Molecular simulation of adsorption and transport diffusion of model fluids in carbon nanotubes

Grand canonical Monte Carlo (GCMC) and dual-control-volume grand canonical molecular dynamics (DCV-GCMD) simulations were carried out with Lennard-Jones model fluids in carbon nanotubes, with the objective of investigating the effect of varying molecular properties on adsorption and diffusion. The influence of the molecular weight, and the Lennard Jones parameters σ (a measure of the molecule size) and ? (a measure of the interaction strength) on adsorption isotherms, fluxes, and transport diffusivities was studied. For these simulations, the properties of component 1 in the mixture were held constant and one of the properties of component 2 was changed systematically. Furthermore, the validity of Graham's law, which relates the fluxes of two counter diffusing species to their molecular weight, was investigated on a molecular level. Graham's law is fulfilled for the whole range of molecular weights and Lennard-Jones parameters σ investigated. However, large deviations were observed for large values of ?₂. Here, the interaction of the two components in the mixture becomes so strong that component 1 is dragged along by component 2.     

D2/H2 quantum sieving in microporous carbons: a theoretical study on the effects of pore size and pressure

The adsorption of hydrogen and deuterium in slit-shaped carbon pores is studied by grand canonical Monte Carlo simulations. All interactions are assumed to be of Lennard–Jones type, while the Feynman–Hibbs expression is used to account for quantum effects. The interaction energy of both isotopes inside the slit pore space is discussed thoroughly. Furthermore, pure component adsorption isotherms of both isotopes were simulated at 77?K for pressures up to 20?bar in slit pores having widths of up to 2.0?nm. According to our simulations, in equilibrium, slit pores reveal slight deuterium selectivity over hydrogen, and this quantum-based selectivity depends both on pressure and pore size.     

Adsorption of paracresol in silicalite-1 and pure silica faujasite. A comparison study using molecular simulation

This paper presents the results on the Grand-Canonical Monte Carlo simulations of the adsorption of the paracresol uremic toxin and water into the silicalite-1 and pure silica faujasite zeolites. The co-adsorption of water and paracresol seems to proceed along a cooperation effect between the toxin and the solvent. A model of adsorption that accounts for the effect of the solvent has been elaborated and verified using experimental isotherms. The model is based on the Langmuir isotherm in which an apparent adsorption enthalpy is used that changes with the concentration of the solute. The new expression for the isotherm reproduces the experimental isotherm with good accuracy and physical interpretation is given to justify the model.     

Heterogeneity of activated carbons in adsorption of phenols from aqueous solutions—Comparison of experimental isotherm data and simulation predictions

Surface heterogeneity of activated carbons is usually characterized by adsorption energy distribution (AED) functions which can be estimated from the experimental adsorption isotherms by inverting integral equation. The experimental data of phenol adsorption from aqueous solution on activated carbons prepared from polyacrylonitrile (PAN) and polyethylene terephthalate (PET) have been taken from literature. AED functions for phenol adsorption, generated by application of regularization method have been verified. The Grand Canonical Monte Carlo (GCMC) simulation technique has been used as verification tool. The definitive stage of verification was comparison of experimental adsorption data and those obtained by utilization GCMC simulations. Necessary information for performing of simulations has been provided by parameters of AED functions calculated by regularization method.     

Elucidating alkane adsorption in sodium-exchanged zeolites from molecular simulations to empirical equations

Configurational-bias Monte Carlo (CBMC) simulations provide adsorption isotherms, Henry coefficients and heats of adsorption of linear alkanes in sodium-exchanged MFI- and FAU-type zeolites. These simulations were carried out using our newly developed force field that reproduces experimental sodium positions in the dehydrated zeolites, and successfully predicts alkane adsorption properties over a wide range of sodium cation densities, temperatures, and pressures. We derived empirical expressions from the simulation data to describe the adsorption of linear alkanes in MFI- and FAU-type zeolites. These expressions afford a suitable substitute for complex CBMC simulations. In the low coverage regime we provide simple expressions that adequately describe the Henry coefficient and adsorption enthalpy of n-alkanes as a function of sodium density and temperature. The predicted Henry coefficients and heats of adsorption compare extremely well to available experimental data. In the high coverage regime we provide an expression for saturation capacities of linear alkanes in the zeolite. This expression, combined with the expression for the Henry coefficients, provides of the complete adsorption isotherms of pure adsorbents and mixtures, in good agreement with the adsorption isotherms obtained from CBMC.     

Grand canonical Monte Carlo simulation of isotherm for hydrogen adsorption on nanoporous siliceous zeolites at room temperature

Zeolites belong to a most prominent class of nanoporous materials which have been considered as potential sorbents for hydrogen storage. The adsorption of hydrogen molecules on purely siliceous zeolites such as ACO, MEP, ASV, ANA, RWY, and RHO, which encompass a range of different pore structures and their chemical compositions has been simulated employing Grand Canonical Monte Carlo (GCMC) procedure for a temperature range of 250-325 K, and a pressure range of 0-10 kbar. The effects of pore structure of zeolites, temperature and pressure on the hydrogen adsorption has been examined. The results clearly show that the number of adsorbed hydrogen molecules at high pressure, only depends on pore diameter, and the temperature effect on the adsorption decreases with decrease in the number of adsorbed of hydrogen molecules.     

Molecular simulation of adsorption of NO and CO2 mixtures by a Cu-BTC metal organic framework

Environmental problems due to the discharge of gases, including NO and CO₂, in addition, diseases caused by improper concentration of NO and CO₂ in vivo must be resolved. In this study, Grand canonical Monte Carlo (GCMC) simulations are combined with density functional theory (DFT) to calculate the adsorption of NO and CO₂ from a dual-component mixture to the Cu-BTC metal organic framework. The results show that the adsorption isotherms for various molar ratios of the gaseous mixture followed a Langmuir distribution. At higher pressures more CO₂ than NO was adsorbed by Cu-BTC, with NO showing a tendency to desorb. However, better results for adsorption of NO were observed at lower pressures. For the different pressure and molar ratios of the gaseous mixture examined, more CO₂ than NO was always adsorbed. Compared with three-way catalysts, Cu-BTC offers benefits to adsorption of CO₂ and NO from gaseous mixtures without increased durability problems.     

A new simulation method for the determination of phase equilibria in mixtures in the grand canonical ensemble

A grand canonical Monte Carlo (GCMC) simulation method is presented for the determination of the phase equilibria of mixtures. The coexistence is derived by expanding the pressure into a Taylor series as a function of the temperature and the chemical potentials that are the independent intensive variables of the grand canonical ensemble. The coefficients of the Taylor series can be calculated from ensemble averages and fluctuation formulae that are obtained from GCMC simulations in both phases. The method is able to produce the equilibrium data in a certain domain of the (T, p) plane from two GCMC simulations. The vapour-liquid equilibrium results obtained for a Lennard-Jones mixture agree well with the corresponding Gibbs ensemble Monte Carlo data.     

Characterization of nanoporous carbons by combining CO2 and H2 sorption data with the Monte Carlo simulations

The Monte Carlo method in its grand ensemble variant (GCMC) is used in combination with experimental data in order to characterize microporous carbons and obtain the optimal pore size distribution (PSD). In particular, the method is applied in the case of AX-21 carbon. Adsorption isotherms of CO₂ (253 and 298 K) and H₂ (77 K) up to 20 bar have been measured, while the computed isotherms resulted from the GCMC simulations for several pore widths up to 3.0 nm. For the case of H₂ at 77 K quantum corrections were introduced with the application of the Feynman-Hibbs (FH) effective potential. The adsorption isotherms were used either individually or in a combined manner in order to deduce PSDs and their reliability was examined by the ability to predict the experimental adsorption isotherms. The combined approach was found to be capable of reproducing more accurately all the available experimental isotherms.     

Adsorption of selenium wires in silicalite-1 zeolite: a first order transition in a microporous system

A tight binding grand canonical Monte Carlo simulation of the adsorption of selenium in silicalite-1 zeolite is presented. The calculated adsorption-desorption isotherms exhibit characteristic features of a first order transition, unexpected for adsorption in a microporous system with pore size of the order of 0.5 to 0.6 nm. We analyze this behavior as a result of the favored twofold coordinated chain structure of selenium that grows inside the complex three-dimensional microchannel network of silicalite. This analysis is confirmed by simpler calculations of a lattice gas-type model.     

A new equation of state for associating Lennard–Jones fluids with two sites: small bond angle

ABSTRACT

We developed a new equation of state for Lennard–Jones spheres with two short-ranged, directional association sites. The theory is novel in that association is dependent on bond angle between the two sites, and formation of self-assembled linear and cyclic clusters is predicted in the model. The competition between ring and chain formations at various densities and temperatures is predicted by the theory and verified by Monte Carlo simulations. It was found that closed-loop structures become important at low temperatures and densities. Also, at fixed association energy, intensifying the Lennard–Jones energy reduces the extent of association in the fluid. The theory and simulation are in excellent agreement.     

BC3复合纳米管的储氢性能研究

采用巨正则蒙特卡罗方法（GCMC）研究了BC3复合纳米管的物理吸附储氢性能,获得了该纳米管在不同温度和压强下的吸附等温线,及其在不同条件下的物理储氢吸附量,并和相应的碳纳米管进行了对比研究。结果表明,BC3纳米管在所有条件下的储氢性能均优于相应的碳纳米管,因而它是一种比碳纳米管更强的氢存储介质,并从纳米管和H2分子以及H2分子和H2分子之间的平均总相互作用能的分布情况等因素出发解释了这两种纳米管有不同储氢行为的原因。     

Multibaric–multithermal ensemble simulations for fluid systems

We present new generalized-ensemble molecular dynamics and Monte Carlo simulation methods, which we refer to as the multibaric–multithermal algorithms. The multibaric–multithermal simulations perform random walks widely both in the potential-energy space and in the volume space. From only one simulation run, therefore, one can calculate isobaric–isothermal-ensemble averages in wide ranges of temperature and pressure. We test the effectiveness of this algorithm by applying it to a Lennard–Jones 12-6 potential system.     

Computation of partial molar properties using continuous fractional component Monte Carlo

ABSTRACT

An alternative method for calculating partial molar excess enthalpies and partial molar volumes of components in Monte Carlo (MC) simulations is developed. This method combines the original idea of Frenkel, Ciccotti, and co-workers with the recent continuous fractional component Monte Carlo (CFCMC) technique. The method is tested for a system of Lennard–Jones particles at different densities. As an example of a realistic system, partial molar properties of a [NH₃, N₂, H₂] mixture at chemical equilibrium are computed at different pressures ranging from P = 10 to 80 MPa. Results obtained from MC simulations are compared to those obtained from the PC-SAFT Equation of State (EoS) and the Peng–Robinson EoS. Excellent agreement is found between the results obtained from MC simulations and PC-SAFT EoS, and significant differences were found for PR EoS modelling. We find that the reaction is much more exothermic at higher pressures.     

Long range relationship between Morse and Lennard–Jones potential energy functions

Arising from the use of the Morse function–which is well-known for its applicability for describing bonded interaction energy–in van der Waals systems, an attempt is made herein to express parameters of the Lennard–Jones potential function in terms of the Morse function to enable normalized comparison. In a departure from previous work where the parameter relationships enforce equal curvature at the minimum well-depth, the present approach replaces this rule with equal area above the curves for 1?≤?(r/R)?≤?∞. Results show good approximations of the Morse function to the Lennard–Jones curve and vice versa. Comparison with the previous relation for short range interaction shows that the present relations offer superior agreement with the Lennard–Jones function over a longer range. The conversion relations provide a cost-effective, less time-consuming and reasonably reliable method for obtaining Morse parameters from those of the Lennard–Jones function and vice versa.     

Surface phase transitions of multiple-site associating fluids

Surface phase transitions of Lennard–Jones (LJ) based two- and four-site associating fluids have been studied for various associating strengths using grand-canonical transition matrix Monte Carlo simulations. Our results suggest that, in the case of a smooth surface, represented by a LJ 9-3-type potential, multiple-site associating fluids display a prewetting transition within a certain temperature range. However, the range of the prewetting transition decreases with increasing associating strength and increasing number of sites on the fluid molecules. With the addition of associating sites on the surface, a quasi-2D vapor–liquid transition may appear, which is observed at a higher surface site density for weaker associating fluids. The prewetting transition at lower associating strength is found to shift towards the quasi-2D vapor–liquid transition with increasing surface site density. However, for highly associating fluids, the prewetting transition is still intact, but shifts slightly towards the lower temperature range. Adsorption isotherms, chemical potentials and density profiles are used to characterize surface phase transitions.     

单壁碳纳米管低温及常温下储氢行为的模拟计算研究

采用巨正则系综蒙特卡罗方法, 通过含有此方法模块的GULP软件, 系统地研究了扶手椅式单壁碳纳米管在低温和常温下的储氢性能, 给出了5种半径的扶手椅管在液氮温度(77 K)和常温(280 K)下的吸附等温线, 同一管径在不同温度不同压强下氢分子在碳纳米管中的分布构型图等. 对77 K和280 K下不同压强不同管径的碳纳米管储氢能力做了较为全面的对比分析, 最后根据模拟计算的结果, 对碳纳米管储氢能力的强化提出了一些建设性意见.     

Hydrophilic and hydrophobic adsorption on Y zeolites

The uniform large micropores of hydrothermally stable Y zeolites are used widely to confine both polar and non-polar molecules. This paper compares the physisorption of water, methanol, cyclohexane, benzene and other adsorbates over various Y zeolites. These adsorbents are commercial products with reproducibly controllable physical and chemical characteristics. Results indicate that the type I isotherms typical for micropore adsorption can turn into type II or type III isotherms depending on either or both the hydrophobicity of the adsorbent and the polarity of the adsorbate. Methanol produced a rare type V isotherm not reported over zeolites before. Canonical and grand canonical Monte Carlo molecular simulations with Metropolis importance sampling reproduced the experimental isotherms and showed characteristic geometric patterns for molecules confined in Na-X, Na-Y, dealuminated Y, and ZSM5 structures. Adsorbate—adsorbate interactions seem to determine the micropore condensation of both polar and non-polar molecules. Exchanged ions and lattice defects play a secondary role in shaping the adsorption isotherms. The force field of hydrophobic Y appears to exert an as yet unexplored sieving effect on adsorbates having different dipole moments and partial charge distributions. This mechanism is apparently different from both the monolayer formation controlled adsorption on hydrophobic mesopores and macropores and the polarizability and small-pore opening controlled micropore confinement in hydrophobic ZSM5.     

Adsorption and interfacial phenomena of a Lennard-Jones fluid adsorbed in slit pores: DFT and GCMC simulations

ABSTRACT

Confinement of fluids in porous media leads to the presence of solid–fluid (SF) interfaces that play a key role in many different fields. The experimental characterisation of SF interfacial properties, in particular the surface tension, is challenging or not accessible. In this work, we apply mean-field density functional theory (DFT) to determine the surface tension and also density profile of a Lennard-Jones fluid in slit-shaped pores for realistic amounts of adsorbed molecules. We consider the pore walls to interact with fluid molecules through the well-known 10-4-3 Steele potential. The results are compared with those obtained from Monte Carlo simulations in the Grand Canonical Ensemble (GCMC) using the test-area method. We analyse the effect on the adsorption and interfacial phenomena of volume and energy factors, in particular, the pore diameter and the ratio between SF and fluid–fluid dispersive energy parameters, respectively. Results from DFT and GCMC simulations were found to be comparable, which points to their reliability.     

Monte Carlo study of binary mixtures adsorbed on square lattices

The monolayer adsorption of interacting binary mixtures on 2D square lattices has been studied through grand canonical Monte Carlo simulation in the framework of the lattice-gas model. The process has been monitored through total and partial isotherms and differential heats of adsorption corresponding to both species of the mixture. Repulsive lateral interactions between the adsorbed particles have been considered, resulting in a rich variety of structural orderings in the adlayer. At the end of this work, the phase diagram characterizing the transitions occurring in the system has been determined. A nontrivial interdependence between the partial surface coverage of both species was observed and discussed.