Understanding the Role of Open Metal Sites in MOFs for the Efficient Separation of Benzene/Cyclohexane Mixtures
Abstract: Separating C6 cyclic hydrocarbons, specifically benzene and cyclohexane, presents a significant industrial challenge due to their similar physicochemical properties. We conducted Monte Carlo simulations in the Grand-Canonical ensemble to acquire adsorption properties and separation performance data for benzene and cyclohexane in three metal-organic frameworks featuring coordinatively unsaturated metal sites (Ni-MOF-74, Ni-ClBBTA, and Ni-ClBTDD). The separation performance of these MOFs was analyzed and compared with literature data for adsorbents of different natures, demonstrating superior performance. Additionally, we explored the molecular origins of this effective separation, examining the pore-filling mechanism, interaction of guest molecules with metal centers, and mutual interactions of each adsorbate. Our results highlight that the selected adsorbents, with remarkable loading capacity, can efficiently separate both compounds in a mixture with exceptional effectiveness.
- D. Galbraith, S. A. Gross, and D. Paustenbach, Benzene and human health: A historical review and appraisal of associations with various diseases, Critical Reviews in Toxicology 40, 1 (2010).
- R. Duarte-Davidson, Benzene in the environment: an assessment of the potential risks to the health of the population, Occupational and Environmental Medicine 58, 2 (2001).
- J. G. Villaluenga and A. Tabe-Mohammadi, A review on the separation of benzene/cyclohexane mixtures by pervaporation processes, Journal of Membrane Science 169, 159 (2000).
- A. E. Yildirim, N. D. Hilmioglu, and S. Tulbentci, Separation of benzene/cyclohexane mixtures by pervaporation using PEBA membranes, Desalination 219, 14 (2008).
- A. Yamasaki, T. Shinbo, and K. Mizoguchi, Pervaporation of benzene/cyclohexane and benzene/n-hexane mixtures through PVA membranes, Journal of Applied Polymer Science 64, 1061 (1997).
- D. Crespo and R. T. Yang, Adsorption of organic vapors on single-walled carbon nanotubes, Industrial & Engineering Chemistry Research 45, 5524 (2006a).
- M. Eddaoudi, H. Li, and O. M. Yaghi, Highly porous and stable metal-organic frameworks: structure design and sorption properties, Journal of the American Chemical Society 122, 1391 (2000a).
- G. Deng and Z. Wang, Triptycene-based microporous cyanate resins for adsorption/separations of benzene/cyclohexane and carbon dioxide gas, ACS Applied Materials & Interfaces 9, 41618 (2017).
- M. Kotzabasaki and G. E. Froudakis, Review of computer simulations on anti-cancer drug delivery in MOFs, Inorganic Chemistry Frontiers 5, 1255 (2018).
- D. Yang and B. C. Gates, Catalysis by metal organic frameworks: Perspective and suggestions for future research, ACS Catalysis 9, 1779 (2019).
- J. R. Karra and K. S. Walton, Effect of open metal sites on adsorption of polar and nonpolar molecules in metal-organic framework cu-BTC, Langmuir 24, 8620 (2008).
- P. D. C. Dietzel, V. Besikiotis, and R. Blom, Application of metal–organic frameworks with coordinatively unsaturated metal sites in storage and separation of methane and carbon dioxide, Journal of Materials Chemistry 19, 7362 (2009).
- R. T. Yang and E. S. Kikkinides, New sorbents for olefin/paraffin separations by adsorption via pi-complexation, AIChE Journal 41, 509 (1995).
- A. Khelifa, Z. Derriche, and A. Bengueddach, Adsorption of propene on NaX zeolite exchanged with zn2+{}^{+}start_FLOATSUPERSCRIPT + end_FLOATSUPERSCRIPT and cu2+{}^{+}start_FLOATSUPERSCRIPT + end_FLOATSUPERSCRIPT, Applied Catalysis A: General 178, 61 (1999).
- N. Rai and J. I. Siepmann, Transferable potentials for phase equilibria. 10. explicit-hydrogen description of substituted benzenes and polycyclic aromatic compounds, The Journal of Physical Chemistry B 117, 273 (2012).
- S. L. Mayo, B. D. Olafson, and W. A. Goddard, DREIDING: a generic force field for molecular simulations, The Journal of Physical Chemistry 94, 8897 (1990).
- D. Dubbeldam, A. Torres-Knoop, and K. S. Walton, On the inner workings of monte carlo codes, Molecular Simulation 39, 1253 (2013).
- C. R. Martinez and B. L. Iverson, Rethinking the term “pi-stacking”, Chemical Science 3, 2191 (2012).
- I. Dance, Distance criteria for crystal packing analysis of supramolecular motifs, New Journal of Chemistry 27, 22 (2002).
- R. Sips, On the Structure of a Catalyst Surface, The Journal of Chemical Physics 16, 490 (1948).
- M. Eddaoudi, H. Li, and O. M. Yaghi, Highly porous and stable metal-organic frameworks: structure design and sorption properties, Journal of the American Chemical Society 122, 1391 (2000b).
- D. Crespo and R. T. Yang, Adsorption of organic vapors on single-walled carbon nanotubes, Industrial & Engineering Chemistry Research 45, 5524 (2006b).
- A. L. Myers and J. M. Prausnitz, Thermodynamics of mixed-gas adsorption, AIChE Journal 11, 121 (1965).
- Z. Qiao, Q. Xu, and J. Jiang, Computational screening of hydrophobic metal–organic frameworks for the separation of h2s and co2 from natural gas, J. Mater. Chem. A 6, 18898 (2018).
- M. S. Shah, M. Tsapatsis, and J. I. Siepmann, Identifying optimal zeolitic sorbents for sweetening of highly sour natural gas, Angewandte Chemie International Edition 55, 5938 (2016), https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201600612 .
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