Negative Gas Adsorption Transitions and Pressure Amplification Phenomena in Porous Frameworks

Overview

Journal Chem Soc Rev

Date 2025 Jan 27

PMID 39866063

Authors

Simon Krause

Jack D Evans

Volodymyr Bon

Irena Senkovska

Francois-Xavier Coudert

Gulliaume Maurin

Eike Brunner

Philip L Llewellyn

Stefan Kaskel

Affiliations

Soon will be listed here.

Abstract

Nanoporous solids offer a wide range of functionalities for industrial, environmental, and energy applications. However, only a limited number of porous materials are responsive, the nanopore dynamically alters its size and shape in response to external stimuli such as temperature, pressure, light or the presence of specific molecular stimuli adsorbed inside the voids deforming the framework. Adsorption-induced structural deformation of porous solids can result in unique counterintuitive phenomena. Negative gas adsorption (NGA) is such a phenomenon which describes the spontaneous release of gas from an "overloaded" nanoporous solid adsorption-induced structural contraction leading to total pressure amplification (PA) in a closed system. Such pressure amplifying materials may open new avenues for pneumatic system engineering, robotics, damping, or micromechanical actuators. In this review we illustrate the discovery of NGA in DUT-49, a mesoporous metal-organic framework (MOF), and the subsequent examination of conditions for its observation leading to a rationalization of the phenomenon. We outline the development of decisive experimental and theoretical methods required to establish the mechanism of NGA and derive key criteria for observing NGA in other porous solids. We demonstrate the application of these design principles in a series of DUT-49-related model compounds of which several also exhibit NGA. Furthermore, we provide an outlook towards applying NGA as a pressure amplification material and discuss possibilities to discover novel NGA materials and other counterintuitive adsorption phenomena in porous solids in the future.

References

Krause S, Evans J, Bon V, Senkovska I, Ehrling S, Stoeck U . Adsorption Contraction Mechanics: Understanding Breathing Energetics in Isoreticular Metal-Organic Frameworks. J Phys Chem C Nanomater Interfaces. 2022; 122(33):19171-19179. PMC: 9115760. DOI: 10.1021/acs.jpcc.8b04549. View

Roztocki K, Bon V, Senkovska I, Matoga D, Kaskel S . A Logic Gate Based on a Flexible Metal-Organic Framework (JUK-8) for the Concomitant Detection of Hydrogen and Oxygen. Chemistry. 2022; 28(59):e202202255. PMC: 9804503. DOI: 10.1002/chem.202202255. View

Krause S, Bon V, Senkovska I, Tobbens D, Wallacher D, Pillai R . The effect of crystallite size on pressure amplification in switchable porous solids. Nat Commun. 2018; 9(1):1573. PMC: 5910435. DOI: 10.1038/s41467-018-03979-2. View

Schaper L, Keupp J, Schmid R . Molecular Dynamics Simulations of the Breathing Phase Transition of MOF Nanocrystallites II: Explicitly Modeling the Pressure Medium. Front Chem. 2021; 9:757680. PMC: 8575409. DOI: 10.3389/fchem.2021.757680. View

Su Y, Otake K, Zheng J, Horike S, Kitagawa S, Gu C . Separating water isotopologues using diffusion-regulatory porous materials. Nature. 2022; 611(7935):289-294. DOI: 10.1038/s41586-022-05310-y. View

Bon V, Krause S, Senkovska I, Grimm N, Wallacher D, Tobbens D . Massive Pressure Amplification by Stimulated Contraction of Mesoporous Frameworks*. Angew Chem Int Ed Engl. 2021; 60(21):11735-11739. PMC: 8251781. DOI: 10.1002/anie.202100549. View

Miura H, Bon V, Senkovska I, Ehrling S, Watanabe S, Ohba M . Tuning the gate-opening pressure and particle size distribution of the switchable metal-organic framework DUT-8(Ni) by controlled nucleation in a micromixer. Dalton Trans. 2017; 46(40):14002-14011. DOI: 10.1039/c7dt02809a. View

Tiba A, Tivanski A, MacGillivray L . Size-Dependent Mechanical Properties of a Metal-Organic Framework: Increase in Flexibility of ZIF-8 by Crystal Downsizing. Nano Lett. 2019; 19(9):6140-6143. DOI: 10.1021/acs.nanolett.9b02125. View

Durholt J, Fraux G, Coudert F, Schmid R . Ab Initio Derived Force Fields for Zeolitic Imidazolate Frameworks: MOF-FF for ZIFs. J Chem Theory Comput. 2019; 15(4):2420-2432. DOI: 10.1021/acs.jctc.8b01041. View

10.

Rice A, Martin C, Galitskiy V, Berseneva A, Leith G, Shustova N . Photophysics Modulation in Photoswitchable Metal-Organic Frameworks. Chem Rev. 2019; 120(16):8790-8813. DOI: 10.1021/acs.chemrev.9b00350. View

11.

Kolbe F, Krause S, Bon V, Senkovska I, Kaskel S, Brunner E . High-Pressure in Situ Xe NMR Spectroscopy: Insights into Switching Mechanisms of Flexible Metal-Organic Frameworks Isoreticular to DUT-49. Chem Mater. 2022; 31(16):6193-6201. PMC: 9115758. DOI: 10.1021/acs.chemmater.9b02003. View

12.

Seo J, Bonneau C, Matsuda R, Takata M, Kitagawa S . Soft secondary building unit: dynamic bond rearrangement on multinuclear core of porous coordination polymers in gas media. J Am Chem Soc. 2011; 133(23):9005-13. DOI: 10.1021/ja201484s. View

13.

Li L, Lin R, Krishna R, Wang X, Li B, Wu H . Flexible-Robust Metal-Organic Framework for Efficient Removal of Propyne from Propylene. J Am Chem Soc. 2017; 139(23):7733-7736. DOI: 10.1021/jacs.7b04268. View

14.

Colon Y, Snurr R . High-throughput computational screening of metal-organic frameworks. Chem Soc Rev. 2014; 43(16):5735-49. DOI: 10.1039/c4cs00070f. View

15.

Iacomi P, Zheng B, Krause S, Kaskel S, Maurin G, Llewellyn P . Low Temperature Calorimetry Coupled with Molecular Simulations for an In-Depth Characterization of the Guest-Dependent Compliant Behavior of MOFs. Chem Mater. 2022; 32(8):3489-3498. PMC: 9115757. DOI: 10.1021/acs.chemmater.0c00417. View

16.

Shekhah O, Belmabkhout Y, Chen Z, Guillerm V, Cairns A, Adil K . Made-to-order metal-organic frameworks for trace carbon dioxide removal and air capture. Nat Commun. 2014; 5:4228. PMC: 4083436. DOI: 10.1038/ncomms5228. View

17.

Evans J, Coudert F . Macroscopic Simulation of Deformation in Soft Microporous Composites. J Phys Chem Lett. 2017; 8(7):1578-1584. DOI: 10.1021/acs.jpclett.7b00397. View

18.

Walenszus F, Bon V, Evans J, Krause S, Getzschmann J, Kaskel S . On the role of history-dependent adsorbate distribution and metastable states in switchable mesoporous metal-organic frameworks. Nat Commun. 2023; 14(1):3223. PMC: 10239506. DOI: 10.1038/s41467-023-38737-6. View

19.

Evans J, Krause S, Kaskel S, Sweatman M, Sarkisov L . Exploring the thermodynamic criteria for responsive adsorption processes. Chem Sci. 2019; 10(19):5011-5017. PMC: 6530534. DOI: 10.1039/c9sc01299k. View

20.

Fujiwara A, Watanabe S, Miyahara M . Flow Microreactor Synthesis of Zeolitic Imidazolate Framework (ZIF)@ZIF Core-Shell Metal-Organic Framework Particles and Their Adsorption Properties. Langmuir. 2021; 37(13):3858-3867. DOI: 10.1021/acs.langmuir.0c03378. View