Molecular Dynamics Simulation of Ice Crystal Growth Inhibition by Hexadecyl-trimethyl-ammonium Bromide.

Recent experiments have found hexadecyl-trimethyl-ammonium bromide (CTAB) to have superior ice nucleation inhibition properties [ J. Phys. Chem. B 121, 6580]. The mechanism of how the inhibition takes place remains unclear. Therefore, molecular dynamics was used to simulate ice crystallization of a water/CTAB/ice system. The ice crystallization rate for a pure water system was compared for the basal [0001], first prism [101̅0], and secondary prism plane [112̅0], where the basal plane grew the slowest followed by the first prism plane. When CTAB was added to the ice-liquid water system, crystallization was clearly impeded. Even when ice starts growing away from the CTAB molecule, the hydrophilic head would at some point protrude and get caught in the water/ice interface. Once the head of the CTAB was encapsulated in the advancing interface, the hydrophobic body would wriggle around and disrupt the formation of hydrogen bond networks that are essential for ice growth. When the interface clears the length of the body of the CTAB molecule, ice crystallization resumes at its normal pace. In summary, the inhibition of ice growth is a combination of the hydrophilic head acting as an anchor and the dynamic motion of the hydrophobic tail hindering stable hydrogen bonding for ice growth.

Separation of water-ethanol solutions with carbon nanotubes and electric fields.

Bioethanol has been used as an alternative energy source for transportation vehicles to reduce the use of fossil fuels. The separation of water-ethanol solutions from fermentation processes is still an important issue in the production of anhydrous ethanol. Using molecular dynamics simulations, we investigate the effect of axial electric fields on the separation of water-ethanol solutions with carbon nanotubes (CNTs). In the absence of an electric field, CNT-ethanol van der Waals interactions allow ethanol to fill the CNTs in preference to water, i.e., a separation effect for ethanol. However, as the CNT diameter increases, this ethanol separation effect significantly decreases owing to a decrease in the strength of the van der Waals interactions. In contrast, under an electric field, the energy of the electrostatic interactions within the water molecule structure induces water molecules to fill the CNTs in preference to ethanol, i.e., a separation effect for water. More importantly, the electrostatic interactions are dependent on the water molecule structure in the CNT instead of the CNT diameter. As a result, the separation effect observed under an electric field does not diminish over a wide CNT diameter range. Moreover, CNTs and electric fields can be used to separate methanol-ethanol solutions too. Under an electric field, methanol preferentially fills CNTs over ethanol in a wide CNT diameter range.

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.

Phase diagram of water in carbon nanotubes.

A phase diagram of water in single-walled carbon nanotubes at atmospheric pressure is proposed, which summarizes ice structures and their melting points as a function of the tube diameter up to 1.7 nm. The investigation is based on extensive molecular dynamics simulations over numerous thermodynamic states on the temperature-diameter plane. Spontaneous freezing of water in the simulations and the analysis of ice structures at 0 K suggest that there exist at least nine ice phases in the cylindrical space, including those reported by x-ray diffraction studies and those unreported by simulation or experiment. Each ice has a structure that maximizes the number of hydrogen bonds under the cylindrical confinement. The results show that the melting curve has many local maxima, each corresponding to the highest melting point for each ice form. The global maximum in the melting curve is located at approximately 11 A, where water freezes in a square ice nanotube.

Water­methanol separation with carbon nanotubes and electric fields.

Methanol is used in various applications, such as fuel for transportation vehicles, fuel cells, and in chemical industrial processes. Conventionally, separation of methanol from aqueous solution is by distillation. However, this method consumes a large amount of energy; hence development of a new method is needed. In this work, molecular dynamics simulations are performed to investigate the effect of an electric field on water­methanol separation by carbon nanotubes (CNTs) with diameters of 0.81 to 4.07 nm. Without an electric field, methanol molecules fill the CNTs in preference to water molecules. The preference of methanol to occupy the CNTs over water results in a separation effect. This separation effect is strong for small CNT diameters and significantly decreases with increasing diameter. In contrast, under an electric field, water molecules strongly prefer to occupy the CNTs over methanol molecules, resulting in a separation effect for water. More interestingly, the separation effect for water does not decrease with increasing CNT diameter. Formation of water structures in CNTs induced by an electric field has an important role in the separation of water from methanol.