RESEARCH ARTICLE

Mechanism of ethanol/water reverse separation through a functional graphene membrane: a molecular simulation investigation

  • Quan Liu 1,2 ,
  • Xian Wang 1 ,
  • Yanan Guo , 2 ,
  • Gongping Liu , 2 ,
  • Kai-Ge Zhou 3
Expand
  • 1. School of Chemical Engineering, Analytical and Testing Center, Anhui University of Science and Technology, Huainan 232001, China
  • 2. State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, China
  • 3. Haihe Laboratory of Sustainable Chemical Transformations, Tianjin 300192, China
guoyn@njtech.edu.cn
gpliu@njtech.edu.cn

Received date: 13 Jul 2022

Accepted date: 27 Aug 2022

Published date: 15 Mar 2023

Copyright

2022 Higher Education Press

Abstract

Reverse-selective membranes have attracted considerable interest for bioethanol production. However, to date, the reverse-separation performance of ethanol/water is poor and the separation mechanism is unclear. Graphene-based membranes with tunable apertures and functional groups have shown substantial potential for use in molecular separation. Using molecular dynamics simulations, for the first time, we reveal two-way selectivity in ethanol/water separation through functional graphene membranes. Pristine graphene (PG) exhibits reverse-selective behavior with higher ethanol fluxes than water, resulting from the preferential adsorption for ethanol. Color flow mappings show that this ethanol-permselective process is initiated by the presence of ethanol-enriched and water-barren pores; this has not been reported in previous studies. In contrast, water molecules are preferred for hydroxylated graphene membranes because of the synergistic effects of molecular sieving and functional-group attraction. A simulation of the operando condition shows that the PG membrane with an aperture size of 3.8 Å achieves good separation performance, with an ethanol/water separation factor of 34 and a flux value of 69.3 kg∙m‒2∙h‒1∙bar‒1. This study provides new insights into the reverse-selective mechanism of porous graphene membranes and a new avenue for efficient biofuel production.

Cite this article

Quan Liu , Xian Wang , Yanan Guo , Gongping Liu , Kai-Ge Zhou . Mechanism of ethanol/water reverse separation through a functional graphene membrane: a molecular simulation investigation[J]. Frontiers of Chemical Science and Engineering, 2023 , 17(3) : 347 -357 . DOI: 10.1007/s11705-022-2246-z

Acknowledgments

This work was financially supported by the University Natural Science Research Project of Anhui Province (Grant No. KJ2020A0286), the Anhui Provincial Natural Science Foundation (Grant No. 2108085QB50), and the Natural Science Foundation of Jiangsu Province (Grant No. BK20220002). The numerical calculations in this paper have been done on the supercomputing system in the Supercomputing Center of University of Science and Technology of China.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://dx.doi.org/10.1007/s11705-022-2246-z and is accessible for authorized users.
1
Merkel T C, Freeman B D, Spontak R J, He Z, Pinnau I, Meakin P, Hill A J. Ultrapermeable, reverse-selective nanocomposite membranes. Science, 2002, 296(5567): 519–522

DOI

2
Khakpay A, Scovazzo P. Reverse-selective behavior of room temperature ionic liquid based membranes for natural gas processing. Journal of Membrane Science, 2018, 545: 204–212

DOI

3
Yu S, Qin B, Yang F, Xie M, Xue L, Zhao Z, Wang K. Unlocking the limits of diffusion and adsorption of metal-crosslinked reduced graphene oxide membranes for gas separation. Applied Surface Science, 2022, 586: 152868

DOI

4
Lau C H, Li P, Li F, Chung T S, Paul D R. Reverse-selective polymeric membranes for gas separations. Progress in Polymer Science, 2013, 38(5): 740–766

DOI

5
Mushardt H, Kramer V, Hülagü D, Brinkmann T, Kraume M. Development of solubility selective mixed matrix membranes for gas separation. Chemie ingenieur technik, 2014, 86(1–2): 83–91

DOI

6
Ahmed I, Pa N F C, Nawawi M G M, Rahman W A W A. Modified polydimethylsiloxane/polystyrene blended IPN pervaporation membrane for ethanol/water separation. Journal of Applied Polymer Science, 2011, 122(4): 2666–2679

DOI

7
Cheng X Q, Konstas K, Doherty C M, Wood C D, Mulet X, Xie Z, Ng D, Hill M R, Lau C H, Shao L. Organic microporous nanofillers with unique alcohol affinity for superior ethanol recovery toward sustainable biofuels. ChemSusChem, 2017, 10(9): 1887–1891

DOI

8
Sanaeepur H, Ebadi Amooghin A, Bandehali S, Moghadassi A, Matsuura T, van der Bruggen B. Polyimides in membrane gas separation: monomer’s molecular design and structural engineering. Progress in Polymer Science, 2019, 91: 80–125

DOI

9
Li Y, Chung T S, Cao C, Kulprathipanja S. The effects of polymer chain rigidification, zeolite pore size and pore blockage on polyethersulfone (PES)-zeolite a mixed matrix membranes. Journal of Membrane Science, 2005, 260(1): 45–55

DOI

10
Mao H, Zhen H G, Ahmad A, Zhang A S, Zhao Z P. In situ fabrication of MOF nanoparticles in PDMS membrane via interfacial synthesis for enhanced ethanol permselective pervaporation. Journal of Membrane Science, 2019, 573: 344–358

DOI

11
Pan Y, Zhu T, Xia Q, Yu X, Wang Y. Constructing superhydrophobic ZIF-8 layer with bud-like surface morphology on PDMS composite membrane for highly efficient ethanol/water separation. Journal of Environmental Chemical Engineering, 2021, 9(1): 104977

DOI

12
Pan Y, Yu X. Preparation of zeolitic imidazolate framework-91 and its modeling for pervaporation separation of water/ethanol mixtures. Separation and Purification Technology, 2020, 237: 116330

DOI

13
He X, Wang T, Huang J, Chen J, Li J. Fabrication and characterization of superhydrophobic PDMS composite membranes for efficient ethanol recovery via pervaporation. Separation and Purification Technology, 2020, 241: 116675

DOI

14
Zhu T, Xu S, Yu F, Yu X, Wang Y. ZIF-8@GO composites incorporated polydimethylsiloxane membrane with prominent separation performance for ethanol recovery. Journal of Membrane Science, 2020, 598: 117681

DOI

15
Zhu T, Yu X, Yi M, Wang Y. Facile covalent crosslinking of zeolitic imidazolate framework/polydimethylsiloxane mixed matrix membrane for enhanced ethanol/water separation performance. ACS Sustainable Chemistry & Engineering, 2020, 8(33): 12664–12676

DOI

16
Kang J, Choi Y, Kim J P, Kim J H, Kim J Y, Kwon O, Kim D I, Kim D W. Thermally-induced pore size tuning of multilayer nanoporous graphene for organic solvent nanofiltration. Journal of Membrane Science, 2021, 637: 119620

DOI

17
Liu Y, Bai Z, Lin G, Wang L, Xu X, He L, Liu X. Covalent cross-linking mediated TA-APTES NPs to construct a high-efficiency GO composite membrane for dye/salt separation. Applied Surface Science, 2022, 584: 152595

DOI

18
Liu G, Jin W, Xu N. Graphene-based membranes. Chemical Society Reviews, 2015, 44(15): 5016–5030

DOI

19
Moreno C, Vilas-Varela M, Kretz B, Garcia-Lekue A, Costache M V, Paradinas M, Panighel M, Ceballos G, Valenzuela S O, Peña D, Mugarza A. Bottom-up synthesis of multifunctional nanoporous graphene. Science, 2018, 360(6385): 199–203

DOI

20
Jang J, Nam Y T, Kim D, Kim Y J, Kim D W, Jung H T. Turbostratic nanoporous carbon sheet membrane for ultrafast and selective nanofiltration in viscous green solvents. Journal of Materials Chemistry A: Materials for Energy and Sustainability, 2020, 8(17): 8292–8299

DOI

21
Gravelle S, Yoshida H, Joly L, Ybert C, Bocquet L. Carbon membranes for efficient water−ethanol separation. Journal of Chemical Physics, 2016, 145(12): 124708

DOI

22
Kommu A, Singh J K. Separation of ethanol and water using graphene and hexagonal boron nitride slit pores: a molecular dynamics study. Journal of Physical Chemistry C, 2017, 121(14): 7867–7880

DOI

23
Liu Q, Chen M, Mao Y, Liu G. Theoretical study on Janus graphene oxide membrane for water transport. Frontiers of Chemical Science and Engineering, 2021, 15(4): 913–921

DOI

24
Liu Q, Gupta K M, Xu Q, Liu G, Jin W. Gas permeation through double-layer graphene oxide membranes: the role of interlayer distance and pore offset. Separation and Purification Technology, 2019, 209: 419–425

DOI

25
Liu Q, Wu Y, Wang X, Liu G, Zhu Y, Tu Y, Lu X, Jin W. Molecular dynamics simulation of water−ethanol separation through monolayer graphene oxide membranes: significant role of O/C ratio and pore size. Separation and Purification Technology, 2019, 224: 219–226

DOI

26
Cohen-Tanugi D, Grossman J C. Water desalination across nanoporous graphene. Nano Letters, 2012, 12(7): 3602–3608

DOI

27
Li H, Lv W, Xu J, Hu J, Liu H. Can flexible framework fillers keep breathing in mixed matrix membranes to enhance separation performance?. Journal of Membrane Science, 2020, 614: 118426

DOI

28
Gupta K M, Liu J, Jiang J. A molecular simulation protocol for membrane pervaporation. Journal of Membrane Science, 2019, 572: 676–682

DOI

29
Liu Q, Zhu H, Liu G, Jin W. Efficient separation of (C1–C2) alcohol solutions by graphyne membranes: a molecular simulation study. Journal of Membrane Science, 2022, 644: 120139

DOI

30
Jorgensen W L, Chandrasekhar J, Madura J D, Impey R W, Klein M L. Comparison of simple potential functions for simulating liquid water. Journal of Chemical Physics, 1983, 79(2): 926–935

DOI

31
Jorgensen W L, Maxwell D S, Tirado-Rives J. Development and testing of the OPLS all-atom force field on conformational energetics and properties of organic liquids. Journal of the American Chemical Society, 1996, 118(45): 11225–11236

DOI

32
Wennberg C L, Murtola T, Páll S, Abraham M J, Hess B, Lindahl E. Direct-space corrections enable fast and accurate Lorentz–Berthelot combination rule Lennard–Jones lattice summation. Journal of Chemical Theory and Computation, 2015, 11(12): 5737–5746

DOI

33
van der Spoel D, Lindahl E, Hess B, Groenhof G, Mark A E, Berendsen H J. GROMACS: fast, flexible, and free. Journal of Computational Chemistry, 2005, 26(16): 1701–1718

DOI

34
Humphrey W, Dalke A, Schulten K. VMD: visual molecular dynamics. Journal of Molecular Graphics, 1996, 14(1): 33–38

DOI

35
Wei W, Liu J, Jiang J. Atomistic simulation study of polyarylate/zeolitic-imidazolate framework mixed-matrix membranes for water desalination. ACS Applied Nano Materials, 2020, 3(10): 10022–10031

DOI

36
Cohen-Tanugi D, Grossman J C. Water permeability of nanoporous graphene at realistic pressures for reverse osmosis desalination. Journal of Chemical Physics, 2014, 141(7): 074704

DOI

37
Liu J, Wei W, Jiang J. A highly rigid and conjugated microporous polymer membrane for solvent permeation and biofuel purification: a molecular simulation study. ACS Sustainable Chemistry & Engineering, 2020, 8(7): 2892–2900

DOI

38
Guo Y, Xie W, Li H, Li J, Hu J, Liu H. Construction of hydrophobic channels on Cu(I)-MOF surface to improve selective adsorption desulfurization performance in presence of water. Separation and Purification Technology, 2022, 285: 120287

DOI

39
An S, Lu C, Xu Q, Lian C, Peng C, Hu J, Zhuang X, Liu H. Constructing catalytic crown ether-based covalent organic frameworks for electroreduction of CO2. ACS Energy Letters, 2021, 6(10): 3496–3502

DOI

40
Cohen-Tanugi D, Lin L C, Grossman J C. Multilayer nanoporous graphene membranes for water desalination. Nano Letters, 2016, 16(2): 1027–1033

DOI

41
Zhang L, Wu G, Jiang J. Adsorption and diffusion of CO2 and CH4 in zeolitic imidazolate framework-8: effect of structural flexibility. Journal of Physical Chemistry C, 2014, 118(17): 8788–8794

DOI

42
Nakagawa K, Araya S, Ushio K, Kunimatsu M, Yoshioka T, Shintani T, Kamio E, Tung K L, Matsuyama H. Controlling interlayer spacing and organic solvent permeation in laminar graphene oxide membranes modified with crosslinker. Separation and Purification Technology, 2021, 276: 119279

DOI

43
Wang J, Zhang P, Liang B, Liu Y, Xu T, Wang L, Cao B, Pan K. Graphene oxide as an effective barrier on a porous nanofibrous membrane for water treatment. ACS Applied Materials & Interfaces, 2016, 8(9): 6211–6218

DOI

Outlines

/