Configurational-bias Monte Carlo Simulations Research Articles

Halogen-Decorated Metal-Organic Frameworks for Efficient and Selective CO2 Capture, Separation, and Chemical Fixation with Epoxides under Mild Conditions.

In the present work, three novel halogen-appended cadmium(II) metal-organic frameworks [Cd2(L1)2(4,4'-Bipy)2]n·4n(DMF) (1), [Cd2(L2)2(4,4'-Bipy)2]n·3n(DMF) (2), and [Cd(L3)(4,4'-Bipy)]n·2n(DMF) (3) [where L1 = 5-{(4-bromobenzyl)amino}isophthalate; L2 = 5-{(4-chlorobenzyl)amino}isophthalate; L3 = 5-{(4-fluorobenzyl)amino}isophthalate; 4,4'-Bipy = 4,4'-bipyridine; and DMF = N,N'-dimethylformamide] have been synthesized under solvothermal conditions and characterized by various analytical techniques. The single-crystal X-ray diffraction analysis demonstrated that all the MOFs feature a similar type of three-dimensional structure having a binuclear [Cd2(COO)4(N)4] secondary building block unit. Moreover, MOFs 1 and 2 contain one-dimensional channels along the b-axis, whereas MOF 3 possesses a 1D channel along the a-axis. In these MOFs, the pores are decorated with multifunctional groups, i.e., halogen and amine. The gas adsorption analysis of these MOFs demonstrate that they display high uptake of CO2 (up to 5.34 mmol/g) over N2 and CH4. The isosteric heat of adsorption (Qst) value for CO2 at zero loadings is in the range of 18-26 kJ mol-1. In order to understand the mechanism behind the better adsorption of CO2 by our MOFs, we have also performed configurational bias Monte Carlo simulation studies, which confirm that the interaction between our MOFs and CO2 is stronger compared to those with N2 and CH4. Various noncovalent interactions, e.g., halogen (X)···O, Cd···O, and O···O, between CO2 and the halogen atom, the Cd(II) metal center, and the carboxylate group from the MOFs are observed, respectively, which may be a reason for the higher carbon dioxide adsorption. Ideal adsorbed solution theory (IAST) calculations of MOF 1 demonstrate that the obtained selectivity values for CO2/CH4 (50:50) and CO2/N2 (15:85) are ca. 28 and 193 at 273 K, respectively. However, upon increasing the temperature to 298 K, the selectivity value (S = 34) decreases significantly for the CO2/N2 mixture. We have also calculated the breakthrough analysis curves for all the MOFs using mixtures of CO2/CH4 (50:50) and CO2/N2 (50:50 and 15:85) at different entering gas velocities and observed larger retention times for CO2 in comparison with other gases, which also signifies the stronger interaction between our MOFs and CO2. Moreover, due to the presence of Lewis acidic metal centers, these MOFs act as heterogeneous catalysts for the CO2 fixation reactions with different epoxides in the presence of tetrabutyl ammonium bromide (TBAB), for conversion into industrially valuable cyclic carbonates. These MOFs exhibit a high conversion (96-99%) of epichlorohydrin (ECH) to the corresponding cyclic carbonate 4-(chloromethyl)-1,3-dioxolan-2-one after 12 h of reaction time at 1 bar of CO2 pressure, at 65 °C. The MOFs can be reused up to four cycles without compromising their structural integrity as well as without losing their activity significantly.

Fundamental insights into the variety of factors that influence water/alcohol membrane permeation selectivity

The primary objective of this article is to develop a fundamental understanding of water/methanol and water/ethanol mixture permeation across microporous membrane constructs. Configurational-Bias Monte Carlo (CBMC) simulations were undertaken for water/methanol and water/ethanol mixture adsorption in all-silica zeolites (CHA, DDR, FAU, LTA) and ZIF-8. Additionally, Molecular Dynamics (MD) simulations were used to determine the intra-crystalline diffusivities in water/alcohol mixtures. The combination of CBMC and MD simulations allow the calculation of membrane permeation selectivities. This study provides insights into the influence of the structural properties of the microporous layer on the permeation selectivity. Another key result that emerges is that the water/alcohol permeation selectivity becomes increasingly in favor of water as the feed mixtures becomes richer in alcohol. The reason for the dependence can be traced to strong hydrogen bonding between water and alcohol molecular pairs resulting in cluster formation and enhanced water ingress; these results provide a rationalization of a number of membrane permeation studies in the literature. A corollary to the reported results is that the use of the Ideal Adsorbed Solution Theory (IAST) is unable to provide a quantitative description of mixture adsorption equilibrium and thermodynamic non-idealities need to be accounted for in modelling membrane permeation of water/alcohol mixtures.

Kinetics of zeolite-catalyzed heptane hydroisomerization and hydrocracking with CBMC-modeled adsorption terms: Zeolite Beta as a large pore base case

A reactor model that deconvolutes thermodynamics of adsorption of hydrocarbon in the pores of zeolite Beta, obtained by Configurational-bias Monte Carlo simulations, from intrinsic, intraporous kinetics of hydroisomerization and hydrocracking reactions, provides a good quantitative description of all significant reactions in the kinetic network for interconversion and cracking of different heptane isomers. Activation enthalpies obtained for intraporous reactions follow the expected order according to the carbenium ion formalism:methyl shift< ethyl shift < isom(B) ∼ crack(B2) < crack(B1) < crack(C) ∼ crack(D) < crack(E)and apparently within each isomerization class, in terms of carbenium ions formally involved:sec → tert < sec → sec ∼ tert → tert < tert → sec.except for the ethyl shift reaction forming 3-ethylpentane. Cracking happens primarily through 2,4-dimethylpentane (type B2), regardless of the initial reactant. The model can be subsequently used to separate the effect of pore structure on selective adsorption and on intraporous reaction kinetics. Zeolite Beta will serve as a base case for a comparison of different zeolite structures.

Nonane and Hexanol Adsorption in the Lamellar Phase of a Nonionic Surfactant: Molecular Simulations and Comparison to Ideal Adsorbed Solution Theory

Adsorption of n-nonane/1-hexanol (C9/C6OH) mixtures into the lamellar phase formed by a 50/50 w/w triethylene glycol mono-n-decyl ether (C10E3)/water system was studied using configurational-bias Monte Carlo simulations in the osmotic Gibbs ensemble. The interactions were described by the Shinoda-Devane-Klein coarse-grained force field. Prior simulations probing single-component adsorption indicated that C9 molecules preferentially load near the center of the bilayer, increasing the bilayer thickness, whereas C6OH molecules are more likely to be found near the interface of the polar and nonpolar moieties, swelling the bilayer in the lateral dimension. Here, we extend this work to binary C9/C6OH adsorption to probe whether the difference in the spatial preferences may lead to a synergistic effect and enhanced loadings for the mixture. Comparing loading trends and the thermodynamics of binary adsorption to unary adsorption reveals that C9-C9 interactions lead to the largest enhancement, whereas C9-C6OH and C6OH-C6OH interactions are less favorable for this bilayer system. Ideal adsorbed solution theory yields satisfactory predictions of the binary loading.

Highlighting the Anti-Synergy between Adsorption and Diffusion in Cation-Exchanged Faujasite Zeolites.

Using configurational-bias Monte Carlo simulations of adsorption equilibrium and molecular dynamics simulations of guest diffusivities of CO2, CH4, N2, and O2 in FAU zeolites with varying amounts of extra-framework cations (Na+ or Li+), we demonstrate that adsorption and diffusion do not, in general, proceed hand-in-hand. Stronger adsorption often implies reduced mobility. The anti-synergy between adsorption and diffusion has consequences for the design and development of pressure-swing adsorption and membrane separation technologies for CO2 capture and N2/O2 separations.

Adsorption separation of liquid-phase C5-C6 alkynes and olefins using FAU zeolite adsorbents

Isoprene is of great importance as a valuable monomer for most chemical industries owing to the increasing demand for synthetic rubber. To obtain polymer-grade olefins, the removal of alkyne compounds from isoprene is mandatory and challenging. Adsorption separation using zeolites is one of the most promising alternatives for alkyne/olefin separation. Herein, a combination of batch, fixed bed column experiments and configurational-bias grand canonical Monte Carlo (CB-GCMC) simulations was applied to study alkyne’s selective adsorption from binary liquid-phase isoprene/1-pentyne mixtures in faujasite (FAU) zeolites. The adsorption separation performance, including the adsorption capacity and selectivity, was obtained based on the liquid-phase measurement method developed in this study. FAU zeolites exhibited 218 mg/g alkyne adsorption capacity and relatively high adsorption selectivity at low alkyne concentrations. Liquid adsorption separation of linear alkyne/olefin mixtures, covering 1-pentyne/1-pentene (C5) and 1-hexyne/1-hexene (C6), in FAU zeolites, was performed further to investigate the separation performance for alkynes and olefins. The binary isotherms for the 1-pentyne/isoprene system and extended studied olefin/alkyne systems were reproduced well by CB-GCMC simulations. The visualized average occupation profiles of adsorbate molecules in FAU zeolites showed that alkyne and olefin molecules were mainly distributed near the 4-rings and 6-rings. The concentrated areas were arranged perpendicular to each other.

Using the spreading pressure to inter-relate the characteristics of unary, binary and ternary mixture permeation across microporous membranes

The primary objective of this article is to investigate the possibility of inter-relating the characteristics of unary, binary, and ternary mixtures across microporous zeolite membranes. Towards this end, we performed Configurational-Bias Monte Carlo (CBMC) simulations of mixture adsorption equilibrium, and Molecular Dynamics (MD) simulations of guest diffusivities in unary (CO2, CH4, N2, and H2), binary (CO2/CH4, CO2/N2, CH4/N2, CO2/H2), and ternary (CO2/CH4/N2, CO2/CH4/H2, CO2/N2/H2) mixtures in four zeolites: CHA, DDR, MFI, and FAU. The combined CBMC and MD data are used to obtain fundamental insights into the adsorption, diffusion, and permeation characteristics of the variety of guest/host combinations. Application of the Myers-Prausnitz theory shows that the adsorption selectivity for the i-j pair, Sads,ij, in ternary mixtures has practically the same value as for the binary i-j mixture, provided the comparison is made as the same surface potential Φ, a convenient and practical proxy for the spreading pressure π, that is calculable on the basis of the data on the unary isotherms of the constituent guests. For the mixtures investigated, departures from thermodynamic idealities do not cause deviations from the uniqueness of the Sads,ij vs Φ dependence because the ratios of the activity coefficients γi/γj also appear to uniquely depend on Φ.The surface potential Φ is also the thermodynamically correct metric to describe the loading dependence of diffusivities. Compared at the same Φ, the diffusion selectivity for the i-j pair, Sdiff,ij, in ternary mixtures has practically the same value as for the binary i-j mixture. Consequently, the permeation selectivity, Sperm,ij=Sads,ij×Sdiff,ij is also uniquely dependent on Φ. When compared at the same Φ, the component permeabilities, Πi for CO2, CH4, and N2 are found to be independent of the partners in the binary and ternary mixtures investigated and have practically the same as the values for the corresponding unary permeabilities.

The shape selectivity of zeolites in isobutane alkylation: An investigation using CBMC and MD simulations

The adsorption and diffusion behaviors of C8 isomers and C9 component as main products of the isobutane alkylation catalyzed by zeolites with different topologies were investigated using configurational bias Monte Carlo (CBMC) and MD simulations in this work. The adsorption capacity of zeolites at 353 K and 2.0 MPa relies on their pore volume with the order of FAU > BEA > LTL > MOR. The diffusion coefficient of C8 and C9 molecules increases with the decrease of loading and the increase of temperature, and the more compact molecules diffuse slower than the slimmer ones at low loadings while quicker at higher loadings. It was found that for zeolites, small adsorption heat of C8 isomers, or large molecular diffusion coefficient would correspond to a high selectivity of target alkylates. Particularly, BEA zeolite with large RPLD/LCD shows high reaction selectivity, rendering it a good candidate catalyst for C4 alkylation.

Partial Order–Disorder Transformation of Interpenetrated Porous Coordination Polymers

Controlling interpenetration and flexibility behaviors is intriguing and fundamental for porous coordination polymers. We report exceptional interpenetration behaviors involving controllable partia...

How Reliable Is the Ideal Adsorbed Solution Theory for the Estimation of Mixture Separation Selectivities in Microporous Crystalline Adsorbents?

Microporous crystalline adsorbents such as zeolites and metal–organic frameworks (MOFs) have potential use in a wide variety of separation applications. The adsorption selectivity Sads is a key metric that quantifies the efficacy of any microporous adsorbent in mixture separations. The Ideal Adsorbed Solution Theory (IAST) is commonly used for estimating the value of Sads, with unary isotherms of the constituent guests as data inputs. There are two basic tenets underlying the development of the IAST. The first tenet mandates a homogeneous distribution of adsorbates within the pore landscape. The second tenet requires the surface area occupied by a guest molecule in the mixture to be the same as that for the corresponding pure component. Configurational-bias Monte Carlo (CBMC) simulations are employed in this article to highlight several scenarios in which the IAST fails to provide a quantitatively correct description of mixture adsorption equilibrium due to a failure to conform to either of the two tenets underpinning the IAST. For CO2 capture with cation-exchanged zeolites and MOFs with open metal sites, there is congregation of CO2 around the cations and unsaturated metal atoms, resulting in failure of the IAST due to an inhomogeneous distribution of adsorbates in the pore space. Thermodynamic non-idealities also arise due to the preferential location of CO2 molecules at the window regions of 8-ring zeolites such as DDR and CHA or within pockets of MOR and AFX zeolites. Thermodynamic non-idealities are evidenced for water/alcohol mixtures due to molecular clustering engendered by hydrogen bonding. It is also demonstrated that thermodynamic non-idealities can be strong enough to cause selectivity reversals, which are not anticipated by the IAST.

Efficient and Highly Selective CO2 Capture, Separation, and Chemical Conversion under Ambient Conditions by a Polar-Group-Appended Copper(II) Metal–Organic Framework

A polar sulfone-appended copper(II) metal-organic framework (MOF; 1) has been synthesized from the dual-ligand approach comprised of tetrakis(4-pyridyloxymethylene)methane and dibenzothiophene-5,5'-dioxide-3,7-dicarboxylic acid under solvothermal conditions. This has been studied by different techniques that included single-crystal X-ray diffractometry, based on which the presence of Lewis acidic open-metal sites as well as polar sulfone groups aligned on the pore walls is identified. MOF 1 displays a high uptake of CO2 over N2 and CH4 with an excellent selectivity (S = 883) for CO2/N2 (15:85) at 298 K under flue gas combustion conditions. Additionally, the presence of Lewis acidic metal centers facilitates an efficient size-selective catalytic performance at ambient conditions for the conversion of CO2 into industrially valuable cyclic carbonates. The experimental investigations for this functional solvent-free heterogeneous catalyst are also found to be in good correlation with the computational studies provided by configurational bias Monte Carlo simulation for both CO2 capture and its conversion.

Using Molecular Simulations to Unravel the Benefits of Characterizing Mixture Permeation in Microporous Membranes in Terms of the Spreading Pressure.

The separation performance of microporous crystalline materials in membrane constructs is dictated by a combination of mixture adsorption and intracrystalline diffusion characteristics; the permeation selectivity Sperm is a product of the adsorption selectivity Sads and the diffusion selectivity, Sdiff. The primary objective of this article is to gain fundamental insights into Sads and Sdiff by use of molecular simulations. We performed configurational-bias Monte Carlo (CBMC) simulations of mixture adsorption equilibrium and molecular dynamics (MD) simulations of guest self-diffusivities of a number of binary mixtures of light gaseous molecules (CO2, CH4, N2, H2, and C2H6) in a variety of microporous hosts of different pore dimensions and topologies. Irrespective of the bulk gas compositions and bulk gas fugacities, the adsorption selectivity, Sads, is found to be uniquely determined by the adsorption potential, Φ, a convenient and practical proxy for the spreading pressure π that is calculable using the ideal adsorbed solution theory for mixture adsorption equilibrium. The adsorption potential Φ is also a proxy for the pore occupancy and is the thermodynamically appropriate yardstick to determine the loading and composition dependences of intracrystalline diffusivities and diffusion selectivities, Sdiff. When compared at the same Φ, the component permeabilities, Πi for CO2, CH4, and N2, determinable from CBMC/MD data, are found to be independent of the partners in the various mixtures investigated and have practically the same values as the values for the corresponding unary permeabilities. In all investigated systems, the H2 permeability in a mixture is significantly lower than the corresponding unary value. These reported results have important practical consequences in process development and are also useful for screening of materials for use as membrane devices.

Using Molecular Simulations for Elucidation of Thermodynamic Nonidealities in Adsorption of CO2-Containing Mixtures in NaX Zeolite.

Cation-exchanged zeolites are of potential use in pressure swing adsorption (PSA) technologies for CO2 capture applications. Published experimental data for CO2/CH4, CO2/N2, and CO2/C3H8 mixture adsorption in NaX zeolite, also commonly referred to by its trade name 13X, have demonstrated that the ideal adsorbed solution theory (IAST) fails to provide adequately accurate estimates of mixture adsorption equilibrium. In particular, the IAST estimates of CO2/CH4 and CO2/N2 selectivities are significantly higher than those realized in experiments. For CO2/C3H8 mixtures, the IAST fails to anticipate the selectivity reversal phenomena observed in experiments. In this article, configurational-bias Monte Carlo (CBMC) simulations are employed to provide confirmation of the observed thermodynamic nonidealities in adsorption of CO2/CH4, CO2/N2, and CO2/C3H8 mixtures in NaX zeolite. The CBMC simulations provide valuable insights into the root cause of the failure of the IAST, whose applicability mandates a homogeneous distribution of adsorbates within the pore landscape. By sampling 105 equilibrated spatial locations of individual guest molecules within the cages of NaX zeolite, the radial distribution functions (RDFs) of each of the pairs of guest molecules are determined. Examination of the RDFs clearly reveals congregation effects, wherein the CO2 guests occupy positions in close proximity to the Na+ cations. The positioning of the partner molecules (CH4, N2, or C3H8) is further removed from the CO2 guest molecules; consequently, the competition in mixture adsorption faced by the partner molecules is less severe than that anticipated by the IAST. The important message to emerge from this article is the need for quantification of thermodynamic nonideality effects in mixture adsorption.

Selective Adsorption of C6, C8, and C10 Linear α-Olefins from Binary Liquid-Phase Olefin/Paraffin Mixtures Using Zeolite Adsorbents: Experiment and Simulations

The adsorption separation of gaseous olefin/paraffin using porous materials has been extensively studied from both experimental and molecular simulation perspectives, while the adsorption separation of liquid-phase olefin/paraffin has been much less studied. One of the most important reasons for this is that it is difficult to measure the actual adsorption capacity of liquid-phase adsorption separation directly through experiments, and the simulation results of most studies are compared to gas-phase measurements. In this paper, the selective adsorption of linear α-olefins from three binary liquid-phase olefin/paraffin mixtures, 1-hexene/n-hexane (C6), 1-octene/n-octane (C8), and 1-decene/n-decane (C10), by zeolite adsorbents was systematically investigated using batch adsorption experiments and configurational-bias grand canonical Monte Carlo (CB-GCMC) simulations. In the batch experiments, based on the liquid-phase measurement method of the actual adsorption capacity that we developed, a modified commercial 5A zeolite with a relatively large pore volume and surface area was used for adsorption. The results showed that the modified 5A zeolite had larger actual adsorption capacities for C6 and C8 linear α-olefins, which increased by 51% and 56%, respectively, than the standard 5A zeolite that was used in our previous work. The adsorption isotherms of C6, C8, and C10 in the 5A and 13X zeolites were calculated by CB-GCMC simulations. The visualized results of density profiles showed that the olefin molecules were densely distributed at the edge of the zeolite cages and that there were cases where a single molecule was adsorbed over two adjacent cages. The good agreement between the experimental and simulated data proves the completeness of the liquid-phase measurement method that we developed and the reliability of the simulation prediction.

Elucidation of Selectivity Reversals for Binary Mixture Adsorption in Microporous Adsorbents.

The adsorption selectivity, Sads, is a key metric that quantifies the efficacy of any adsorbent in mixture separations. It is common practice to use ideal adsorbed solution theory (IAST) for estimating the value of Sads, using unary isotherm data inputs. In a number of experimental investigations, the phenomena of selectivity reversals and adsorption azeotropy (Sads = 1) have been reported in the published literature; such reversals may result from changes in mixture compositions, pressures, or pore loadings. In many cases, IAST is unable to anticipate such selectivity reversals. In this article, configurational-bias Monte Carlo simulations are used to gain insights into the phenomena of selectivity reversals. Two fundamentally different scenarios of selectivity reversals have been identified. In the first scenario, selectivity reversals are caused by inhomogeneous distribution of adsorbates due to preferential location and siting of a guest species in the pore space. For example, CO2 locates preferentially in the side pockets of mordenite and in window regions of DDR, CHA, and LTA zeolites. CO2 also congregates around the extra-framework cations of NaX zeolite. IAST fails to anticipate such selectivity reversals because its development relies on the assumption that the competition between guest species is uniform within the pore space. In the second scenario, selectivity reversals are caused by entropy effects that manifest near pore saturation conditions; the component that is preferentially adsorbed is the one that has the higher packing efficiency. For a homologous series of compounds, the component with the smaller chain length is favored at high pore occupancies. For adsorption of mixtures of alkane isomers within the intersecting channel network of MFI zeolite, the linear isomer is favored on the basis of entropic considerations.

Polar Sulfone-Functionalized Oxygen-Rich Metal-Organic Frameworks for Highly Selective CO2 Capture and Sensitive Detection of Acetylacetone at ppb Level.

A rational combination of an oxygen-rich pyridyl substituted tetrapodal ligand, tetrakis(4-pyridyloxymethylene)methane (TPOM), and a polar sulfone-functionalized conjugated bent dicarboxylate linker, dibenzothiophene-5,5'-dioxide-3,7-dicarboxylic acid (H2(3,7-DBTDC)), with d10 metal centers, Zn(II) and Cd(II), has led to the construction of two new three-dimensional (3D) metal-organic frameworks,{[Zn2(TPOM)(3,7-DBTDC)2]·7H2O·DMA}n (1) and {[Cd2(TPOM)(3,7-DBTDC)2]·6H2O·3DMF}n (2). Single-crystal X-ray analysis indicates that 1 is a 3D framework with a dinuclear repeating unit having two different Zn(II) centers (tetrahedral and square pyramidal) and 2 is a 3D framework comprised of a dinuclear repeating unit with one crystallographically independent distorted pentagonal bipyramidal Cd(II) coordinated to chelating/bridging carboxylates and nitrogen atoms of the TPOM ligand. In both cases, the pores are aligned with oxygen atoms of the TPOM ligand and decorated with polar sulfone moieties. On the basis of the stability established by thermogravimetric analysis and powder X-ray diffraction (PXRD) and the presence of large solvent accessible voids (25.4% for 1 and 40.6% for 2), gas sorption studies of different gases (N2, CO2, and CH4) and water vapor have been explored for both 1 and 2. The CO2 sorption isotherm depicts type I isotherm with an uptake of 93.6 cm3 g-1 (for 1) and 100.6 cm3 g-1 (for 2) at 195 K. Additionally, sorption of CO2 is highly selective over that of N2 and CH4 for both 1 and 2 due to the strong quadrupolar interactions between sulfone moieties and CO2 molecules. Configurational bias Monte Carlo (CBMC) molecular simulation has further justified the highly selective CO2 capture. On the other hand, the luminescence nature of 1 and 2 has been employed for highly selective detection of acetylacetone in aqueous methanol with a limit of 59 ppb in 1 and 66 ppb in 2, which are among the best reported values so far in the literature. The Stern-Volmer plots, spectral overlap, density functional theory calculations, CBMC simulation, and time-resolved lifetime measurements have been utilized for an extensive mechanistic study. The exclusive selectivity for acetylacetone in 1 and 2 have been confirmed by competitive selectivity test. Both exhibited good recyclability and stability after sensing experiments analyzed by fluorescence, PXRD, and field emission scanning electron microscopy studies.

Temperature effects on the spatial distribution of electrolyte mixtures at the aqueous liquid-vapor interface.

The microscopic picture of ions at the aqueous liquid-vapor interface continues to be an important and active area of research. Both experiments and simulations have shown that certain ions, such as Br- and I-, prefer to adsorb at the interface, but there is not yet a consensus as to the relative importance of various ion-specific properties that influence surface solvation. In a previous study, we systematically explored the effect of ion size on determining whether or not a monovalent ion would adsorb at the surface, and found that, for electrolyte mixtures represented by non-polarizable models, the larger/smaller anions are enriched/depleted at the interface. Here, we extend that study to include temperature effects enabling a van't Hoff analysis of the enthalpic and entropic contributions. We perform configurational-bias Monte Carlo simulations in the Gibbs ensemble to investigate the partitioning of mixtures of differently sized ions at the aqueous liquid-vapor interface from 284.09 K to 347.22 K at a pressure of 1 atm. Ions are represented using our own previously developed models that vary only in size (i.e., the Lennard-Jones σ parameter changes, while all other parameters are held constant across ion types). System properties studied include surface tension, interfacial width, ion surface excess, number density profiles, z-dependent transfer free energy, enthalpy, entropy, and anion-cation coordination numbers.

Occupancy Dependency of Maxwell-Stefan Diffusivities in Ordered Crystalline Microporous Materials.

Molecular dynamics simulation data for a variety of binary guest mixtures (H2/CO2, Ne/CO2, CH4/CO2, CO2/N2, H2/CH4, H2/Ar, CH4/Ar, Ar/Kr, Ne/Ar, CH4/C2H6, CH4/C3H8, C2H6C3H8, CH4/nC4H10, and CH4/nC5H11) in zeolites (MFI, BEA, ISV, FAU (all-silica), NaY, NaX, LTA, CHA, DDR) and metal–organic frameworks (MOFs) (IRMOF-1, CuBTC, MgMOF-74) show that the Maxwell–Stefan (M–S) diffusivities, Đ1, Đ2, Đ12, are strongly dependent on the molar loadings. The main aim of this article is to develop a fundamental basis for describing the loading dependence of M–S diffusivities. Using the ideal adsorbed solution theory, a thermodynamically rigorous definition of the occupancy, θ, is derived; this serves as a convenient proxy for the spreading pressure, π, and provides the correct metric to describe the loading dependence of diffusivities. Configurational-bias Monte Carlo simulations of the unary adsorption isotherms are used for the calculation of the spreading pressure, π, and occupancy, θ. The M–S diffusivity, Đi, of either constituent in binary mixtures has the same value as that for unary diffusion, provided the comparison is made at the same θ. Furthermore, compared at the same value of θ, the M–S diffusivity Đi of any component in a mixture does not depend on it partner species. The Đi versus θ dependence is amenable to simple interpretation using lattice-models. The degree of correlations, defined by the ratio Đ1/Đ12, that characterizes mixture diffusion shows a linear increase with occupancy θ, implying that correlations become increasingly important as pore saturation conditions are approached.

Probing Additive Loading in the Lamellar Phase of a Nonionic Surfactant: Gibbs Ensemble Monte Carlo Simulations Using the SDK Force Field.

Understanding solute uptake into soft microstructured materials, such as bilayers and worm-like and spherical micelles, is of interest in the pharmaceutical, agricultural, and personal care industries. To obtain molecular-level insight on the effects of solutes loading into a lamellar phase, we utilize the Shinoda-Devane-Klein (SDK) coarse-grained force field in conjunction with configurational-bias Monte Carlo simulations in the osmotic Gibbs ensemble. The lamellar phase is comprised of a bilayer formed by triethylene glycol mono- n-decyl ether (C10E3) surfactants surrounded by water with a 50:50 surfactant/water weight ratio. We study both the unary adsorption isotherm and the effects on bilayer structure and stability caused by n-nonane, 1-hexanol, and ethyl butyrate at several different reduced reservoir pressures. The nonpolar n-nonane molecules load near the center of the bilayer. In contrast, the polar 1-hexanol and ethyl butyrate molecules both load with their polar bead close to the surfactant head groups. Near the center of the bilayer, none of the solute molecules exhibits a significant orientational preference. Solute molecules adsorbed near the polar groups of the surfactant chains show a preference for orientations perpendicular to the interface, and this alignment with the long axis of the surfactant molecules is most pronounced for 1-hexanol. Loading of n-nonane leads to an increase of the bilayer thickness, but does not affect the surface area per surfactant. Loading of polar additives leads to both lateral and transverse swelling. The reduced Henry's law constants of adsorption (expressed as a molar ratio of additive to surfactant per reduced pressure) are 0.23, 1.4, and 14 for n-nonane, 1-hexanol, and ethyl butyrate, respectively, and it appears that the SDK force field significantly overestimates the ethyl butyrate-surfactant interactions.

Investigating the non-idealities in adsorption of CO2-bearing mixtures in cation-exchanged zeolites

• Non-idealities are caused by inhomogeneous distribution of adsorbates. • The extent of thermodynamic non-idealities also depend on the Si/Al ratio. • Models for activity coefficients must include the influence of the adsorption potential. • Non-ideal adsorption may influence separation performance of fixed bed adsorbers. Cation-exchanged zeolites have significant potential for capture of CO 2 from a wide variety of mixtures containing N 2 , H 2 , alkanes and alkenes. The strong coulombic interactions of CO 2 with extra-framework cations result in strong binding and selective capture. Published experimental data on mixture adsorption indicate that the Ideal Adsorbed Solution Theory (IAST) fails to provide accurate estimates of mixture adsorption equilibrium. The reasons for the quantitative failure of IAST estimates are investigated with the aid of Configurational-Bias Monte Carlo (CBMC) simulations of mixture adsorption. Computational snapshots indicate that the failure of the IAST is traceable to inhomogeneous distribution of adsorbates within the zeolite framework.