Separation principle of xylene isomers and ethylbenzene with hydrogen-bonded host frameworks via first-principles calculation

Su Hwan Kim; Ju Hyun Park; Eun Min Go; Woo-Sik Kim; Sang Kyu Kwak

Journal of Industrial and Engineering Chemistry, Vol.85, 276-281, May, 2020

DOI10.1016/j.jiec.2020.02.010 Export Citation

Separation principle of xylene isomers and ethylbenzene with hydrogen-bonded host frameworks via first-principles calculation

Su Hwan Kim, Ju Hyun Park, Eun Min Go, Woo-Sik Kim^{1, †}, and Sang Kyu Kwak^†

Department of Energy Engineering, School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan 44919, Republic of Korea
¹Department of Chemical Engineering, College of Engineering, Kyung Hee University, Yongin 17104, Republic of Korea

E-mail:,

Separation of molecular isomers, which have similar physical properties, is hardly achieved with conventional separation methods based on phase equilibria. However, using selective inclusion of target molecules into dismantlable molecular framework allows molecular isomers to be effectively separated from one another. For that purpose, we consider the hydrogen-bonded organic framework (HOF), which can undergo solvent-mediated crystallization. Herein, we theoretically elucidated the separation mechanism of the mixture of xylene isomers (i.e., o-, m-, and p-xylene) and ethyl benzene (EB) using guanidinium (G) cation and organosulfonate anion (S) host systems (i.e., 2(G) + 4,4' -biphenyldisulfonate (G2BPDS) and 2(G) + 2,6-naphthalenedisulfonate (G2NDS) GS-host systems). Density functional theory (DFT) calculations were carried out to investigate separation mechanisms in terms of thermodynamics (i.e., formation energy, interaction energies of guest-host and guest-guest, and vacancy formation energy) and kinetics (i.e., surface energy) considering the solvent-mediated crystallization process. We theoretically predicted that G2BPDS system could effectively separate EB from xylene isomers, and G2NDS system could separate each xylene isomer by sequential separation process.

Keywords:Hydrogen-bonded organic framework;(HOF);Density functional theory (DFT) calculation;Xylene isomers;Separation;Thermodynamics;Kinetics

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[2] Marchetti P, Solomon MFJ, Szekely G, Livingston AG, Chem. Rev., 114(21), 10735 (2014)

[3] Ruthbven DM, Principles of Adsorption and Adsorption Processes, Wiley & Sons, New York, 1984.

[4] Xomeritakis G, Lai ZP, Tsapatsis M, Ind. Eng. Chem. Res., 40(2), 544 (2001)

[5] Maier NM, Franco P, Lindner W, J. Chromatogr. A, 906(1-2), 3 (2001)

[6] Buser HR, Rappe C, Anal. Chem., 56(3), 442 (1984)

[7] Armstrong DW, Anal. Chem., 59(2), 84A (1987)

[8] El Osta R, Carlin-Sinclair A, Guillou N, Walton RI, Vermoortele F, Maes M, de Vos D, Millange F, Chem. Mater., 24(14), 2781 (2012)

[9] Alaerts L, Kirschhock CEA, Maes M, van der Veen MA, Finsy V, Depla A, Martens JA, Baron GV, Jacobs PA, Denayer JFM, De Vos DE, Angew. Chem.-Int. Edit., 46(23), 4293 (2007)

[10] Torres-Knoop A, Krishna R, Dubbeldam D, Angew. Chem. Int. Ed., 54(30), 7774 (2014)

[11] McDaniel JG, Schmidt JR, J. Phys. Chem. C, 116(26), 14031 (2012)

[12] Gu ZY, Yan XP, Angew. Chem.-Int. Edit., 49, 1477 (2010)

[13] He YB, Xiang SC, Chen BL, J. Am. Chem. Soc., 133(37), 14570 (2011)

[14] Adachi T, Ward MD, Accounts Chem. Res., 49(12), 2669 (2016)

[15] Xue M, Lie B, Qiu SL, Chen BL, Mater. Today, 19(9), 503 (2016)

[16] Pivovar AM, Holman KT, Ward MD, Chem. Mater., 13(9), 3018 (2001)

[17] Luo XZ, Jia XJ, Deng JH, Zhong JL, Liu HJ, Wang KJ, Zhong DC, J. Am. Ceram. Soc., 135(32), 11684 (2013)

[18] Swift JA, Pivovar AM, Reynolds AM, Ward MD, J. Am. Chem. Soc., 120(24), 5887 (1998)

[19] Holman HT, Pivovar AM, Swift JA, Ward MD, Accounts Chem. Res., 34(2), 107 (2001)

[20] Swift JA, Reynolds AM, Ward MD, Chem. Mater., 10(12), 4159 (1998)

[21] Russell VA, Evans CC, Li WJ, Ward MD, Science, 276(5312), 575 (1997)

[22] Holman KT, Ward MD, Angew. Chem.-Int. Edit., 39(9), 1653 (2000)

[23] Evans CC, Sukarto L, Ward MD, J. Am. Chem. Soc., 121(2), 320 (1999)

[24] Russell VA, Etter MC, Ward MD, J. Am. Chem. Soc., 116(5), 1941 (1994)

[25] Russell VA, Etter MC, Ward MD, Chem. Mater., 6(8), 1206 (1994)

[26] Russell VA, Ward MD, J. Mater. Chem., 7(7), 1123 (1997)

[27] Holman KT, Martin SM, Parker DP, Ward MD, J. Am. Chem. Soc., 123(19), 4421 (2001)

[28] Wu DX, Deng K, Zeng QD, Wang C, J. Phys. Chem. B, 109(47), 22296 (2005)

[29] Lemonnier JF, Floquet S, Kachmar A, Rohmer MM, Benard M, Marrot J, Terazzi E, Piguet C, Cadot E, Dalton Trans., 28, 3043 (2007)

[30] Jiang S, ter Horst JH, Cryst. Growth Des., 11, 256 (2011)

[31] Hou J, Wu S, Li R, Dong W, Gong J, Cryst. Res. Technol., 47(8), 888 (2012)

[32] Segall MD, Lindan PJD, Probert MJ, Pickard CJ, Hasnip PJ, Clark SJ, Payne MC, J. Phys. Condens. Matter, 14(11), 2717 (2002)

[33] Tkatchenko A, Scheffler M, Phys. Rev. Lett., 102(7), 073005 (2009)

[34] Perdew JP, Burke K, Wang Y, Phys. Rev. B, 54(23), 16533 (1996)

[35] Perdew JP, Zunger A, Phys. Rev. B, 23(10), 5048 (1981)

[36] Hamann DR, Schluter M, Chiang C, Phys. Rev. Lett., 43(20), 1494 (1979)

[37] Broyden CG, IMA J. Appl. Math., 6(1), 76 (1970)

[38] Monkhorst HJ, Pack JD, Phys. Rev. B, 13(12), 5188 (1976)

[39] Lee S, Choi A, Kim WS, Myerson AS, Cryst. Growth Des., 11(11), 5019 (2011)