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Isotherms of individual pores by gas adsorption crystallography

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.

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.), CEM, 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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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 or 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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