Water Molecules In Carbon Nanotubes Research Articles

Close-Packed Ices in Nanopores.

Water molecules in any of the ice polymorphs organize themselves into a perfect four-coordinated hydrogen-bond network at the expense of dense packing. Even at high pressures, there seems to be no way to reconcile the ice rules with the close packing. Here, we report several close-packed ice phases in carbon nanotubes obtained from molecular dynamics simulations of two different water models. Typically they are in plastic states at high temperatures and are transformed into the hydrogen-ordered ice, keeping their close-packed structures at lower temperatures. The close-packed structures of water molecules in carbon nanotubes are identified with those of spheres in a cylinder. We present design principles of hydrogen-ordered, close-packed structures of ice in nanotubes, which suggest many possible dense ice forms with or without nonzero polarization. In fact, some of the simulated ices are found to exhibit ferroelectric ordering upon cooling.

Hormones Nanofiltration in Carbon Nanotubes and Boron Nitride Nanotubes Using Uniform External Electric Field Through Molecular Dynamics.

Hormones are a dangerous group of molecules that can cause harm to humans. This study based on classical molecular dynamics proposes the nanofiltration of wastewater contaminated by hormones from a computer simulation study, in which the water and the hormone were filtered in two single-walled nanotube compositions. The calculations were carried out by changing the intensities of the electric field that acted as a force exerting pressure on the filtration along the nanotube, in the simulation time of 100 ps. The hormones studied were estrone, estradiol, estriol, progesterone, ethinylestradiol, diethylbestrol, and levonorgestrel in carbon nanotubes (CNTs) and boron nitride (BNNTs). The most efficient nanofiltrations were for fields with low intensities in the order of 10-8 au and 10-7 au. The studied nanotubes can be used in membranes for nanofiltration in water treatment plants due to the evanescent field potential caused by the action of the electric field inside. Our data showed that the action of EF in conjunction with the van der Walls forces of the nanotubes is sufficient to generate the attractive potential. Evaluating the transport of water molecules in CNTs and BNNTs, under the influence of the electric field, a sequence of simulations with the same boundary conditions was carried out, seeking to know the percentage of water molecules filtered in the nanotubes.

Water molecules in CNT-Si3N4 membrane: Properties and the separation effect for water-alcohol solution.

Water confined in carbon nanotubes (CNTs) has been intensively studied because of its unique properties and potential for various applications and is often embedded in silicon nitride (Si3N4) membranes. However, the understanding of the influence of Si3N4 on the properties of water in CNTs lacks clarity. In this study, we performed molecular dynamics simulations to investigate the effect of the Si3N4 membrane on water molecules inside CNTs. The internal electric field generated in the CNTs by the pointcharges of the Si3N4 membrane changes the structure and dynamical properties of water in the nanotubes, causing it to attain a disordered structure. The Si3N4 membrane decreases the diffusivity of water in the CNTs; this is because the Coulomb potential energy (i.e., electrostatic interaction) of water decreases owing to the presence of Si3N4, whereas the Lennard-Jones potential energy (i.e., van der Waals interaction) does not change significantly. Furthermore, electrostatic interactions make the water structure more stable in the CNTs. As a result, the Si3N4 membrane enhances the separation effect of the water-methanol mixture with CNTs in the presence of an external electric field. Furthermore, the threshold of the external electric field strength to induce water-methanol separation with CNTs is reduced owing to the presence of a silicon nitride membrane.

Characterization of water structure in carbon nanotubes by various order parameters

Various order parameters have been suggested to characterize the local structure of liquid water in bulk. Characterization the local structure of water molecules in the confined systems by various order parameters is important but still unclear. In this work, a series of popular order parameters are used to analyze the local structure of water molecules in carbon nanotubes (CNTs) by molecular dynamics simulation. Based on the value of order parameters, the different structures of water molecules in CNTs and in bulk were discussed. The orientational tetrahedral order (q) and translational tetrahedral order (Sk) are much better than local structure index (LSI) to describe the local structure of water in CNTs. We also demonstrated that the local structure of water molecules in the CNT(40,40) is almost the same with that in bulk. The findings could give us a guideline to investigate the water molecules in confined system.

Molecular Dynamics Simulation of the Nanofluidic Energy Absorption System Under Mid-speed Loading

In this work, a nanofluidic energy absorption system (NEAS) under mid-speed loading is investigated by using molecular dynamics simulation. Usually, two types of dynamic and quasi-static loadings have been applied on NEAS. In the dynamic loadings, NEAS is taken under high-speed loadings in the range of 5 m/s up to 1000 m/s, and in the quasi-static loadings, it is taken under low-speed loadings in the range of less than or equal to 0.0005 m/s. Here, to investigate the performance of NEAS under mid-speed loading, four loading rates of 0.2, 0.4, 0.8 and 1.0 m/s are considered. Also, four armchair CNTs (8,8), (10,10), (12,12) and (14,14) were selected to study the effects of nanotube size. The results of simulations showed that contact angle which shows the hydrophobicity of carbon nanotube (CNT) is reduced on average 3.6% by increasing the loading rate in all CNTs, leading to an average 41.7% decrease of infiltration pressure and an average 16% reduction of absorbed energy density in all CNTs. No friction is observed at the loading rate of 0.2 m/s in all CNTs during movement of water molecules in CNT. But, at the other loading rates, friction is increased by increasing the loading rate, leading to an average 24.8% reduction of the absorbed energy efficiency of NEAS in all CNTs. Also, contact angle, infiltration pressure, absorbed energy density and efficiency are decreased by increasing the CNT diameter.

Structures of Water Molecules in Carbon Nanotubes Induced with Electric Fields and its Application for Water-Methanol Separation

Water confined in carbon nanotubes (CNTs) under the influence of an electric field has interesting properties that are potential for nanofluidic-based applications. With molecular dynamics simulations, this work shows that the electric field induces formation of ordered structures of water molecules in the CNTs. Formation of the ordered structures strengthens the electrostatic interaction between the water molecules. As a result, water strongly prefers to fill CNTs over methanol and it produces a separation effect. Interestingly, the separation effect with the electric field does not decrease for a wide range of CNT diameter.

Water transport within carbon nanotubes on a wave.

Water molecules possess discontinuous properties in confined surroundings as compared to the bulk, their transport velocity shows a step change with the increase in the radius of hydrophobic carbon nanotubes (CNTs). Here, we report that the chain of water molecules in CNTs behaves as a "spring" owing to hydrogen bonding. Thus, the transport of water molecules in confined systems proceeds as a wave motion with eigen frequencies in the terahertz region which is determined by the CNT size. Water velocities derived from molecular dynamics (MD) fit well with the ones from finite element methods (FEM) on consideration of both the no-slip and slip boundary conditions for CNT diameters less than 1 nm and more than 1 nm, respectively. The present work helps clarify the features of mass and momentum transfers in confined surroundings, and provides perspectives for mass transfer applications.

Unraveling the mechanism of selective ion transport in hydrophobic subnanometer channels

Recently reported synthetic organic nanopore (SONP) can mimic a key feature of natural ion channels, i.e., selective ion transport. However, the physical mechanism underlying the K(+)/Na(+) selectivity for the SONPs is dramatically different from that of natural ion channels. To achieve a better understanding of the selective ion transport in hydrophobic subnanometer channels in general and SONPs in particular, we perform a series of ab initio molecular dynamics simulations to investigate the diffusivity of aqua Na(+) and K(+) ions in two prototype hydrophobic nanochannels: (i) an SONP with radius of 3.2 Å, and (ii) single-walled carbon nanotubes (CNTs) with radii of 3-5 Å (these radii are comparable to those of the biological potassium K(+) channels). We find that the hydration shell of aqua Na(+) ion is smaller than that of aqua K(+) ion but notably more structured and less yielding. The aqua ions do not lower the diffusivity of water molecules in CNTs, but in SONP the diffusivity of aqua ions (Na(+) in particular) is strongly suppressed due to the rugged inner surface. Moreover, the aqua Na(+) ion requires higher formation energy than aqua K(+) ion in the hydrophobic nanochannels. As such, we find that the ion (K(+) vs. Na(+)) selectivity of the (8, 8) CNT is ∼20× higher than that of SONP. Hence, the (8, 8) CNT is likely the most efficient artificial K(+) channel due in part to its special interior environment in which Na(+) can be fully solvated, whereas K(+) cannot. This work provides deeper insights into the physical chemistry behind selective ion transport in nanochannels.

Structures of water molecules in carbon nanotubes under electric fields.

Carbon nanotubes (CNTs) are promising for water transport through membranes and for use as nano-pumps. The development of CNT-based nanofluidic devices, however, requires a better understanding of the properties of water molecules in CNTs because they can be very different from those in the bulk. Using all-atom molecular dynamics simulations, we investigate the effect of axial electric fields on the structure of water molecules in CNTs having diameters ranging from (7,7) to (10,10). The water dipole moments were aligned parallel to the electric field, which increases the density of water inside the CNTs and forms ordered ice-like structures. The electric field induces the transition from liquid to ice nanotubes in a wide range of CNT diameters. Moreover, we found an increase in the lifetime of hydrogen bonds for water structures in the CNTs. Fast librational motion breaks some hydrogen bonds, but the molecular pairs do not separate and the hydrogen bonds reform. Thus, hydrogen bonds maintain the water structure in the CNTs, and the water molecules move collectively, decreasing the axial diffusion coefficient and permeation rate.

Transport characteristics of water molecules in carbon nanotubes investigated by using molecular dynamics simulation

The transport characteristics of water molecules in carbon nanotubes (CNTs) is studied in this work using molecular dynamics simulation method. The effect of channel diameter, defects and the inter-layer spacing on the transport of water molecules is studied by subjecting the flow of water molecules through CNTs under pressure. The findings show that the efficiency of water transport in CNTs can be improved by deploying bigger SWCNTs. In addition defects in the nano-fluidic system will also reduce the transport efficiency of water molecules. Additionally, for the case of double walled CNTs (DWCNTs), it is found that the inter-layer spacing in a DWCNT has a significant influence on the rapid transport of water molecules. The transport characteristics of water molecules in CNTs have been systematically and comprehensively studied using the MD simulations and the discussions are presented in this paper.

Study and Investigation of Interaction and Association of Water Molecules in Carbon Nanotubes and Calculation of Their Thermodynamics Properties Using Molecular Dynamics Simulation: A Mathematical Approach

Study and Investigation of Interaction and Association of Water Molecules in Carbon Nanotubes and Calculation of Their Thermodynamics Properties Using Molecular Dynamics Simulation: A Mathematical Approach

Combining molecular dynamics simulation and transition state theory to evaluate solid-liquid interfacial friction in carbon nanotube membranes

A molecular dynamics (MD) methodology based on Eyring theory of reaction rates is proposed for investigating solid-liquid interfacial properties crucial to the development of many nanotechnology applications. The method involves the calculation of activation energy required for the flow process directly from the MD trajectory information. We have applied this methodology to study the behavior of water in hydrophobic confinement in carbon nanotubes (CNTs) and also between graphene sheets. In the case of confined water molecules in CNTs and between graphene sheets the degree of confinement and curvature effects were found to have more influence on the solid-liquid interfacial friction, with almost negligible friction below a certain characteristic dimension in both the cases. This behavior of confined and unconfined water molecules is explained on the basis of molecular interactions and subsequent changes in the activation energy. Analysis based on this method also revealed that a finite amount of friction does exist at the channel entry and exit region. This could limit the flow of liquid molecules through the nanochannels and hence needs to be taken into account in the design of nanofluidic devices.

Molecular Dynamics Simulation Study of the Structural Characteristics of Water Molecules Confined in Functionalized Carbon Nanotubes

Molecular dynamics (MD) simulations were performed to study the structural properties of water molecules confined in functionalized carbon nanotubes (CNTs). Four CNTs, two armchair-type (6, 6), (7, 7) and two zigzag-type (10, 0), (12, 0) CNTs, representing different helicities and different diameters, were chosen and functionalized at their open ends by the hydrophilic -COOH and the hydrophobic -CH3 groups. The structural properties of water molecules inside the functionalized CNTs, including the orientation distributions of dipole moment and O-H bonds, the length of the single-file water chain, and the average number of hydrogen bonds, were analyzed during a process of simulations. MD simulation results in this work showed that the -CH3 functional groups exert little special effects on the structural properties of water molecules. It is mainly due to the relatively small size of the -CH3 group and its hydrophobic nature, which is consistent with hydrophobic CNTs. For CNTs functionalized by -COOH groups, the configurations of -COOH groups, incurvature or excurvature, determine whether water molecules can enter the CNTs. The incurvature or excurvature configurations of -COOH groups are the results of synergy effects of the CNTs' helicity and diameter and control the flow direction of water molecules in CNTs.

Helicity and temperature effects on static properties of water molecules confined in modified carbon nanotubes

Carbon nanotubes show exceptional properties that render them promising candidates as building blocks for nanostructured materials. Many ambitious applications, ranging from molecular detection to membrane separation, require the delivery of fluids, in particular aqueous solutions, through the interior of carbon nanotubes (CNT). To foster such applications, an understanding of the properties of water molecules confined in carbon nanotubes at the molecular level is needed. In this work we report a study of temperature and helicity effects on static properties of water molecules confined in modified CNT by molecular dynamics simulations. It was found that the temperature has little effect on the confined water molecules in carbon nanotubes. But on the other hand, the simulation results showed that because of the difference in helicity between (6, 6) and (10, 0) CNTs, the modification by hydrophilic carboxyl acid functional groups (-COOH) results in a different response to the CNTs, which in turn have control over the flow direction of water molecules in these CNTs.