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Tunable acetylene sorption by flexible catenated metal–organic frameworks

Nature Chemistry volume 14, pages 816–822 (2022)Cite this article

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Abstract

The safe storage of flammable gases, such as acetylene, is essential for current industrial purposes. However, the narrow pressure (P) and temperature range required for the industrial use of pure acetylene (100 < P < 200 kPa at 298 K) and its explosive behaviour at higher pressures make its storage and release challenging. Flexible metal–organic frameworks that exhibit a gated adsorption/desorption behaviour—in which guest uptake and release occur above threshold pressures, usually accompanied by framework deformations—have shown promise as storage adsorbents. Herein, the pressures for gas uptake and release of a series of zinc-based mixed-ligand catenated metal–organic frameworks were controlled by decorating its ligands with two different functional groups and changing their ratio. This affects the deformation energy of the framework, which in turn controls the gated behaviour. The materials offer good performances for acetylene storage with a usable capacity of ~90 v/v (77% of the overall amount) at 298 K and under a practical pressure range (100–150 kPa).

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Fig. 1: Schematic representation of the S-shape adsorption isotherms of Zn-CAT-(X)n depending on guest pressure and the ratio of bdc–NO2/bdc/bdc–NH2 linkers in the MOF.
Fig. 2: Presentation of the Zn-CAT-(X)n derivatives as soft porous crystal candidates.
Fig. 3: Tunable acetylene uptake and release sorptions.
Fig. 4: Efficiency of Zn-CAT-(X)n for acetylene storage.

Data availability

X-ray crystallographic data have been deposited at the CCDC (http://www.ccdc.cam.ac.uk/) under CCDC no. 2036574 (as-synthesized Zn-CAT-(NO2)100) and no. 2036575 (activated Zn-CAT-(NO2)100). A copy of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/. All other data supporting the findings of this study are available within the article and its Supplementary Information. Source data are provided with this paper. The source data for Supplementary Figs. 29–32 are available in Supplementary Data 3. Data are also available from the corresponding author upon reasonable request.

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Acknowledgements

This work was supported by Air Liquide via the 2016 Air Liquide Scientific Challenge, a KAKENHI Grant-in-Aid for Specially Promoted Research (JP25000007), Scientific Research (S) (JP18H05262) and Early-Career Scientists (JP19K15584) from the Japan Society of the Promotion of Science. Synchrotron X-ray diffraction measurements were performed at the Japan Synchrotron Radiation Institute, Super Photon Ring – 8 GeV (proposal nos 2018B1820 and 2019A1136). We acknowledge iCeMS Analysis Centre for access to analytical facilities.

We are grateful to CNRS-Kyoto LIA ‘SMOLAB’. In addition, we thank Air Liquide Japan, P. Ginet and L. Prost, as well as the technical staff for advice and experimental assistance.

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Authors and Affiliations

  1. Institute for Integrated Cell-Material Sciences (WPI-iCeMS), Kyoto University, Sakyo-ku, Japan

    Mickaele Bonneau, Jia-Jia Zheng, Alexandre Legrand, Kunihisa Sugimoto, Ken-ichi Otake & Susumu Kitagawa

  2. Air Liquide Laboratories, Innovation Campus Tokyo, Yokosuka, Japan

    Christophe Lavenn & Tomofumi Ogawa

  3. Element Strategy Initiative for Catalyst and Batteries, Kyoto University, Nishikyo-ku, Japan

    Jia-Jia Zheng & Shigeyoshi Sakaki

  4. Japan Synchrotron Radiation Research Institute/SPring-8, Sayo, Japan

    Kunihisa Sugimoto

  5. Chimie Paris Tech, PSL University, CNRS, Institut de Recherche de Chimie Paris, Paris, France

    Francois-Xavier Coudert

  6. Air Liquide R&D, Les Loges-en-Josas, France

    Regis Reau

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Contributions

S.K., C.L. and R.R. formulated the project. M.B. and C.L. synthesized the compounds and collected the gas adsorption data. M.B. and C.L. analysed all adsorption data. M.B. and C.L. collected and analysed the 1H NMR, thermogravimetric analysis and powder X-ray diffraction data. K.-i.O. and K.S. collected and analysed the synchrotron X-ray diffraction data. A.L. and M.B. collected all scanning electron microscopy images and ultraviolet–visible spectroscopy and infrared analysis data. F.-X.C. performed the thermodynamics calculations. J.-J.Z. and S.S. performed the quantum chemical calculations. T.O. and C.L. built and collected the sorption data from the acetylene experimental set-up. M.B., K.-i.O., A.L., J.-J.Z., F.-X.C. and S.K. wrote the paper, and all authors contributed to revising the paper.

Corresponding author

Correspondence to Susumu Kitagawa.

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Competing interests

R. Réau is senior scientific director of research and development and group senior fellow of Air Liquide, France. C. Lavenn, research project manager, and T. Ogawa are employed at Air Liquide Laboratories Innovation Campus in Tokyo, Japan. S. Kitagawa was partially funded by Air Liquide in the frame of a collaboration research agreement between Air Liquide and Kyoto University. The other authors do not declare any competing interests.

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Nature Chemistry thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–49, Tables 1–5 and Discussion.

Supplementary Data 1

Crystallographic data for the activated Zn-CAT-(NO2) (CCDC no. 2036575).

Supplementary Data 2

Crystallographic data for the as-synthesized Zn-CAT-(NO2) (CCDC no. 2036574).

Supplementary Data 3

Source data for Supplementary Figs. 29–32.

Source data

Source Data Fig. 2

Source data for Fig. 2c.

Source Data Fig. 3

Source data for Fig. 3a–d.

Source Data Fig. 4

Source data for Fig. 4a–c.

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Bonneau, M., Lavenn, C., Zheng, JJ. et al. Tunable acetylene sorption by flexible catenated metal–organic frameworks. Nat. Chem. 14, 816–822 (2022). https://doi.org/10.1038/s41557-022-00928-x

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