Computational Screening of Nanoporous Materials for Hexane and Heptane Isomer Separation

Yongchul G. Chung, Peng Bai, Maciej Haranczyk, Karson T. Leperi, Peng Li, Hongda Zhang, Timothy C. Wang, Tim Duerinck, Fengqi You, Joseph T Hupp, Omar K. Farha, J. Ilja Siepmann, Randall Q. Snurr

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Abstract

Computational high-throughput screening was carried out to assess a large number of experimentally reported metal-organic frameworks (MOFs) and zeolites for their utility in hexane isomer separation. Through the work, we identified many MOFs and zeolites with high selectivity (SL+M > 10) for the group of n-hexane, 2-methylpentane, and 3-methylpentane (linear and monobranched isomers) versus 2,2-dimethylbutane and 2,3-dimethylbutane (dibranched isomers). This group of selective sorbents includes VICDOC (Fe2(BDP)3), a MOF with triangular pores that is known to exhibit high isomer selectivity and capacity. For three of these structures, the adsorption isotherms for a 10-component mixture of hexane and heptane isomers were calculated. Subsequent simulations of column breakthrough curves showed that the DEYVUA MOF exhibits a longer process cycle time than VICDOC MOF or MRE zeolite, which are previously reported, high-performing materials, illustrating the importance of capacity in designing MOFs for practical applications. Among the identified candidates, we synthesized and characterized a MOF in a new copper form with high predicted adsorbent capacity (qL+M > 1.2 mol/L) and moderately high selectivity (SL+M ≈ 10). Finally, we examined the role of pore shape in hexane isomer separations, especially of triangular-shaped pores. We show through the potential energy surface and three-dimensional siting analyses that linear alkanes do not populate the corners of narrow triangular channels and that structures with nontriangular pores can efficiently separate hexane isomers. Detailed thermodynamic analysis illustrates how differences in the free energy of adsorption contribute to shape-selective separation in nanoporous materials.

Original languageEnglish
Pages (from-to)6315-6328
Number of pages14
JournalChemistry of Materials
Volume29
Issue number15
DOIs
Publication statusPublished - Aug 8 2017

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Heptanes
Hexanes
Heptane
Hexane
Isomers
Screening
Metals
Zeolites
Potential energy surfaces
Alkanes
Sorbents
Adsorption isotherms
Paraffins
Adsorbents
Free energy
Copper
Throughput
Thermodynamics
Adsorption

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Cite this

Chung, Y. G., Bai, P., Haranczyk, M., Leperi, K. T., Li, P., Zhang, H., ... Snurr, R. Q. (2017). Computational Screening of Nanoporous Materials for Hexane and Heptane Isomer Separation. Chemistry of Materials, 29(15), 6315-6328. https://doi.org/10.1021/acs.chemmater.7b01565

Computational Screening of Nanoporous Materials for Hexane and Heptane Isomer Separation. / Chung, Yongchul G.; Bai, Peng; Haranczyk, Maciej; Leperi, Karson T.; Li, Peng; Zhang, Hongda; Wang, Timothy C.; Duerinck, Tim; You, Fengqi; Hupp, Joseph T; Farha, Omar K.; Siepmann, J. Ilja; Snurr, Randall Q.

In: Chemistry of Materials, Vol. 29, No. 15, 08.08.2017, p. 6315-6328.

Research output: Contribution to journalArticle

Chung, YG, Bai, P, Haranczyk, M, Leperi, KT, Li, P, Zhang, H, Wang, TC, Duerinck, T, You, F, Hupp, JT, Farha, OK, Siepmann, JI & Snurr, RQ 2017, 'Computational Screening of Nanoporous Materials for Hexane and Heptane Isomer Separation', Chemistry of Materials, vol. 29, no. 15, pp. 6315-6328. https://doi.org/10.1021/acs.chemmater.7b01565
Chung, Yongchul G. ; Bai, Peng ; Haranczyk, Maciej ; Leperi, Karson T. ; Li, Peng ; Zhang, Hongda ; Wang, Timothy C. ; Duerinck, Tim ; You, Fengqi ; Hupp, Joseph T ; Farha, Omar K. ; Siepmann, J. Ilja ; Snurr, Randall Q. / Computational Screening of Nanoporous Materials for Hexane and Heptane Isomer Separation. In: Chemistry of Materials. 2017 ; Vol. 29, No. 15. pp. 6315-6328.
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