Carbon nanotubes show exceptional physical properties that render them promising candidates as building blocks for nanostructured materials. Many ambitious applications, ranging from gene therapy to membrane separations, require the delivery of fluids, in particular aqueous solutions, through the interior of carbon nanotubes. To foster these and other applications, it is necessary to understand the thermodynamic and transport properties of water confined within long narrow carbon nanotubes. Previous theoretical work considered either short carbon nanotubes or short periods of time. By conducting molecular dynamics simulations in the microcanonical ensemble for water confined in infinitely long carbon nanotubes of diameter 1.08 nm, we show here that confined water molecules diffuse through a fast ballistic motion mechanism for up to 500 ps at room temperature. By comparing the results obtained for the diffusion of water to those obtained for the diffusion of a reference Lennard-Jones fluid, we prove here that long-lasting hydrogen bonds are responsible for the ballistic diffusion of water clusters in narrow carbon nanotubes, as opposed to spatial mismatches between pore-fluid and fluid-fluid attractive interactions which, as shown previously by others, are responsible for the concerted motion of simple fluids in molecular sieves. Additionally we prove here for the first time that, despite the narrow diameter of the carbon nanotubes considered which may suggest the existence of single-file diffusion, when the trajectories of confined water are studied at time scales in excess of 500 ps, a Fickian-type diffusion mechanism prevails. Our results are important for designing nano fluidic apparatuses to develop, for example, novel drug-delivery devices.

The structure and dynamic properties of interfacial water at the graphite and silica solid surfaces were investigated using molecular dynamics simulations. The effect of surface properties on the characteristics of interfacial water was quantified by computing density profiles, radial distribution functions, surface density distributions, orientation order parameters, and residence and reorientation correlation functions. In brief, our results show that the surface roughness, chemical heterogeneity, and surface heterogeneous charge distribution affect the structural and dynamic properties of the interfacial water molecules, as well as their rate of exchange with bulk water. Most importantly, our results indicate the formation of two distinct water layers at the SiO2 surface covered by a large density of hydroxyl groups. Further analysis of the data suggests a highly confined first layer where the water molecules assume preferential hydrogen-down orientation and a second layer whose behavior and characteristics are highly dependent on those of the first layer through a well-organized hydrogen bond network. The results suggest that water−water interactions, in particular hydrogen bonds, may be largely responsible for macroscopic interfacial properties such as adsorption and contact angle.

Although carbon nanotubes have attracted enormous research interest, their practical application is still hindered, primarily, by the difficulty of separating them into samples monodispersed in diameter, chirality, and length. Recent advances show that ultracentrifugating carbon nanotube dispersions stabilized by surfactants is a promising route for achieving the desired separation. For further perfectioning this procedure it is necessary to know how surfactants adsorb on nanotubes of different diameters, which determines the nanotube-surfactant aggregate effective density and the nanotube-nanotube potential of mean force. Because only limited experimental data are available to elucidate these phenomena, we report here an extensive all-atom molecular dynamics study on the morphology of sodium dodecyl sulfate (SDS) surfactant aggregates adsorbed on (6,6), (12,12), and (20,20) single walled carbon nanotubes at room conditions. Our calculations reveal that the nanotube diameter is the primary factor that determines the morphology of the aggregates because of a competition between the entropic and energetic advantage encountered by the surfactants when they wrap one nanotube, and the enthalpic penalty faced during this process due to bending of the surfactant molecule. The data are in qualitative agreement with the neutron scattering results reported by Yurekli et al. [J. Am. Chem. Soc. 2004, 126, 9902], and for the first time provide an atomic-level description helpful in designing better separation, as well as stabilization techniques for aqueous carbon nanotube dispersions.

Inter facial water properties at the alumina surface were investigated via all-atom equilibrium molecular dynamics simulations at ambient temperature. Al-terminated and OHterminated alumina surfaces were considered to assess the structural and dynamic behavior of the first few hydration layers in contact with the substrates. Density profiles suggest water layering up to ∼10 Å from the solid substrate. Planar density distribution data indicate that water molecules in the first interfacial layer are organized in well-defined patterns dictated by the atomic terminations of the alumina surface. Interfacial water exhibits preferential orientation and delayed dynamics compared to bulk water. Water exhibits bulk-like behavior at distances greater than ∼10 Å from the substrate. The formation of an extended hydrogen bond network within the first few hydration layers illustrates the significance of water-water interactions on the structural properties at the interface.

Molecular dynamics simulations were employed to study the transport of water and ions through pores created on the basal plane of one graphene sheet (GS). Graphene pore diameters ranged from 7.5 to 14.5 Å. Different pore functionalities were considered, obtained by tethering various functional groups to the terminal carbon atoms. The ease of ion and water translocation across the pores was monitored by calculating the potential of mean force along the direction perpendicular to the GS pore. The results indicate that effective ion exclusion can be achieved only using nonfunctionalized (pristine) pores of diameter ~7.5 Å, whereas the ions can easily penetrate pristine pores of diameters ~10.5 and 14.5 Å. Carboxyl functional groups can enhance ion exclusion for all pores considered, but the effect becomes less pronounced as both the ion concentration and the pore diameter increase. When compared to a carbon nanotube of similar pore diameter, our results suggest that GS pores functionalized with COO(-) groups are more effective in excluding Cl(-) ions from passing through the membrane. Our results suggest that narrow graphene pores functionalized with hydroxyl groups remain effective at excluding Cl(-) ions even at moderate solution ionic strength. The results presented could be useful for the design of water desalination membranes.