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Mini Review
Anomalies of Ionic/Molecular Transport
in Nano- and Sub-Nano Confinement
Miao Wang, Yaqi Hou, Lejian Yu, and Xu Hou
Nano Lett., Just Accepted Manuscript • DOI: 10.1021/acs.nanolett.0c02999 • Publication Date (Web): 27 Aug 2020
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Anomalies of Ionic/Molecular Transport in Nano-
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10 and Sub-Nano Confinement
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Miao Wang, † Yaqi Hou, ‡ Lejian Yu, ‡ Xu Hou†, ‡, §, ⊥, *
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16 †Research
17 Institute for Biomimetics and Soft Matter, Fujian Provincial Key Laboratory for Soft
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19 Functional Materials Research, Jiujiang Research Institute, College of Physical Science and
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21 Technology, Xiamen University, Xiamen 361005, China
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23 ‡State
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Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and
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26 Chemical Engineering, Xiamen University, Xiamen 361005, China
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28 §Collaborative Innovation Center of Chemistry for Energy Materials, Xiamen University,
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Xiamen 361005, China
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⊥Tan Kah Kee Innovation Laboratory, Xiamen 361102, Fujian, China
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37 KEYWORDS: Nano- and sub-nano confinement, Ionic/Molecular transport, Static and
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39 dynamic structures, Nanofluidics, Anomalous behaviors
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43 ABSTRACT: Understanding and exploring the transport behaviors of ions and molecules in
44 the nano- and sub-nano confinement has a great meaning to the fields of nanofluidics and basic
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transport physics. With the rapid progress on nanofabrication technology and effective
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47 characterization protocols, more and more anomalous transport behaviors have been repeatedly
48 observed that the ions/molecules inside small confinement can behave dramatically different
49 from bulk systems and present new mechanisms. In this Mini Review, we summarize the recent
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51 advances in the anomalous ionic/molecular transport behaviors in nano- and sub-nano
52 confinement. Our discussion includes the ionic/molecular transport of various confinement
53 with different surface properties, static structures, and dynamic structures. Furthermore, we
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provide a brief overview of the latest applications of nanofluidics in membrane separation and
56 energy conversion.
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4 Ions and molecules are the building blocks of most matters, and the researches exploring their
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7 behaviors are aiming to provide more insights into the bases of physics, chemistry, material
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9 science, and even life. Owing much to the recent developments in nanofabrication technologies,
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12 the capabilities of investigating ions and molecules in nano- and sub-nanometer confinement
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with different direct characterization measures are enhanced, and a wide range of applications
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17 are enabled, such as substance detection,1-6 biosensors,7-10 ionic diode,11, 12 logic circuits,13 drug
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20 release,14 nanofluidics,15 catalyzes,16 and energy conversion17, 18 and harvesting,19 etc. In a
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22 confinement sizing between 1 and 100 nm, the surfaces and interfaces can exert paramount
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25 influences on the transport and interactive behaviors of ions and molecules compared to the
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confinement with microscales or bigger. This is due to the increased specific surface area that
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30 amplifies the interaction of the interfaces, thus aggravating the van der Waals forces and
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33 electrostatic forces. The exaggerated repulsive and attractive forces in nanoscales can induce
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35 rather different ionic/molecular behaviors from bulk systems, which are referred to as
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38 anomalous behaviors. If the confinement was downsized to sub-nano confinement (<1 nm), or
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even monatomic spaces, the short-range steric forces become stronger for ions/molecules.
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43 Under the interactions of short-range steric/hydration forces, the classical mechanics, and
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46 thermodynamic equations, such as the Navier-Stokes, Kelvin, and Hertz-Knudsen are
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48 challenged.20
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51 Most recently, the anomalous ionic/molecular transport behaviors have been observed in
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nano- and sub-nano confinement, which are all unexpected and distinctive from those in bulk
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56 systems. A counter-intuitive example finds that the diffusive transport of neutral molecules in
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59 nano-confinement (<5 nm) matches that of charged molecules, as though the former carry an
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4 effective charge.21 Other emerging anomalies have been discovered in succession, such as
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7 massive radius-dependent water flow slippage,22 ultrafast water evaporation,23 extreme phase
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9 transition,24 distinct diffusions of electrically neutral molecules,25 quantized and strongly
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12 nonlinear ionic transport,26, 27 ultrafast ion sieving,28 and increased ion mobility,29 etc.
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Lately, the anomalous transport behaviors of nanoscale confined fluids, including fluid
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17 transport, fluid evaporation and condensation, have been well discussed in detail by Zhong et
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20 al.,20 which will not be further discussed in this review. Here, we will specifically focus on the
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22 study of anomalous transport behaviors of ions and molecules within nano- and sub-nano
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25 confinement. This review is organized into four sections. The first section introduces the recent
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advances in the anomalies of ionic/molecular transport within nano- and sub-nano
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30 confinement. In the second section, we will discuss them from surface properties, static
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33 structure, and dynamic structure, as illustrated in Figure 1. In the third section, we will further
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35 present the latest applications in nanofluidics. In the last section, we will give an outlook for
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38 future challenges and opportunities to drive the development of this field.
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58 Figure 1. The schematic of anomalous transport behaviors in nano and sub-nano confinement derived
59 from surface properties, static structure, and dynamic structure. The d and k represent the inner diameter
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and curvature of a nanochannel/nanotube, respectively. The inset with a dotted rectangle in the upper
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5 left corner shows the inner surface slippage flow of water molecules in a carbon nanotube, which is
6 designed according to Ref. 22. The inset with a dotted oval in the upper right corner shows a unipolar
7 solution of counter ions created inside a silica nanotube with an inner diameter (d) smaller than the
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9 Debye length for the ions, which is designed according to Ref. 45. The inset with a dotted oval in the
10 lower left corner shows ionic transport through geometric confined angstrom-scale graphite 2D spacing
11 channel, which is designed according to Ref. 51. The inset with a dotted rectangle in the lower right
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corner shows dynamic ionic rectification in asymmetrically curved carbon nanochannels, which is
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14 designed according to Ref. 66. The middle fan-shaped region shows the different distribution of
15 hydrated cation in a range from nano to sub-nano confinement, which is designed with inspiration from
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Ref. 56.
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20 Surface Properties. The ionic/molecular transport behavior is affected by the interactions
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22 between the transport components and the surface of confinement. For various transport ions
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25 and molecules, the interactions are closely related to the instincts or acquired physical and
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chemical properties of the surface, which can be further regulated by surface functionalization.
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30 Consequently, the surface properties appear to be of essence in understanding the
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33 ionic/molecular transport behavior in confinement. Especially, the change of sliding solid-
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35 liquid interface, the topography and hydrophilicity, and the surface charges are primary points
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38 to impact those properties of the confinement surface, which can be used to analyze and discuss
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various anomalous transport behaviors in nano and sub-nano confinement, such as ultra-fast
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43 flows of water,22, 30-32 non-linear transport mechanisms,26, 33 asymmetric ion transport with high
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46 selectivity34, unexpected diffusion and aggregation behavior,25, 35 etc. The functionalization
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48 approaches of surface including the responsive molecular modification strategy,36, 37 the
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51 symmetric and asymmetric strategies38, 39 and synergic design of asymmetric structures and
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asymmetric modifications34, which can endow the confinement of picturesque transport
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56 behaviors, such as unidirectional selective ion pumping, and high-efficiently responsive
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59 switch. The ionic/molecular transport in various functionalized nano- and sub-nano
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4 confinement have been described in detail by Ding et al.,40 Zhang et al.,36 Acar,39 and will not
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7 be considered in this review. This section is mainly concerned with the role of surface
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9 properties from surface slippage, surface wettability, and surface charge.
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12 For surface slippage, superfast water transport has been discovered in graphitic
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nanoconduits (carbon nanotubes (CNTs) and graphene nanochannels)30, 31 due to the hexagonal
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17 arrangement of hybridized carbon atoms forming a nearly frictionless slip surface. Majumder
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20 et al. have found that the observed flow velocity through an array of aligned carbon nanotubes
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22 is four to five orders of magnitude faster than that would be predicted from conventional fluid-
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25 flow theory. The observed flow velocity is 43.9 cm/s at 1 bar whereas the expected flow
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velocity is 0.00057 cm/s at 1 bar with the initial permeability of 1.01 cm3/cm2 min bar in carbon
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30 nanotube array.30 They attributed this high fluid velocity to the almost frictionless interface at
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33 the CNTs wall. Holt et al. also have measured fast water flow through sub-2 nm CNTs
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35 exceeding values calculated from continuum hydrodynamics models by more than three orders
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38 of magnitude.31 Furthermore, Secchi et al. have discovered extraordinarily large radius-
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dependent surface slippage in CNT by constructing a nano-jet experimental setup to study the
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43 flow property of the jet hydrodynamics in an individual CNT with extremely high sensitivity.
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46 They thought that the CNT has nearly frictionless liquid-solid interfaces resulting in the sliding
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48 surface that could generate an ultrahigh massive flow slippage to water (the inset with a dotted
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51 rectangle in the upper left corner of Figure 1).22 Similarly, enhanced water permeability had
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been found in a sub-nanometer carbon nanotube porins (CNTPs). The water could be confined
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56 down to a single-file chain and the intermolecular hydrogen bonds were rearranged to enter the
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59 CNT (Figure 2a). 32
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4 Although flow enhancement can be established by graphite nano conduits, how to regulate
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7 the water transport behaviors at the nano scale is still a challenge. Further understanding of
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9 water flow enhancement and surface slippage as a function of confinement and surface
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12 properties could guide in rational design of functional membranes for energy and
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environmental applications, such as nanofiltration and lab-on-a-chip. Therefore, accurate
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17 measurement of slip length in single graphitic conduits seems urgently needed.41, 42 Xie et al.
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20 have accurately measured the slip length in a single graphene nanochannel based on capillary
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22 flow mechanisms by a hybrid design of nanochannels.43 They found that the slip length of
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25 graphene nanochannels is about 16 nm, and there is a wide distribution range from 0-200 nm,
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which is independent of the height of the channel and mainly depends on the slip effect of the
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30 substrate. All these works have promoted the understanding of water transport in
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33 carbon/graphene nanoconfinement and substantiated the significant influence of surface
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35 slippage on ions/water molecule transport inside, which can indicate the vital application
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38 prospects in the separation process, energy conversion, and fabrication of precise fluidic micro-
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devices, etc.
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43 For surface wettability, changing the surface topography and hydrophilicity can have
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46 major effects on the confined ionic/molecular transport thus contributing to in-depth
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48 understanding of many challenging problems in interface chemistry and fluidic mechanisms.
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51 The ionic transport mechanism varies in a hydrophilic nanochannel (size of 2 nm). The proton
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mobility is found to be four times higher than the bulk value at low concentrations. The
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56 researchers speculated that the overlapped hydration layers formed by hydrogen-bonding
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59 network in the hydrophilic surface of the nanochannel may be the possible reason causing it.29
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4 Wu et al. have studied the effect of surface wettability on water transport in nanoconfinement.44
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7 They found through experiments that, compared to the bulk water, the water flux in hydrophilic
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9 nanochannels was reduced by an order of magnitude because of multilayer sticking, while the
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12 water flux in hydrophobic nanochannels will be increased by seven orders of magnitude due to
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the weak interface interaction between confinement and water. The stronger the interaction of
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17 the interface behaves, the worse the motion behavior of confined water molecules is. Therefore,
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20 the strong hydrophobicity of the confinement surface can enhance the confined water flux.
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22 Besides, enhanced water vapor transport across hydrophobic nanochannels of varied
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25 length was carried out to estimate the tangential momentum accommodation coefficient for
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exploring the momentum changes to the water molecules colliding with the wall of
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30 nanochannels (Figure 2b).35 Moreover, Zhang et al. have discussed the wettability and
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33 application of nanochannels and proposed a concept of "quantum-confined superfluid" to
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35 demonstrate the ultrafast transport behaviors in biological or artificial nanochannels, in which
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38 molecules/ions appeared to pass through one by one in a chain.33 Studies over the years have
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shown that the effect of surface wettability on the transport behavior of confined ions and
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43 molecules depends on their spatial size and viscosity in the interface region. Especially when
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46 the nanoconfinement is smaller than 10 nm, the effect of wettability will become increasingly
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51 Although both experimental measurements and molecular dynamics have been used to
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study the wettability of various dimensional spaces, including the impact of the hydrophilic-
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4 further lucubrating and proving. These studies will promote the development of basic
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7 disciplines such as surface chemistry and fluid dynamics, and have significant practical
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28 Figure 2. The ultra-fast water molecular transport in nano- and sub-nano confinement. (a) Enhanced
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water permeability in a CNT porins, and the hydrogen-bonding pattern and water diffusion inside it.
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31 Reprinted with permission from Ref. 32. Copyright 2017 The American Association for the
32 Advancement of Science. (b) Capillary induced water vapor permeation through FTS-modified
33 hydrophobic nanochannel (80 nm deep × 30 µm wide × 2.5 mm long). FTS: (heptadecafluoro-1,1,2,2-
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35 tetrahydrodecyl) trichlorosilane. Reprinted with permission from Ref. 35. Copyright 2018 Royal
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39 For surface charge, many anomalous ionic/molecular transport behaviors can be ascribed
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42 to the surface charge properties within the confinement. An inner surface charged
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44 nanochannel was proposed to form a unipolar ionic field-effect transistor when its diameter
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47 is smaller than the Debye length due to the created unipolar solution of counterions inside it
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50 (the inset with a dotted oval in the upper right corner of Figure 1).45 Because of the uniquely
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52 crowded intermolecular forces under severe nanoconfinement, the transport behaviors of ions
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55 can be influenced by the interfacial electrical double layer (EDL) induced by a charged
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4 polymeric membranes can interact with partially dehydrated alkali metal ions specifically,
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7 which results in a high selectivity and transport rate of alkali metal ions over heavy metal ions
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9 to achieve a balance between permeability and selectivity (Figure 3a).28 Other than ions, the
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12 charged alumina nanochannel surface can also cause an inductive dipole in neutral molecules,
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such as phenol. The electrons in p or π orbitals of the hydroxyl group of phenol are polarized
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17 by the charged alumina surface, and this results in the changes the interactions between phenol
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20 molecules and nanochannels, which decreases the diffusion flux of molecules in the EDL
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22 other than the free diffusion in the bulk phase (Figure 3b).25 Besides, Li et al. demonstrated
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25 that the degree of evaporation differs under nanoscale confinements. They thought it was
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originated from surface-charge-induced concentration changes of hydronium ions inside.23
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40 Figure 3. Ionic/molecular transport behaviors in charged nanopores/channels. (a) Ultra-fast ion
41 sieving in polymer nanopores with a negatively charged inner surface as the pore size increases. A
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trade-off between high selectivity and permeability can be controlled by the pore size. Reprinted with
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44 permission under a creative commons license from Ref. 28.
45 www.creativecommons.org/licenses/by/4.0/. Copyright 2018 Springer Nature. We have relabeled the
46 “Heavy metal ions” and “Alkali metal ions” instead of the original label location of “Cation ions”. (b)
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48 Phenol molecules diffusion behaviors transporting through charged alumina nanochannels, which
49 depends on the thickness of the EDL. Reprinted with permission from Ref. 25. Copyright 2010
50 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Besides the differences caused by the charged and uncharged surfaces mentioned above,
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56 changing the surface potential and charge density also can induce many unusual ionic transport
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4 membranes was achieved by changing the surface potential at low voltage. Especially, sub-
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7 2 nm confined ion diffusion can be strongly modulated by the surface potential-induced EDL
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9 due to its strong ion-ion correlations under severe nanoconfinement.46 With a pH-tunable
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12 zwitterionic surface, the surface charge density can also be tuned by changing pH and further
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regulate current rectification behaviors.47 Kavokine et al. showed that when the channels were
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17 charged with a gating electrode, the oppositely charged ions inside the channels can form
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20 ‘Bjerrum pairs’ and causes ionic Coulomb blockade, which results in quantized and strongly
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22 nonlinear ionic transport. This peculiar mechanism can be used in advanced ionic machinery,
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25 such as an ion pump.26 If combing hydrophobic graphene with amphiphilic nano fibrillated
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cellulose (NFC), the nanometer-thick graphite flakes were wrapped by NFC fibers to form
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30 multiple two-dimensional confined domain layer space, and the cations interacting with the
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33 negative charges on the walls of the channel could form an ultra-fast cation stream.48
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35 Overall, surface charge density and distribution can affect the thickness of the EDL in
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38 confinement and thus influencing the motility or diffusion of ions and molecules transported
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inside. These findings explain the transport mechanism of ions and molecules in the charged
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43 confinement and can be further extended to the study of nanofluidics. They have great potential
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46 to be applied in the enrichment and separation of ions/molecules.
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48 Static Structure. It is generally believed that the geometric characteristics of the
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51 confinement structures also plays a crucial role in determining the ionic/molecular transport
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behaviors. From the static and dynamic point of view, we will depict these confinement
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56 structures as static structures and dynamic structures. The section of static structure focus on
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59 the influence of the fixed shape, size, and dimension of the confinement on the transport
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4 properties, while the dynamic structure emphasizes the dynamically active control of
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7 ionic/molecular transport through the deformation of the confinement. With the rapid
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9 development of nanofabrication technology49 and the in-depth study of low-dimensional
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12 materials,50-54 more and more special ionic/molecular transport behaviors in nano and sub-nano
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confinement structures have been discovered and understood. Next, we will introduce and
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17 discuss the development of this field from the static structure.
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20 Over the decades, researchers have developed multifarious static structures of
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22 confinement, which can be divided into zero-dimensional (0D) pores, one-dimensional (1D)
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25 channels/tubes, two-dimensional (2D) channels/slits, and three-dimensional (3D) porous
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materials (Figure 4). Nanopores are 0D nanoconfinement pierced in solid-state membrane
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30 (Figure 4a). According to the length-to-diameter ratio, nanopores are defined with pore
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33 diameter larger than depth. When pore depth is much larger than diameter, the structure is
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35 generally referred to as a nanochannel, which can be viewed as 1D confinement (Figure 4b).7
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38 The preparation methods of nanopores and nanochannels mainly include direct drilling method,
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van der Waals assembly method, vacuum self-assembly method, and organic synthesis method.
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43 It is worth mentioning that the design and development of asymmetric artificial nanochannels
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46 have received great attention which is inspired by biological nanochannels that also have
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48 asymmetric structures (Figure 4b).55 Besides, the tubular structures, such as titania nanotubes,
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51 titanate nanotubes, silicon nanotubes, cadmium sulfide nanotubes, and CNTs, etc. are also the
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components in 1D confinements (Figure 4b). One of them, CNTs is the most representative
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56 one due to their adjustable nanoscale sizes and helical symmetry of carbon atoms that enable
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4 nearly frictionless interfaces. Thus, it can serve as an ideal fluidic experimental research
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7 model.15
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9 Recently, the confinement structures have been expanded from 1D to 2D nano planar
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12 channels46, 48 and angstrom slits51 (Figure 4c) using two sheets, based on which more precise
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size control can be achieved by adjusting the distance between layers. The confinement size
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17 can be further reduced to limit the ions/molecules in an ultra-small space to challenge the
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20 unknown mechanisms of action. For example, the development of angstrom slits makes the
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22 monoatomic space possible, hence the hydrated ions were found to be dehydrated to enter the
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25 monoatomic confinement which size is small than themselves.51 In addition, the utilization of
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nanoporous materials as 3D structures integrate 2D structures (Figure 4d), which are called
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30 "honeycomb" or "foam" materials because their shape is like the hexagonal structure of a
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33 honeycomb. 3D porous materials can be made of carbides, nitrides, borides, and silicide of
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35 various metals, alloys, and refractory metals. Considering the more complicated trajectory of
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38 motion, the 3D structures bring more complex ionic and molecular transport behaviors than 1D
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and 2D, but it manifests a higher transport flux. A variety of confinement structures provide
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43 convenient conditions and a plenty of stable platforms for the study of ionic/molecular transport
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Figure 4. The static confinement structures in the anomalies of ionic/molecular transport behaviors. (a)
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Zero-dimensional pore with regular and controllable size. (b) One-dimensional channels with
24 cylindrical (symmetric) and conical (asymmetric) shape, and one-dimensional tube with adjustable radii.
25 (c) Two-dimensional planar channels prepared by adjusting the distance between layers, and angstrom
26 slits capable of monoatomic layer confinement. (d) The three-dimensional porous materials.
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29 To explore the rules and secrets of ionic/molecular transport behaviors inside the static
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31 confinements, more and more static confinements with high accuracy and super small size have
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34 been created. The carbide-derived carbons (CDCs) were used to reduce the average pore
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diameter of capacitor materials, and when the pore diameter of the CDCs is smaller than 1 nm,
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39 the phenomenon of dramatically increased capacitance was found in this material (Figure 5a).
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42 It was presumed that the carbon capacitance would continually decrease along with the
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44 decrease of pore sizes, but an anomalously large increase in carbon capacitance was spotted
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47 after the pore becoming smaller than the size of solvated electrolyte ions.56 In addition, the
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nanoscale graphite stacked-junctions were prepared by varying the effective in-plane area
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52 down to the submicron scale. The effective in-plane area had a greater effect on the I-V
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55 characteristic of nanoscale graphite stacked-junctions.57 However, there existed an obstacle
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57 that traditional top-down or bottom-up strategies were difficult to prepare atomic-level
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4 precision nanoconfinements. Recently, these puzzles have been overcome that
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7 nanoconfinements with atomic precision and adjustable size have been prepared.50 By
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9 exploiting the atomic flatness of graphene, researchers fabricated the nanochannels with
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12 atomic-scale control utilizing microfabrication techniques. The maximum velocity of water in
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these nanochannels could reach 1 m/s when transmitting through the capillary effect, which
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36 Figure 5. Ionic/molecular transport behaviors in the static structure of nano- and sub-nano confinement.
37 (a) Dramatically increase in carbon capacitance when the pore size is smaller than 1 nm. Reprinted with
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permission from Ref. 56. Copyright 2006 The American Association for the Advancement of Science.
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40 (b) Dehydrated ions transport through angstrom-scale slits. Reprinted with permission from Ref. 51.
41 Copyright 2017 The American Association for the Advancement of Science. (c) Single layered water
42
molecules flowing through the one-atom-high channel. Reprinted with permission from Ref. 54.
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44 Copyright 2019 The American Association for the Advancement of Science.
45
46
47 The anomalies are more apparent as the static confinement becomes extremely narrow
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50 and small. For example, the traditional opinions are held that ions with a diameter larger than
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52 the size of the slits are impermeable, which is overturned in a two-atomic scale and two-
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55 dimensional confined slits with a height of approximately 6.7 Å. In this confinement, hydrated
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57 ions can be transported into it by squeezing or removing the hydration layer (Figure 5b, also
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4 shown as an example in the inset with a dotted oval in the lower left corner of Figure 1).51
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7 Meanwhile, if the confinement size is reduced to the angstrom-scale, the narrow slits will
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9 amplify the interaction force between the gas molecules, resulting in some peculiar gas
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12 transport behaviors. The increase in the transmission rate of gas molecules was attributed to
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many specular reflections of them. In these of molybdenum disulfide (MoS2) slits, an obvious
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17 ballistic transmission mechanism was showed.52 And, when the angstrom-scale slit was subject
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20 to weak external disturbances (mechanical pressure and electric field), its transmission
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22 performance greatly changed. The friction between the water molecules/ions and the inner
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25 surface of slits walls greatly affects its transmission dynamics.53 Further reducing the height of
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the confinement to about 3.4 Å barely allowed the selective passage of single-layered water
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30 molecules, and all ions except protons were excluded by steric effects (Figure 5c).54
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33 Above all, the designed static structures with high-precision and advanced features have
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35 enabled the confinement to be controllable and geometrically simulated for the studying of
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38 ionic/molecular transport. These studies on transport behavior in a narrow space ranging from
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0-dimensional, 1-dimensional, 2-dimensional to 3-dimensional, will establish microscopic
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43 scale criteria for the ions and molecules. We believe that in the future smaller and more
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46 complex structures would be possibly constructed to investigate transport behaviors even
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48 below the atomic level. These studies will contribute to nanoscience's perfection and have great
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51 application significance in the fields of catalysis and energy.
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54
Dynamic Structure. For the dynamic structure, we define it as the case that the
55
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57 confinement structure is in an elastic deformation during the process of the ionic and molecular
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4 transport. Compared with the static structure system, the obvious difference of the dynamic
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7 one is the introduction of its active manipulation through dynamic deformation on transport
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9 properties. Because the deformation influence factors of the confinement will have a great
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12 impact on the transport components, there are more interesting and unpredictable
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ionic/molecular transport behaviors, and more meaningful in practical applications in this case,
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17 such as dynamic selective passage,58 trapping and forcing large molecules to deform.59, 60 At
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20 present, there are two approaches to achieve confinement with dynamic structure and
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22 deformation. One is the deformation of the lateral area, which is mainly caused by the applied
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25 pressure or tension to make the confinement space smaller. Another approach is to dynamically
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change the axial curvature of the confinement. For the first approach, the elastic resin materials
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30 (PDMS) characterized by nanolithography technology are used to prepare elastic nanochannels
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33 to achieve lateral area deformation. The prepared elastomeric nanochannels can dynamically
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35 adjust the cross-sectional size of the channel according to the transport molecules or particles,
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38 to achieve molecules/particle separation, enrichment, or trapping58. Moreover, there are reports
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on squeezing nanochannels to expand single molecular chains (Figure 6a)59 and achieve DNA
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43 translocation for detection and manipulation.60
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55
56
Figure 6. Ionic/molecular transport behaviors in dynamically deformed nanochannels. (a) Untethered
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58 DNA and chromatin linearized by narrowing an elastomeric nanochannel filled with solutions of the
59 biopolymers. Reprinted with permission from Ref. 59. Copyright 2012 American Chemical Society. (b)
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Ionic transport behaviors in dynamic carbon nanochannels, which can regulate ion transport through
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5 the switch of dynamic changes in asymmetric curvature. The diameter of the carbon nanochannel is 8
6 nm. The states of i-iv represent four different curvatures, and the red and blue arrows indicate the
7 magnitude of the ion current in their representative directions.
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9
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11 For the second approach, the strategy for changing the curvature of confinement is
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13 inspired by nature that the biological intercellular nanochannels are in uninterrupted bending
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16 change during specific physiological ionic transport process and diseases.61, 62 There have been
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18 some biological reports earlier, pointing out the active influence of membrane curvature
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21 protein, where membrane curvature is mediated by the collaboration of different mechanisms
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24 at different stages of events, especially in very small scale.63-65 Therefore, Wang et al.
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26 constructed a type of dynamic deformable nanochannels with anomalous transport behaviors
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29 based on curvature adjustable CNTs embedded inside an elastomer (the inset with a dotted
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31 rectangle in the lower right corner of Figure 1).66 By applying pressures to the elastomer, the
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34 real-time reversible conversions between ionic rectifier and bi-pass inside the channels are
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37 achieved. In this systems, the asymmetric curvature changes in deformation of the
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39 nanochannels play a dominant role in ionic transport, when the transmembrane voltage is at
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42 the several tens of millivolt level and the ion transport concentration is at the millimole level,
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44 for the potassium ions as the transport ions inside nanochannels (Figure 6b). It was a
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47 coincidence that this level is the same order of magnitude of the physiological level in the
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50 organism. The dynamic asymmetric gradient of curvature in the nanochannels caused a
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52 consequence of a dynamic rectification of the ionic currents. The dynamic behavior of ionic
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55 current flow in such deformable nanochannels should have important counterpart behavior in
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4 biological systems and physiological systems with nanochannels since systems, such as
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7 muscles and tissues, are always deformable.
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10 A reliable artificial dynamic nanoconfinement can provide more possibilities for us to
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13 explore the transport behaviors taking place inside and will be of great instrument in life science
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and soft nanofluidics. Although studies toward dynamic nanoconfinement are still in early
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18 stage, it will be enhanced greatly by the development of both material science and
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21 nanotechnology approaches that can construct more complex systems for studying various
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23 transport behaviors, which can spark various applications in artificial ion channels,
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26 nanofiltration, energy harvesting and beyond.
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Latest Applications in Nanofluidics. The term “latest application” in the context of
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32 nanofluidics does not refer to the commercial products available on the market, and it is can
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35 only be envisioned in the long-term. At present, nanofluidic system represents a new regime in
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37 the study of ion and molecule transport in the extremely small confinements.67, 68 There is an
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40 increasing interest in nano and sub-nano confinement with controllable structures and features,
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42
especially the rise of 2D materials represented by graphene. And the emergence of advanced
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45 nanofluidic characterization equipments and technologies has not only allowed us to study the
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48 transport behavior of the ions/molecules but also enabled the investigation of the fluidic
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50 behaviors. Therefore, many unexpected behaviors and singular transmission characteristics in
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53 nanofluidics have been revealed, and the basic understanding of these fundamental
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mechanisms have the potential to solve the "critical problems" in the application of membrane
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58 science, especially tackling the challenges in membrane separation and energy conversion.
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4 Membrane separation. The anomalous and novel transport mechanisms of ions/molecules
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7 in nano and sub-nano confinement can avoid the trade-off between permeability and selectivity,
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9 and can simultaneously improve the separation coefficient and permeability. Hence it has a
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12 great potential for application in the membrane separation field. Celebi et al. have found that
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the gas was transported in the oligo-layer porous graphene film by a free molecule (overflow)
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17 mechanism, which significantly reduced the frictional collision between the gas molecule and
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20 the channel wall to increase the gas penetration rate. The molecular weight difference was used
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22 to efficiently permeate gas molecules.69 Joshi et al. have studied the penetration behavior of
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25 small molecules in micron-scale graphene oxide (GO) films. They have found that in the dry
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state, due to the vacuum sealing effect between the 2D sheets, the small molecules could not
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30 penetrate. When the GO membrane was soaked in water, it could block molecules with a
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33 hydration radius greater than 4.5 Å like molecular sieves, and molecules smaller than this size
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35 could be permeated and transported at a faster speed under higher capillary pressure between
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38 GO sheets.70 Yang et al. have developed a graphene/CNTs composite nanofiltration membrane
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(GNM/SWNT) with good mechanical strength. In the GNM/SWNT composite nanofiltration
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43 membrane, GNM with high-density sub-nanopores could effectively transport water
44
45
46 molecules, while preventing the flow of solute ions or molecules to achieve size-selective
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48 separation, and the SWNT network structure acted as microscopic support for GNM. The
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51 physical framework thus ensured the structural integrity of the atomic thickness of the GNM.
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53 71
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56 Energy conversion. Nanofluidics is also highly interesting for the efficient and selective
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59 transport of ions, and seawater-freshwater with different concentrations are used to generate
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4 electricity for efficient energy conversion. An evaporation-driven water flow device inducing
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7 electricity generation in nanostructured carbon black film was reported, which stems from
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9 water evaporation and the capillary force driving directional flowing water inside the carbon
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12 black film nanopores. The interaction between carriers in the solid side and ions in the liquid
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side facilitated by functional groups in nanopores.72 Besides, applying the transport of
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17 ions/molecules in nano and sub-nano confinement for highly efficient osmotic energy-electric
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20 conversion has achieved significant progress. Using the higher transmission speed and
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22 selectivity of K+ in single-layer MoS2 porous membranes can achieve high osmotic energy-
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25 electric conversion power density (106 W/m2) due to the hydrophilicity of Mo atoms and the
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negative charge properties of the pore surface in the double KCl solution tank with
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30 concentration difference, which is one million times higher than that obtained by traditional
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33 exchange membrane reverse electrodialysis.19 Siria et al. have found that the inner wall of
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35 boron nitride (BN) nanotubes in contact with the fluid (electrolyte) contains a large amount of
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38 negative charge, which promotes the rapid selective transport of ions. When BN nanotubes are
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in two electrolyte solution tanks with concentration differences, a large osmotic energy-electric
41
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43 conversion can be achieved in a short time. By optimizing the diameter of the nanotube and
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46 the pH value of the solution, the maximum conversion power density can reach 4 kW/m2.73 Liu
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48 et al. have used a polycyclic aromatic hydrocarbon monomer molecule with a core-rim
49
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51 structure to produce a nanoporous carbon membrane with a pore size of 3.6 ± 1.8 nm and
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thickness of 2.0 ± 0.5 nm via the thermal crosslinking methods. More -COO- groups on the
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56 carbon membrane pores made the membrane pores negatively charged. When it was used as a
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4 separator in the middle of the electrolyte solution with higher concentration difference, it has
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7 higher selectivity for ions and shows excellent permeation energy conversion performance.74
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9 Conclusions and Outlook. Understanding ionic/molecular transport in nano- and sub-
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12 nano confinement imparts the ability to manipulate and control the nanofluidics for exploring
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of hydrodynamics and related transports at the smallest scales, and emerging applications. The
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17 increase in relevant publications in this field clearly indicates that studying ionic/molecular
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20 transport behavior in confinement offers a flexible venue to build various nanofluidics. It paves
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22 the way for mimicking the process of ionic/molecular transport in biological systems, as well
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25 as for boosting the development of nanofluidics for real-world applications. It is an emerging
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field that, in many respects, is still in its infancy. At present, the instability and failure of the
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30 confinement surface properties make it still a big challenge in terms of durability and stain
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33 resistance. The study of the super-slip interface, the construction of surface microstructures,
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35 and the contrive of new liquid-based surfaces are all good examples to maintain the stability of
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38 surface properties. In addition, making complex or precisely controlled confinement structures
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still requires high costs and long production processes. The emerging 3D printing technology
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43 provides new routes for the design and construction of static structures. It remains essential for
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46 further investigating the transport mechanism and behaviors in the dynamic confinement
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48 structures due to the multiple influence mechanisms brought by the dynamically changing
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51 space and dynamically interacting of ions/molecules, but it will be enhanced greatly by the
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53
development of both material science and nanotechnology approaches that can construct more
54
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56 complex systems for studying various transport behaviors inside.
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4 The ionic/molecular transport in nano- and sub-nano confinement are substantially
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7 different from those in the macroscopic phase, and understanding these behaviors requires the
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9 development of new processing technologies, characterization methods, and theoretical
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12 understandings. Fortunately, the molecular dynamics simulation analysis offers a valuable
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insight into understanding the dynamics of monoatomic transport behaviors, which has shed
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17 light on that the spatial distribution of interatomic potential near the path of fluid atoms.27 Also,
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20 the possibility of direct visualization and quantification of transport behaviors via nanofluidic
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22 devices instead of classical theories has matured.20 For future progress, it will be important to
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25 further integrate various disciplines such as fluid mechanics, condensed matter physics,
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27
statistical physics, computational chemistry, materials science, physiology, and biology, etc.,
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30 and combine different perspectives to probe the intrinsic mechanisms of the anomalies of
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33 ionic/molecular transport in nano- and sub-nano confinement, and to better promote the
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35 development of this field. It is hoped that these will have further practical applications in the
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38 fields of seawater desalination, power generation, membrane anti-fouling, and soft robots.
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We hope this Mini Review will inspire the active interests of many researchers in the field
41
42
43 of ionic/molecular transport in nano- and sub-nano confinement. We expect that the summary
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46 and discussion in the anomalous ionic/molecular transport behaviors can help to establish a
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48 research methodology, recur to the visualized nanofluidic devices, further, to explore new
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51 physical and chemical transport mechanisms at these ultra-small scales.
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56 AUTHOR INFORMATION
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58
59 Corresponding Author
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4 *Email: houx@xmu.edu.cn
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7 Author Contributions
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10 The manuscript was written through the contributions of all authors. All authors have approved
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12 the final version of the manuscript. The authors thank X. Chen, L. Zhou and W. He for
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14
15 beneficial discussion.
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17
18 Notes
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21 The authors declare no competing financial interest.
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24
25
ACKNOWLEDGMENT
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27 This work was supported by the National Key R&D Program of China (Project No.
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30 2018YFA0209500), the National Natural Science Foundation of China (51706191, 21673197,
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32 21621091, 21975209), the Fundamental Research Funds for the Central Universities
33
34
35 (20720190037), the Natural Science Foundation of Fujian Province of China (No.
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2018J06003).
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40
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