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Isotherms of individual pores by gas adsorption crystallography

Nature Chemistry volume 11, pages 562–570 (2019)Cite this article

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Abstract

Accurate measurements and assessments of gas adsorption isotherms are important to characterize porous materials and develop their applications. Although these isotherms provide knowledge of the overall gas uptake within a material, they do not directly give critical information concerning the adsorption behaviour of adsorbates in each individual pore, especially in porous materials in which multiple types of pore are present. Here we show how gas adsorption isotherms can be accurately decomposed into multiple sub-isotherms that correspond to each type of pore within a material. Specifically, two metal–organic frameworks, PCN-224 and ZIF-412, which contain two and three different types of pore, respectively, were used to generate isotherms of individual pores by combining gas adsorption measurements with in situ X-ray diffraction. This isotherm decomposition approach gives access to information about the gas uptake capacity, surface area and accessible pore volume of each individual pore, as well as the impact of pore geometry on the uptake and distribution of different adsorbates within the pores.

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Fig. 1: Ar adsorption behaviour in the individual pores of PCN-224.
Fig. 2: Ar adsorption behaviour in the individual pores of ZIF-412.
Fig. 3: Decomposition of Ar adsorption isotherms of MOFs into sub-isotherms of individual pores.
Fig. 4: Adsorption behaviour of different adsorbates in individual pores of MOFs.
Fig. 5: Correlation between pore geometry and the adsorption behaviour of different adsorbates.

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Data availability

The data that support the findings in this study are available within the article and its Supplementary Information and/or from the corresponding authors on reasonable request.

Code availability

The program VESTA was coded by K.M. and is available free of charge via public domain at http://jp-minerals.org/vesta/en/.

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Acknowledgements

We acknowledge financial support from BK21+ program, the Center for Hybrid Interface Materials (2013M3A6B1078884) and the National Research Foundation of Korea (2017M2A2A6A01070673) (H.S.C., J.K.K. and O.T.), CℏEM, SPST of ShanghaiTech University (no. EM02161943) (H.S.C. and O.T.), Foreign 1000 Talents Plan, China (O.T.), King Abdulaziz City for Science and Technology, Riyadh, Saudi Arabia (O.M.Y.), National Natural Science Foundation of China (no. 21471118, 91545205 and 91622103) and National Key Basic Research Program of China (no. 2014CB239203) (X.G. and H.D.), NSFC 21522105 (Y.B.Z.) and an Advanced European Research Grant (ERC, no. 321140) (H.S.C. and B.M.W.). We also thank R. Flaig for proofreading the manuscript, and X. Cai for providing the three-dimensional structure illustration of each individual cage.

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Author notes

  1. These authors contributed equally: Hae Sung Cho, Jingjing Yang, Xuan Gong.

Authors and Affiliations

  1. Graduate School of EEWS, KAIST, Daejeon, Republic of Korea

    Hae Sung Cho, Jeung Ku Kang & Osamu Terasaki

  2. School of Physical Science and Technology, ShanghaiTech University, Shanghai, China

    Hae Sung Cho, Yue-Biao Zhang & Osamu Terasaki

  3. Inorganic Chemistry and Catalysis group, Debye Institute for Nanomaterials Science, Faculty of Science, Utrecht University, Utrecht, Netherlands

    Hae Sung Cho & Bert M. Weckhuysen

  4. UC Berkeley-Wuhan University Joint Innovative Center, Institute for Advanced Studies, Wuhan University, Luojiashan, Wuhan, China

    Jingjing Yang, Xuan Gong, Hexiang Deng & Omar M. Yaghi

  5. Department of Chemistry, University of California, Berkeley , Berkeley, CA, USA

    Jingjing Yang & Omar M. Yaghi

  6. Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, USA

    Jingjing Yang & Omar M. Yaghi

  7. Kavli Energy NanoSciences Institute, Berkeley, CA, USA

    Jingjing Yang & Omar M. Yaghi

  8. Key Laboratory of Biomedical Polymers-Ministry of Education, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, China

    Xuan Gong & Hexiang Deng

  9. National Museum of Nature and Science, Tsukuba, Ibaraki, Japan

    Koichi Momma

  10. King Abdulaziz City for Science and Technology, Riyadh, Saudi Arabia

    Omar M. Yaghi

  11. Department of Materials and Environmental Chemistry, Stockholm University, Stockholm, Sweden

    Osamu Terasaki

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Contributions

O.T. and O.M.Y. conceived the idea. O.T., O.M.Y. and H.D. led the project. H.S.C. performed the in situ XRD experiments and analysis. J.Y., X.G., Y.-B.Z. and H.D. prepared the samples, and K.M. coded the computer program VESTA. O.T, H.S.C. and J.K.K. contributed to set up the experimental system. H.S.C., J.Y., X.G., H.D., O.M.Y. and O.T. prepared the first version of the manuscript and all the authors contributed to the final version.

Corresponding authors

Correspondence to Hexiang Deng, Omar M. Yaghi or Osamu Terasaki.

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Supplementary Information

Supplementary data, discussion and methods, Supplementary Figs. 1–52 and Supplementary references 1–11.

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Cho, H.S., Yang, J., Gong, X. et al. Isotherms of individual pores by gas adsorption crystallography. Nat. Chem. 11, 562–570 (2019). https://doi.org/10.1038/s41557-019-0257-2

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