Francisco R. Hung

Molecular modeling of freezing of simple fluids confined within carbon nanotubes

We report Monte Carlo simulation results for freezing of Lennard-Jones carbon tetrachloride confined within model multiwalled carbon nanotubes of different diameters. The structure and thermodynamic stability of the confined phases, as well as the transition temperatures, were determined from parallel tempering grand canonical Monte Carlo simulations and free-energy calculations. The simulations show that the adsorbate forms concentric molecular layers that solidify into defective quasi-two-dimensional hexagonal crystals. Freezing in such concentric layers occurs via intermediate phases that show remnants of hexatic behavior, similar to the freezing mechanism observed for slit pores in previous works. The adsorbate molecules in the inner regions of the pore also exhibit changes in their properties upon reduction of temperature. The structural changes in the different regions of adsorbate occur at temperatures above or below the bulk freezing point, depending on pore diameter and distance of the adsorbate molecules from the pore wall. The simulations show evidence of a rich phase behavior in confinement; a number of phases, some of them inhomogeneous, were observed for the pore sizes considered. The multiple transition temperatures obtained from the simulations were found to be in good agreement with recent dielectric relaxation spectroscopy experiments for CCl(4) confined within multiwalled carbon nanotubes.

Modeling Micelle-Templated Mesoporous Material SBA-15: Atomistic Model and Gas Adsorption Studies

We report the development of a realistic molecular model for mesoporous silica SBA-15, which includes both the large cylindrical mesopores and the smaller micropores in the pore walls. The methodology for modeling the SBA-15 structure involves molecular and mesoscale simulations combined with geometrical interpolation techniques. First, a mesoscale model is prepared by mimicking the synthesis process using lattice Monte Carlo simulations. The main physical features of this mesoscale pore model are then carved out of an atomistic silica block; both the mesopores and the micropores are incorporated from the mimetic simulations. The calculated pore size distribution, surface area, and simulated TEM images of the model structure are in good agreement with those obtained from experimental samples of SBA-15. We then investigate the adsorption of argon in this structure using Grand Canonical Monte Carlo (GCMC) simulations. The adsorption results for our SBA-15 model are compared with those for a similar model that does not include the micropores; we also compare with results obtained in a regular cylindrical pore. The simulated adsorption isotherm for the SBA-15 model shows semiquantitative agreement with the experimental isotherm for a SBA-15 sample having a similar pore size. We observe that the presence of the micropores leads to increased adsorption at low pressure compared to the case of a model without micropores in the pore walls. At higher pressures, for all models, the filling proceeds via the monolayer-multilayer adsorption on the mesopore surface followed by capillary condensation, which is mainly controlled by the mesopore diameter and is not influenced by the presence of the micropores.

Freezing/melting behaviour within carbon nanotubes

We report a study of the freezing and melting of fluids confined within multi-walled carbon nanotubes with an internal diameter of 5 nm, using experimental measurements and molecular simulations. Dielectric relaxation spectroscopy was used to determine the experimental melting points and relaxation times of nitrobenzene and carbon tetrachloride within carbon nanotubes, and parallel tempering Monte Carlo simulations in the grand canonical ensemble were performed for confined carbon tetrachloride. The simulations show that the adsorbate forms concentric layers that solidify into quasi-two-dimensional hexagonal crystals with defects; highly defective microcrystalline regions are formed in the inner layers, owing to the strong geometrical constraints. Our simulations show no formation of common three-dimensional crystalline structures (fcc, hcp, bcc, sc or icosahedral) in confinement. The results suggest the presence of inhomogeneous phases (i.e., combinations of crystalline and liquid regions) within the pore over extended temperature ranges. Our results indicate that the outer layers of adsorbate solidify at temperatures slightly higher than the bulk freezing point, whereas the inner layers freeze at lower temperatures. The simulation results are in good agreement with the experimental measurements.

Freezing and melting of binary mixtures confined in a nanopore

This paper reports on a Grand Canonical Monte Carlo study of the freezing and melting of Lennard–Jones Ar/Kr mixtures confined in a slit pore composed of two strongly attractive structureless walls. For all molar compositions and temperatures, the pore, which has a width of 1.44u2009nm, accommodates two contact layers and one inner layer. Different wall/fluid interactions are considered, corresponding to pore walls that have a larger affinity for either Ar or Kr. The solid/liquid phase diagram of the confined mixture is determined and results compared with data for the bulk mixture. The structure of the confined mixture is studied using 2D order parameters and both positional g(r) and bond orientational G6(r) pair correlation functions. It is found that in the confined solid phase, both the contact and inner layers have a hexagonal crystal structure. It is shown that the freezing temperature of the Ar/Kr confined mixture is higher than the bulk freezing point for all molar compositions. Also, it is found that the freezing temperature becomes larger as the ratio α of the wall/fluid to the fluid/fluid interactions increases, in agreement with previous simulation studies on pure substances confined in nanopores. In the case of pore walls having a stronger affinity for Kr atoms (ε Ar/W<ε Kr/W), it is observed that both the contact and inner layers of the confined mixture undergo, at the same temperature, a transition from the liquid phase to the crystal phase. The freezing of Ar/Kr mixtures confined between the walls having a stronger affinity for Ar (ε Ar/Wu2009>u2009ε Kr/W) is more complex: for Kr molar concentration lower than 0.35, we observe the presence of an intermediate state between all layers being 2D hexagonal crystals and all the layers being liquid. This intermediate state consists of a crystalline contact layer and a liquid-like inner layer. It is also shown that the qualitative variations of the increase of freezing temperature with the molar composition depend on the affinity of the pore wall for the different components. These results confirm that, in addition to the parameter α the ratio of the wall/fluid interactions for the two species, η=ϵAr/W/ϵKr/W, is a key variable in determining the freezing and melting behaviour of the confined mixture.

Freezing and melting of azeotropic mixtures confined in nanopores: experiment and molecular simulation

The paper reports on a qualitative comparison between experimental measurements and molecular simulations of the freezing and melting of azeotropic mixtures confined in nanoporous materials. Dielectric relaxation spectroscopy was used to determine the experimental solid/liquid phase diagram of CCl4/C6H12 mixtures confined in activated carbon fibres. Grand Canonical Monte Carlo simulations combined with the parallel tempering technique were used to model the freezing of the azeotropic Lennard–Jones mixture Ar/CH4 in a graphite slit pore. The structure of the crystal phase in the simulations is investigated by means of positional and bond-orientational pair correlation functions and appropriate bond-order parameters. Both simulations and experiments show that the phase diagram of the confined mixture is of the same type as that for the bulk, but the solid/liquid coexistence lines are located at higher temperatures. The effect of confinement and of the wall/fluid interaction on the location of the azeotrope is discussed.

Adsorption of Gas-Phase Phenanthrene on Atmospheric Water and Ice Films

The adsorption of gas-phase phenanthrene on atmospheric water and ice films was investigated in a flow-tube reactor with a view to understanding the processing of semi-volatile organic compounds by fog and snow. Air-water (ice) interface partition constants were obtained by measuring the mass uptake of phenanthrene vapor on thin water and ice films with varying thickness. Adsorption enthalpies and entropies were obtained from the temperature dependence of the interfacial partition constants. The surface adsorption is the predominant mechanism for the uptake of phenanthrene in water and ice films with small film thickness or at low temperature. The adsorption of phenanthrene to ice resembles that to sub-cooled water and theres no significant difference between the adsorption of phenanthrene to water and that to quasi liquid layer (QLL) if we take into account the uncertainties on the thermodynamic quantities measured. Molecular dynamics simulations of phenanthrene at air/water and air/ice interfaces support these experimental observations. The interfacial air-water and air-ice partition constants of phenanthrene increased greatly in the presence of surface-active substances, indicating that surface active materials effectively enhanced the uptake of organic compounds by atmospheric water and ice films.

Freezing/melting of Lennard-Jones fluids in carbon nanotubes

We report molecular simulation and experimental results for the freezing/melting behavior of Lennard-Jones fluids adsorbed in pores of cylindrical geometry, using simple models for multiwalled carbon nanotubes (MWNTs) of inner diameter 5nm. For cylindrical pores, our results for a D=9.7σff MWNT show no formation of regular three-dimensional crystalline structures. They also suggest that the outer layers experience an increase in the freezing temperature, while the inner layers provoke a depression in the freezing temperature with respect to the bulk freezing point. Dielectric relaxation spectroscopy shows a solid-fluid transition at 234K for CCl4 in these MWNTs that is in qualitative agreement with that determined in our simulations for the inner adsorbed layers.

A Monte Carlo study of capillary condensation of krypton within realistic models of templated mesoporous silica materials

We report molecular simulations of Kr adsorption at 87 and 100 K in three atomistic silica mesopores with an average pore diameter of 6.4 nm: (a) a pore that keeps the morphological features of a MCM-41 mesoscale model, generated from lattice Monte Carlo simulations mimicking its fabrication process; (b) a smooth, regular cylindrical pore; and (c) a cylindrical pore with constriction. Surface roughness and structural defects significantly affect Kr adsorption: marked differences were observed in the adsorption isotherms, isosteric heat curves and pore filling mechanisms for the three pore models. Our results suggest that the molecular-level surface disorder for the first pore model is too high, but its roughness at larger length scales (10-50 A), as determined from simulated SANS spectrum, is in agreement with experimental results. The dense phase of Kr inside the three pore models exhibits a liquid-like global structure, even though the temperatures considered are well below the bulk triple point.

Modeling triblock surfactant templated mesoporous silicas (MCF and SBA-15) : A mimetic simulation study

We have developed models for templated mesoporous silicas such as Mesostructured Cellular Foams and SBA-15. The first part of our work elaborates the effect of oil concentration on the pore morphology of the triblock surfactant templated mesoporous materials. Our Lattice Monte Carlo simulations mimic the synthesis process by equilibrating a mixture of triblock surfactant, oil, water and silica at a constant temperature and density. With increasing oil concentration, we find the pore geometry to change according to the sequence: cylinders → lamellae → mesocells, which is in qualitative agreement with experimental results. In the second part of our work, we develop realistic atomistic models of the SBA-15 material, starting from the mesoscale model obtained from Lattice Monte Carlo simulations. Both the pore surface heterogeneity and the micropores are derived from the mimetic simulations. The simulated TEM and pore size distribution of the model qualitatively resemble the real material.

An experimental study of melting of CCl4 in carbon nanotubes

We report dielectric relaxation spectroscopy measurements of the melting point of carbon tetrachloride confined within open-tip multi-walled carbon nanotubes with two different pore diameters, 4.0 and 2.8 nm. In both cases, a single transition temperature well above the bulk melting point was obtained for confined CCl4. These results contrast with what was obtained in our previous measurements using carbon nanotubes with a pore diameter of 5.0 nm, where multiple transition temperatures both above and below the bulk melting point of CCl4 were observed. Our experimental measurements are consistent with our recent molecular simulation results (F. R. Hung, B. Coasne, E. E. Santiso, K. E. Gubbins, F. R. Siperstein and M. Sliwinska-Bartkowiak, J. Chem. Phys., 2005, 122, 144706). Although the simulations overestimate the temperatures in which melting upon confinement occurs, both simulations and experiments suggest that all regions of adsorbate freeze at the same temperature, and that freezing occurs at higher temperatures upon reduction of the pore diameter.