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Nano Research 2019, 12(3): 587-592 https://doi.org/10.1007/s12274-018-2258-7
Research Article | Issue | Published: 06 December 2018

Water transport through subnanopores in the ultimate size limit: Mechanism from molecular dynamics

Show Author's Information Jiyu Xu1,2,§,  Chongqin Zhu3,§,  Yifei Wang1,2,§,  Hui Li1,4,§,  Yongfeng Huang1,2,  Yutian Shen1,2,  Joseph S. Francisco3,  Xiao Cheng Zeng3( ),  Sheng Meng1,2( )
Institute of Physics,Chinese Academy of Sciences,Beijing,100190,China;
School of Physical Sciences,University of Chinese Academy of Sciences,Beijing,100049,China;
Department of Chemistry, University of Nebraska, Lincoln, NE 68588, USA
Beijing Advanced Innovation Center for Soft Matter Science and Engineering,Beijing University of Chemical Technology,Beijing,100029,China;

§ Jiyu Xu, Chongqin Zhu, Yifei Wang, and Hui Li contributed equally to this work.

Keywords:
molecular dynamics, water transport, graphdiyne, subnanopore, desalination
Topics:
Activation energyHydrogen bonds NanofluidicsVan der Waals forces
Cite this article:
Xu J, Zhu C, Wang Y, et al. Water transport through subnanopores in the ultimate size limit: Mechanism from molecular dynamics. Nano Research, 2019, 12(3): 587-592. https://doi.org/10.1007/s12274-018-2258-7
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Abstract Full text Electronic supplementary material About this article

Ab initio and classical molecular dynamics simulations show that water can flow through graphdiyne—an experimentally fabricated graphene-like membrane with highly dense (2.4 × 1018 pores/m2), uniformly ordered, subnanometer pores (incircle diameter 0.57 nm and van der Waals area 0.06 nm2). Water transports through subnanopores via a chemical-reaction-like activated process. The activated water flow can be precisely controlled through fine adjustment of working temperature and pressure. In contrast to a linear dependence on pressure for conventional membranes, here pressure directly modulates the activation energy, leading to a nonlinear water flow as a function of pressure. Consequently, high flux (1.6 L/Day/cm2/MPa) with 100% salt rejection efficiency is achieved at reasonable temperatures and pressures, suggesting graphdiyne can serve as an excellent membrane for water desalination. We further show that to get through subnanopores water molecule must break redundant hydrogen bonds to form a two-hydrogen-bond transient structure. Our study unveils the principles and atomistic mechanism for water transport through pores in ultimate size limit, and offers new insights on water permeation through nanochannels, design of molecule sieving and nanofluidic manipulation.


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Electronic supplementary material
About this article

Water transport through subnanopores in the ultimate size limit: Mechanism from molecular dynamics

Show Author's information Jiyu Xu1,2,§, Chongqin Zhu3,§, Yifei Wang1,2,§, Hui Li1,4,§, Yongfeng Huang1,2, Yutian Shen1,2, Joseph S. Francisco3, Xiao Cheng Zeng3( ), Sheng Meng1,2( )
Institute of Physics,Chinese Academy of Sciences,Beijing,100190,China;
School of Physical Sciences,University of Chinese Academy of Sciences,Beijing,100049,China;
Department of Chemistry, University of Nebraska, Lincoln, NE 68588, USA
Beijing Advanced Innovation Center for Soft Matter Science and Engineering,Beijing University of Chemical Technology,Beijing,100029,China;

§ Jiyu Xu, Chongqin Zhu, Yifei Wang, and Hui Li contributed equally to this work.

Abstract

Ab initio and classical molecular dynamics simulations show that water can flow through graphdiyne—an experimentally fabricated graphene-like membrane with highly dense (2.4 × 1018 pores/m2), uniformly ordered, subnanometer pores (incircle diameter 0.57 nm and van der Waals area 0.06 nm2). Water transports through subnanopores via a chemical-reaction-like activated process. The activated water flow can be precisely controlled through fine adjustment of working temperature and pressure. In contrast to a linear dependence on pressure for conventional membranes, here pressure directly modulates the activation energy, leading to a nonlinear water flow as a function of pressure. Consequently, high flux (1.6 L/Day/cm2/MPa) with 100% salt rejection efficiency is achieved at reasonable temperatures and pressures, suggesting graphdiyne can serve as an excellent membrane for water desalination. We further show that to get through subnanopores water molecule must break redundant hydrogen bonds to form a two-hydrogen-bond transient structure. Our study unveils the principles and atomistic mechanism for water transport through pores in ultimate size limit, and offers new insights on water permeation through nanochannels, design of molecule sieving and nanofluidic manipulation.

Keywords: molecular dynamics, water transport, graphdiyne, subnanopore, desalination

References(60)

1

Buelke, C.; Alshami, A.; Casler, J.; Lewis, J.; Al-Sayaghi, M.; Hickner, M. A. Graphene oxide membranes for enhancing water purification in terrestrial and space-born applications: State of the art. Desalination 2018, 448, 1138lin.
DOI Google Scholar
2

Pendergast, M. M.; Hoek, E. M. V. A review of water treatment membrane nanotechnologies. Energy Environ. Sci. 2011, 4, 1946-1971.
DOI Google Scholar
3

Shannon, M. A.; Bohn, P. W.; Elimelech, M.; Georgiadis, J. G.; Mariñas, B. J.; Mayes, A. M. Science and technology for water purification in the coming decades. Nature 2008, 452, 301-310.
DOI Google Scholar
4

Elimelech, M.; Phillip, W. A. The future of seawater desalination: Energy, technology, and the environment. Science 2011, 333, 712-717.
DOI Google Scholar
5

Post, V. E. A.; Groen, J.; Kooi, H.; Person, M.; Ge, S. M.; Edmunds, W. M. Offshore fresh groundwater reserves as a global phenomenon. Nature 2013, 504, 71-78.
DOI Google Scholar
6

Yang, L. H.; Gordon, V. D.; Trinkle, D. R.; Schmidt, N. W.; Davis, M. A.; DeVries, C.; Som, A.; Cronan, J. E. Jr.; Tew, G. N.; Wong, G. C. L. Mechanism of a prototypical synthetic membrane-active antimicrobial: Efficient hole-punching via interaction with negative intrinsic curvature lipids. Proc. Natl. Acad. Sci. USA 2008, 105, 20595-20600.
DOI Google Scholar
7

García-Fandiño, R.; Sansom, M. S. P. Designing biomimetic pores based on carbon nanotubes. Proc. Natl. Acad. Sci. USA 2012, 109, 6939-6944.
DOI Google Scholar
8

Kosztin, I.; Schulten, K. Fluctuation-driven molecular transport through an asymmetric membrane channel. Phys. Rev. Lett. 2004, 93, 238102.
DOI Google Scholar
9

Tunuguntla, R. H.; Henley, R. Y.; Yao, Y. C.; Pham, T. A.; Wanunu, M.; Noy, A. Enhanced water permeability and tunable ion selectivity in subnanometer carbon nanotube porins. Science 2017, 357, 792-796.
DOI Google Scholar
10

Murata, K.; Mitsuoka, K.; Hirai, T.; Walz, T.; Agre, P.; Heymann, J. B.; Engel, A.; Fujiyoshi, Y. Structural determinants of water permeation through aquaporin-1. Nature 2000, 407, 599-605.
DOI Google Scholar
11

Tajkhorshid, E.; Nollert, P.; Jensen, M. Ø.; Miercke, L. J. W.; O'connell, J.; Stroud, R. M.; Schulten, K. Control of the selectivity of the aquaporin water channel family by global orientational tuning. Science 2002, 296, 525-530.
DOI Google Scholar
12

Horner, A.; Zocher, F.; Preiner, J.; Ollinger, N.; Siligan, C.; Akimov, S. A.; Pohl, P. The mobility of single-file water molecules is governed by the number of H-bonds they may form with channel-lining residues. Sci. Adv. 2015, 1, e1400083.
DOI Google Scholar
13

Kidambi, P. R.; Boutilier, M. S. H.; Wang, L. D.; Jang, D.; Kim, J.; Karnik, R. Selective nanoscale mass transport across atomically thin single crystalline graphene membranes. Adv. Mater. 2017, 29, 1605896.
DOI Google Scholar
14

Zhu, C. Q.; Li, H.; Meng, S. Transport behavior of water molecules through two-dimensional nanopores. J. Chem. Phys. 2014, 141, 18C528.
DOI Google Scholar
15

Suk, M. E.; Aluru, N. R. Water transport through ultrathin graphene. J. Phys. Chem. Lett. 2010, 1, 1590-1594.
DOI Google Scholar
16

Cohen-Tanugi, D.; Grossman, J. C. Water desalination across nanoporous graphene. Nano Lett. 2012, 12, 3602-3608.
DOI Google Scholar
17

Zhu, C. Q.; Li, H.; Zeng, X. C.; Wang, E. G.; Meng, S. Quantized water transport: Ideal desalination through graphyne-4 membrane. Sci. Rep. 2013, 3, 3163.
DOI Google Scholar
18

Kou, J. L.; Zhou, X. Y.; Lu, H. J.; Wu, F. M.; Fan, J. T. Graphyne as the membrane for water desalination. Nanoscale 2014, 6, 1865-1870.
DOI Google Scholar
19

Lin, S. C.; Buehler, M. J. Mechanics and molecular filtration performance of graphyne nanoweb membranes for selective water purification. Nanoscale 2013, 5, 11801-11807.
DOI Google Scholar
20

Holt, J. K.; Park, H. G.; Wang, Y. M.; Stadermann, M.; Artyukhin, A. B.; Grigoropoulos, C. P.; Noy, A.; Bakajin, O. Fast mass transport through sub-2-nanometer carbon nanotubes. Science 2006, 312, 1034-1037.
DOI Google Scholar
21

Thomas, J. A.; McGaughey, A. J. H. Water flow in carbon nanotubes: Transition to subcontinuum transport. Phys. Rev. Lett. 2009, 102, 184502.
DOI Google Scholar
22

Qin, X. C.; Yuan, Q. Z.; Zhao, Y. P.; Xie, S. B.; Liu, Z. F. Measurement of the rate of water translocation through carbon nanotubes. Nano Lett. 2011, 11, 2173-2177.
DOI Google Scholar
23

Joseph, S.; Aluru, N. Why are carbon nanotubes fast transporters of water? Nano Lett. 2008, 8, 452-458.
DOI Google Scholar
24

Striolo, A. The mechanism of water diffusion in narrow carbon nanotubes. Nano Lett. 2006, 6, 633-639.
DOI Google Scholar
25

Wang, Y. J.; Li, L. B.; Wei, Y. Y.; Xue, J.; Chen, H.; Ding, L.; Caro, J.; Wang, H. H. Water transport with ultralow friction through partially exfoliated g-C3N4 nanosheet membranes with self-supporting spacers. Angew. Chem. , Int. Ed. 2017, 56, 8974-8980.
DOI Google Scholar
26

Xue, M. M.; Qiu, H.; Guo, W. L. Exceptionally fast water desalination at complete salt rejection by pristine graphyne monolayers. Nanotechnology 2013, 24, 505720.
DOI Google Scholar
27

Surwade, S. P.; Smirnov, S. N.; Vlassiouk, I. V.; Unocic, R. R.; Veith, G. M.; Dai, S.; Mahurin, S. M. Water desalination using nanoporous single-layer graphene. Nat. Nanotechnol. 2015, 10, 459-464.
DOI Google Scholar
28

Liu, J.; Shi, G. S.; Guo, P.; Yang, J. R.; Fang, H. P. Blockage of water flow in carbon nanotubes by ions due to interactions between cations and aromatic rings. Phys. Rev. Lett. 2015, 115, 164502.
DOI Google Scholar
29

Han, J.; Fu, J. P.; Schoch, R. B. Molecular sieving using nanofilters: Past, present and future. Lab Chip 2008, 8, 23-33.
DOI Google Scholar
30

Wan, R. Z.; Li, J. Y.; Lu, H. J.; Fang, H. P. Controllable water channel gating of nanometer dimensions. J. Am. Chem. Soc. 2005, 127, 7166-7170.
DOI Google Scholar
31

Li, J. Y.; Gong, X. J.; Lu, H. J.; Li, D.; Fang, H. P.; Zhou, R. H. Electrostatic gating of a nanometer water channel. Proc. Natl. Acad. Sci. USA 2007, 104, 3687-3692.
DOI Google Scholar
32

Gong, X. J.; Li, J. Y.; Zhang, H.; Wan, R. Z.; Lu, H. J.; Wang, S.; Fang, H. P. Enhancement of water permeation across a nanochannel by the structure outside the channel. Phys. Rev. Lett. 2008, 101, 257801.
DOI Google Scholar
33

Li, Y. J.; Xu, L.; Liu, H. B.; Li, Y. L. Graphdiyne and graphyne: From theoretical predictions to practical construction. Chem. Soc. Rev. 2014, 43, 2572-2586.
DOI Google Scholar
34

Zhang, S. L.; Liu, H. B.; Huang, C. S.; Cui, G. L.; Li, Y. L. Bulk graphdiyne powder applied for highly efficient lithium storage. Chem. Commun. 2015, 51, 1834-1837.
DOI Google Scholar
35

Zhang, S. L.; Du, H. P.; He, J. J.; Huang, C. S.; Liu, H. B.; Cui, G. L.; Li, Y. L. Nitrogen-doped graphdiyne applied for lithium-ion storage. ACS Appl. Mater. Interfaces 2016, 8, 8467-8473.
DOI Google Scholar
36

Wang, S.; Yi, L. X.; Halpert, J. E.; Lai, X.Y.; Liu, Y. Y.; Cao, H. B.; Yu, R. B.; Wang, D.; Li, Y. L. A novel and highly efficient photocatalyst based on P25-graphdiyne nanocomposite. Small 2012, 8, 265-271.
DOI Google Scholar
37

Cranford, S. W.; Buehler, M. J. Selective hydrogen purification through graphdiyne under ambient temperature and pressure. Nanoscale 2012, 4, 4587-4593.
DOI Google Scholar
38

Li, G. X.; Li, Y. L.; Liu, H. B.; Guo, Y. B.; Li, Y. J.; Zhu, D. B. Architecture of graphdiyne nanoscale films. Chem. Commun. 2010, 46, 3256-3258.
DOI Google Scholar
39

Qian, X. M.; Ning, Z.Y.; Li, Y. L.; Liu, H. B.; Ouyang, C. B.; Chen, Q.; Li, Y. J. Construction of graphdiyne nanowires with high-conductivity and mobility. Dalton Trans. 2012, 41, 730-733.
DOI Google Scholar
40

Matsuoka, R.; Sakamoto, R.; Hoshiko, K.; Sasaki, S.; Masunaga, H.; Nagashio, K.; Nishihara, H. Crystalline graphdiyne nanosheets produced at a gas/liquid or liquid/liquid interface. J. Am. Chem. Soc. 2017, 139, 3145-3152.
DOI Google Scholar
41

Gao, X.; Li, J.; Du, R.; Zhou, J. Y.; Huang, M. Y.; Liu, R.; Li, J.; Xie, Z. Q.; Wu, L. Z.; Liu, Z. F. et al. Direct synthesis of graphdiyne nanowalls on arbitrary substrates and its application for photoelectrochemical water splitting cell. Adv. Mater. 2017, 29, 1605308.
DOI Google Scholar
42

Bartolomei, M.; Carmona-Novillo, E.; Hernández, M. I.; Campos-Martínez, J.; Pirani, F.; Giorgi, G.; Yamashita, K. Penetration barrier of water through graphynes' pores: First-principles predictions and force field optimization. J. Phys. Chem. Lett. 2014, 5, 751-755.
DOI Google Scholar
43

Yuan, Z.; Govind Rajan, A.; Misra, R. P.; Drahushuk, L. W.; Agrawal, K. V.; Strano, M. S.; Blankschtein, D. Mechanism and prediction of gas permeation through sub-nanometer graphene pores: Comparison of theory and simulation. ACS Nano 2017, 118, 7974-7987.
DOI Google Scholar
44

VandeVondele, J.; Krack, M.; Mohamed, F.; Parrinello, M.; Chassaing, T.; Hutter, J. Quickstep: Fast and accurate density functional calculations using a mixed gaussian and plane waves approach. Comput. Phys. Commun. 2005, 167, 103-128.
DOI Google Scholar
45

Becke, A. D. Density-functional exchange-energy approximation with correct asymptotic behavior. Phys. Rev. A 1988, 38, 3098-3100.
DOI Google Scholar
46

Lee, C.; Yang, W.T.; Parr, R. G. Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. Phys. Rev. B 1988, 37, 785-789.
DOI Google Scholar
47

Goedecker, S.; Teter, M.; Hutter, J. Separable dual-space Gaussian pseudopotentials. Phys. Rev. B 1996, 54, 1703-1710.
DOI Google Scholar
48

Hartwigsen, C.; Gœdecker, S.; Hutter, J. Relativistic separable dual-space Gaussian pseudopotentials from H to Rn. Phys. Rev. B 1998, 58, 3641-3662.
DOI Google Scholar
49

Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 2010, 132, 154104.
DOI Google Scholar
50

Yoo, S.; Xantheas, S. S. Communication: The effect of dispersion corrections on the melting temperature of liquid water. J. Chem. Phys. 2011, 134, 121105.
DOI Google Scholar
51

Pronk, S.; Páll, S.; Schulz, R.; Larsson, P.; Bjelkmar, P.; Apostolov, R.; Shirts, M. R.; Smith, J. C.; Kasson, P. M.; van der Spoel, D. et al. GROMACS 4.5: A high-throughput and highly parallel open source molecular simulation toolkit. Bioinformatics 2013, 29, 845-854.
DOI Google Scholar
52

Berendsen, H. J. C.; Grigera, J. R.; Straatsma, T. P. The missing term in effective pair potentials. J. Phys. Chem. 1987, 91, 6269-6271.
DOI Google Scholar
53

Darden, T.; York, D.; Pedersen, L. Particle mesh ewald: An N⋅log(N) method for ewald sums in large systems. J. Chem. Phys. 1993, 98, 10089-10092.
DOI Google Scholar
54

Berendsen, H. J. C.; Postma, J. P. M.; van Gunsteren, W. F.; DiNola, A.; Haak, J. R. Molecular dynamics with coupling to an external bath. J. Chem. Phys. 1984, 81, 3684-3690.
DOI Google Scholar
55

Sanz, E.; Vega, C.; Abascal, J. L. F.; MacDowell, L. G. Phase diagram of water from computer simulation. Phys. Rev. Lett. 2004, 92, 255701.
DOI Google Scholar
56

Li, M. Y.; Zhang, Y. M.; Jiang, Y. L.; Zhang, Y.; Wang, Y. M.; Zhou, H. M. Mechanical properties of γ-graphyne nanotubes. RSC Adv. 2018, 8, 15659-15666.
DOI Google Scholar
57

Ajori, S.; Ansari, R.; Mirnezhad, M. Mechanical properties of defective γ-graphyne using molecular dynamics simulations. Mater. Sci. Eng. : A 2013, 561, 34-39.
DOI Google Scholar
58

Cohen-Tanugi, D.; Grossman, J. C. Mechanical strength of nanoporous graphene as a desalination membrane. Nano Lett. 2014, 14, 6171-6178.
DOI Google Scholar
59

Kopec, W.; Köpfer, D. A.; Vickery, O. N.; Bondarenko, A. S.; Jansen, T. L. C.; de Groot, B. L.; Zachariae, U. Direct knock-on of desolvated ions governs strict ion selectivity in K+ channels. Nat. Chem. 2018, 10, 813-820.
DOI Google Scholar
60

Zhang, H. C.; Hou, J.; Hu, Y. X.; Wang, P. Y.; Ou, R. W.; Jiang, L.; Liu, J. Z.; Freeman, B. D.; Hill, A. J.; Wang, H. T. Ultrafast selective transport of alkali metal ions in metal organic frameworks with subnanometer pores. Sci. Adv. 2018, 4, eaaq0066.
DOI Google Scholar
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Publication history
Copyright
Acknowledgements

Publication history

Received: 12 September 2018
Revised: 02 November 2018
Accepted: 26 November 2018
Published: 06 December 2018
Issue date: March 2019

Copyright

© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Acknowledgements

Acknowledgements

We acknowledge financial support from Ministry of Science and Technology (No. 2016YFA0300902), the National Natural Science Foundation of China (Nos. 11474328 and 11290164) and Chinese Academy of Sciences (No. XDB070301).

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