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Ethylene/ethane separation in a stable hydrogen-bonded organic framework through a gating mechanism

Nature Chemistry volume 13, pages 933–939 (2021)Cite this article

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Abstract

Porous materials are very promising for the development of cost- and energy-efficient separation processes, such as for the purification of ethylene from ethylene/ethane mixture—an important but currently challenging industrial process. Here we report a microporous hydrogen-bonded organic framework that takes up ethylene with very good selectivity over ethane through a gating mechanism. The material consists of tetracyano-bicarbazole building blocks held together through intermolecular CN···H–C hydrogen bonding interactions, and forms as a threefold-interpenetrated framework with pores of suitable size for the selective capture of ethylene. The hydrogen-bonded organic framework exhibits a gating mechanism in which the threshold pressure required for guest uptake varies with the temperature. Ethylene/ethane separation is validated by breakthrough experiments with high purity of ethylene (99.1%) at 333 K. Hydrogen-bonded organic frameworks are usually not robust, yet this material was stable under harsh conditions, including exposure to strong acidity, basicity and a variety of highly polar solvents.

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Fig. 1: Tuning gate-pressures mechanism for highly selective gas separation.
Fig. 2: Crystal structure of HOF-FJU-1.
Fig. 3: C2H4 and C2H6 sorption and separation in HOF-FJU-1a.
Fig. 4: Single-crystal structure of HOF-FJU-1∙0.94 C2H4.

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Data availability

All data supporting the finding of this study are available within this article and its Supplementary Information. Crystallographic data for the structures in this article have been deposited at the Cambridge Crystallographic Data Centre under deposition nos. CCDC 1878390 (HOF-FJU-1), 1871845 (HOF-FJU-1⊃H2O), 1999088 (HOF-FJU-1a), 1942488 (HOF-FJU-1⊃C2H4) and 1999090 (HOF-FJU-1b). Copies of the data can be obtained free of charge from https://www.ccdc.cam.ac.uk/structures/. Source data are provided with this paper.

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Acknowledgements

We gratefully acknowledge the financial support from the National Natural Science Foundation of China (grant nos. 21975044, 21971038 and 21922810), the Fujian Provincial Department of Science and Technology (grant nos. 2019H6012 and 21019L3004) and the Welch Foundation (grant no. AX-1730).

Author information

Author notes

  1. These authors contributed equally: Yisi Yang, Libo Li, Rui-Biao Lin.

Authors and Affiliations

  1. Fujian Provincial Key Laboratory of Polymer Materials, College of Chemistry and Materials Science, Fujian Normal University, Fuzhou, China

    Yisi Yang, Yingxiang Ye, Zizhu Yao, Fahui Xiang, Shimin Chen, Zhangjing Zhang & Shengchang Xiang

  2. College of Chemistry and Chemical Engineering, Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization, Taiyuan University of Technology, Taiyuan, China

    Libo Li & Ling Yang

  3. Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, TX, United States

    Rui-Biao Lin, Yingxiang Ye & Banglin Chen

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Contributions

Y.S.Y., L.L., R.-B.L., Z.J.Z., S.C.X. and B.L.C. conceived the research idea and designed the experiments. Y.S.Y. performed most of the experiments and analysed the data. L.L. and L.Y. measured the laboratory-scale fixed-bed breakthrough tests of HOF-FJU-1. Y.S.Y., L.L, R.-B.L., Z.J.Z., S.C.X. and B.L.C wrote the paper. All authors discussed the results and commented on the manuscript. Y.S.Y., L.L. and R.-B.L. contributed equally to this work.

Corresponding authors

Correspondence to Zhangjing Zhang, Shengchang Xiang or Banglin Chen.

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Competing interests

The authors declare no competing interests.

Additional information

Peer review information Nature Chemistry thanks Ashleigh Fletcher, Ichiro Hisaki, Claire Hobday and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–39, Tables 1–13 and references.

Supplementary Data 1

Crystallographic data for HOF-FJU-1.

Supplementary Data 2

Structure-factor file for HOF-FJU-1.

Supplementary Data 3

Crystallographic data for HOF-FJU-1a.

Supplementary Data 4

Structure-factor file for HOF-FJU-1a.

Supplementary Data 5

Crystallographic data for HOF-FJU-1b.

Supplementary Data 6

Structure-factor file for HOF-FJU-1b.

Supplementary Data 7

Crystallographic data for HOF-FJU-C2H4.

Supplementary Data 8

Structure-factor file for HOF-FJU-C2H4.

Supplementary Data 9

Crystallographic data for HOF-FJU-H2O.

Supplementary Data 10

Structure-factor file for HOF-FJU-H2O.

Supplementary Data 11

Data for Supplementary Figs. 10,11, 13–22.

Supplementary Data 12

NMR data for Supplementary Figs. 35 (1H NMR spectra of compound 2), 36 (1H NMR spectra of compound 3) and 37 (13C NMR spectra of compound 3).

Supplementary Data 13

Input file for calculations, C2H4 298 K.

Supplementary Data 14

Input file for calculations, C2H4 318 K.

Supplementary Data 15

Input file for calculations, C2H4 333 K.

Supplementary Data 16

Input file for calculations, C2H6 298 K.

Supplementary Data 17

Input file for calculations, C2H6 318 K.

Supplementary Data 18

Input file for calculations, C2H6 333 K.

Source data

Source Data Fig. 1

Source data for Fig. 3l, purity of C2H4 from HOF-FJU-1 during the regeneration processes of the fixed bed at different temperatures.

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Yang, Y., Li, L., Lin, RB. et al. Ethylene/ethane separation in a stable hydrogen-bonded organic framework through a gating mechanism. Nat. Chem. 13, 933–939 (2021). https://doi.org/10.1038/s41557-021-00740-z

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