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Orthogonal-array dynamic molecular sieving of propylene/propane mixtures

Abstract

Rigid molecular sieving materials work well for small molecules with the complete exclusion of large ones1,2,3, and molecules with matching physiochemical properties may be separated using dynamic molecular sieving materials4,5,6. Metal–organic frameworks (MOFs)7,8,9 are known for their precise control of structures and functions on a molecular level10,11,12,13,14,15. However, the rational design of local flexibility in the MOF framework for dynamic molecular sieving remains difficult and challenging. Here we report a MOF material (JNU-3a) featuring one-dimension channels with embedded molecular pockets opening to propylene (C3H6) and propane (C3H8) at substantially different pressures. The dynamic nature of the pockets is revealed by single-crystal-to-single-crystal transformation upon exposure of JNU-3a to an atmosphere of C3H6 or C3H8. Breakthrough experiments demonstrate that JNU-3a can realize high-purity C3H6 (≥99.5%) in a single adsorption–desorption cycle from an equimolar C3H6/C3H8 mixture over a broad range of flow rates, with a maximum C3H6 productivity of 53.5 litres per kilogram. The underlying separation mechanism—orthogonal-array dynamic molecular sieving—enables both large separation capacity and fast adsorption–desorption kinetics. This work presents a next-generation sieving material design that has potential for applications in adsorptive separation.

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Fig. 1: Molecular sieving.
Fig. 2: Crystal structure of JNU-3.
Fig. 3: Gas sorption properties and DSC profiles.
Fig. 4: Binding sites and dynamic gate-opening.
Fig. 5: Breakthrough experiments.
Fig. 6: Recyclability and breakthrough experiment under humid conditions.

Data availability

The data that support the plots within this paper and other finding of this study are available from the corresponding authors upon reasonable request. The X-ray crystallographic coordinates for structures reported in this Article have been deposited at the Cambridge Crystallographic Data Centre (CCDC), under deposition numbers CCDC 2018163–2018167. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via https://www.ccdc.cam.ac.uk/data_request/cif.

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Acknowledgements

We thank W. Chen and A. Zheng from the Wuhan Institute of Physics and Mathematics (WIPM) of Chinese Academy of Sciences for their advice on computational studies. This work was financially supported by the National Natural Science Foundation of China (nos 21731002 and 21975104), the Guangdong Major Project of Basic and Applied Research (no. 2019B030302009), and Guangdong Basic and Applied Basic Research Foundation (no. 2020A1515011005).

Author information

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Authors

Contributions

W.L. and D.L. conceived and designed the research. H.Z., T.W. and X.-J.X. synthesized the compounds. H.Z. collected and analysed the gas adsorption and separation data. H.Z. collected the X-ray diffraction data. R.-J.W. and Y.Z. analysed the X-ray diffraction data. M.X. performed the theoretical calculations. H.Z., W.L. and D.L. prepared the first version of the manuscript, and all authors participated in and contributed to the final version.

Corresponding authors

Correspondence to Weigang Lu or Dan Li.

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Competing interests

The authors declare no competing interests.

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Peer review information Nature thanks the anonymous reviewers for their contribution to the peer review of this work. Peer reviewer reports are available.

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Extended data figures and tables

Extended Data Fig. 1 Coordination environment.

Local coordination environment of Co2+. Co, light blue; C, dark grey; N, blue; O, red; H, white.

Extended Data Fig. 2 Pore structure of JNU-3a.

Connolly surface representation of JNU-3a viewed along the a axis (yellow/grey curved surface).

Extended Data Fig. 3 DSC profiles.

ad, Differential scanning calorimetry of 50/50 mixed-component of C3H6/He (a), C3H8/He (b), C3H6/C3H8 (c), and helium (d) on JNU-3a at 303 K. The flow rate is 5.0 ml min−1.

Extended Data Fig. 4 IAST selectivity.

Calculated IAST adsorption selectivity of C3H6 over C3H8 on JNU-3a for an equimolar mixture of C3H6/C3H8 at 303 K. P, pressure.

Extended Data Fig. 5 Kinetic profiles.

a, C3H6 kinetic adsorption on JNU-3a, Y-abtc and KAUST-7 at 303 K. b, C3H6 kinetic desorption on JNU-3a, Y-abtc and KAUST-7 at 303 K.

Extended Data Fig. 6 Diffusion rate constants.

ac, The calculated C3H6 diffusion rate constants on JNU-3a (a), KAUST-7 (b), and Y-abtc (c), fitted automatically with BEL-Master software according to the Crank theory. C, concentration; C0, initial concentration; Ce, concentration at equilibrium.

Extended Data Fig. 7 DFT calculations.

a, Geometry optimization by DFT for (i) JNU-3a@2C3H6 with fully relaxed geometry and cell parameters; and (ii) JNU-3a@2C3H6′ (the prime symbol is used here to differentiate it from scenario (i)) with fixed geometry and cell parameters. b, The rotation of the dihedral angle of the pyridine plane and triazole plane. Light blue, red, blue, white and grey represent Co, O, N, H and C atoms, respectively. H atoms are omitted in a for clarity.

Extended Data Fig. 8 C3H6 productivity and purity.

Comparison of C3H6 productivity and purity estimated from the experimental breakthrough data of an equimolar C3H6/C3H8 mixture on JNU-3a, KAUST-7 and Y-abtc at different flow rates.

Supplementary information

Supplementary Information

This file contains supplementary text, supplementary tables 1 – 5, supplementary figures 1 – 54 and supplementary references.

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Zeng, H., Xie, M., Wang, T. et al. Orthogonal-array dynamic molecular sieving of propylene/propane mixtures. Nature 595, 542–548 (2021). https://doi.org/10.1038/s41586-021-03627-8

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