–276.

• "Molecular Diffusion in a Flexible Mesoporous Metal–Organic Framework over the Course of Structural Contraction", F. Walenszus, V. Bon, J. D. Evans, S. Kaskel, M. Dvoyashkin, J.Phys.Chem.Lett. 2020, 11, 9696−9701.

• "Structural Transitions of the Metal–Organic Framework DUT-49(Cu) upon Physi- and Chemisorption Studied by in Situ Electron Paramagnetic Resonance Spectroscopy", D. M. Polyukhov, S. Krause, V. Bon, A. S. Poryvaev, S. Kaskel, M. V. Fedin, J. Phys. Chem. Lett. 2020, 11 (15), 5856–5862.
• "Four-dimensional metal-organic frameworks",  J. D. Evans, V. Bon, I. Senkovska, H.-C. Lee, S. Kaskel, Nat. Commun. 2020, 11, 2690.
• "Engineering micromechanics of soft porouscrystals for negative gas adsorption", S. Krause, J. D. Evans, V. Bon, I. Senkovska, S. Ehrling, P. Iacomi, D. M. Többens, D. Wallacher, M. S. Weiss, B. Zheng, P. G. Yot, G. Maurin, P. L. Llewellyn, F.-X. Coudert, S. Kaskel, Chem. Sci. 2020, 11, 9468–9479.

• "The Role of Temperature and Adsorbate on Negative Gas Adsorption in the Mesoporous Metal-Organic Framework DUT-49", S. Krause, J. D. Evans, V. Bon, I. Senkovska, F.-X. Coudert, D. M. Többens, D. Wallacher, N. Grimm, S. Kaskel, Faraday Discuss. 2021, 225, 168-183.

• "Reversible switching between positive and negative thermal expansion in a metal-organic framework DUT-49 J", B. Garai, V. Bon, A. Efimova, M. Gerlach, I. Senkovska, S. Kaskel . Mater. Chem. A 2020, 8, 20420-20428.

• "Impact of Defects and Crystal Size on Negative Gas Adsorption in DUT-49 Analyzed by In Situ¹²⁹Xe NMR Spectroscopy", S. Krause, F. S. Reuter, S. Ehrling, V. Bon, I. Senkovska, S. Kaskel, E. Brunner, Chem. Mater. 2020, 32 (11), 4641–4650.

• "Low Temperature Calorimetry Coupled with Molecular Simulations for an In-Depth Characterization of the Guest-Dependent Compliant Behavior of MOFsP", Iacomi, B. Zheng, S. Krause, S. Kaskel, G. Maurin, P. L. Llewellyn, Chem. Mater. 2020, 32 (8), 3489–3498

• "Tunable Flexibility and Porosity of the Metal–Organic Framework DUT-49 through Postsynthetic Metal Exchange", B. Garai; V. Bon; S. Krause; F. Schwotzer; M. Gerlach; I. Senkovska; S. Kaskel, Chemistry of Materials 2020, 32 (2), 889-896.

• "New insights into solvent-induced structural changes of 13C labelled metal–organic frameworks by solid state NMR", M. Rauche; S. Ehrling; S. Krause; I. Senkovska; S. Kaskel; E. Brunner, Chemical Communications 2019, 55 (62), 9140-9143.

• "High-Pressure in Situ 129Xe NMR Spectroscopy: Insights into Switching Mechanisms of Flexible Metal–Organic Frameworks Isoreticular to DUT-49", F. Kolbe; S. Krause; V. Bon; I. Senkovska; S. Kaskel; E. Brunner, Chemistry of Materials 2019, 31 (16), 6193-6201.

• "Towards general network architecture design criteria for negative gas adsorption transitions in ultraporous frameworks", S. Krause, J. D. Evans, V. Bon, I. Senkovska, P. Iacomi, F. Kolbe, S. Ehrling, E. Troschke, J. Getzschmann, D. M. Többens, A. Franz, D. Wallacher, P. G. Yot, G. Maurin, E. Brunner, P. L. Llewellyn, F.-X. Coudert, S. Kaskel, Nat. Commun. 2019,10 (1), 3632.

• “Exploring the thermodynamic criteria for responsive adsorption processes”, J. Evans, S. Krause, S. Kaskel, M. Sweatman and L. Sarkisov, Chemical Science 2019, 10 (19), 5011-5017.

• “The effect of crystallite size on pressure amplification in switchable porous solids”, S. Krause, V. Bon, I. Senkovska, D. M. Többens, D. Wallacher, R. S. Pillai, G. Maurin and S. Kaskel, Nat. Commun. 2018, 9, 1573.

• “Adsorption Contraction Mechanics: Understanding Breathing Energetics in Isoreticular Metal-Organic Frameworks”, S. Krause, J. Evans, V. Bon, I. Senkovska, S. Ehrling, U Stoeck, P. Yot, P. Iacomi, P. Llewellyn, G. Maurin, F.-X. Coudert and S. Kaskel, J. Phys. Chem. C 2018, 122 (33), 19171–19179.
• “In Situ Monitoring of Unique Switching Transitions in the Pressure-Amplifying Flexible Framework Material DUT-49 by High-Pressure ¹²⁹Xe NMR Spectroscopy”, J. Schaber, S. Krause, S. Paasch, I. Senkovska, V. Bon, D. M. Többens, D. Wallacher, Stefan Kaskel and E. Brunner, J. Phys. Chem. C, 2017, 121, 5195–5200.
• “Origins of Negative Gas Adsorption”, J. D. Evans, L. Bocquet and F.-X. Coudert, Chem 2016, 1, 873–886. 
• “A pressure-amplifying framework material with negative gas adsorption transitions”, S. Krause, V. Bon, I. Senkovska, U Stoeck, D. Wallacher, D. M. Többens, S. Zander, R. S. Pillai, G. Maurin, F.-X. Coudert and S. Kaskel, Nature 2016, 532, 348–352.