Competitive and Synergistic Adsorption of Mixtures of Polar and Nonpolar Gases in Carbonaceous Nanopores.

Most adsorption applications involve mixtures, yet accurate predictions of the adsorption of mixtures remain challenging, in part due to the inability to account for the interplay between adsorbate-adsorbate and adsorbate-adsorbent interactions. This study involves a comprehensive Monte Carlo simulation of the adsorption of two groups of mixtures (namely, supercritical and subcritical ones) in carbon nanopores and quantifies Henry's constants, isotherms, energetics, and density distributions in the pores. When interadsorbate interactions are negligible (e.g., in supercritical mixtures such as mixtures of nonpolar gases), adsorbates behave like ideal gases and the adsorption isotherm can be predicted with the ideal adsorbed solution theory (IAST). However, when interadsorbate interactions become significant, IAST fails. This study reveals that (1) in mixtures of polar and nonpolar gases, the stronger intermolecular interaction for the polar constituent leads to synergistic adsorption that causes the nonpolar adsorbate to desorb and (2) for mixtures of polar gases, such as ethanol and water, the adsorbate-adsorbate interactions are so dominant that the unfavorable adsorbate-adsorbent interactions are overcome, such that water adsorbs onto the hydrophobic adsorbent. The competitive and synergistic interactions highlighted here are expected to be valuable in enhancing gas separations.

Microscopic insights into water adsorption in carbon nanopores - the role of acidic and basic functional groups and their configurations.

Functional groups (FGs) in porous carbon play a pivotal role in water adsorption by nucleating water clusters followed by their coalescence, the process in which precursors are used for filling the confined space typically in the reduced pressure range of 0.3-0.8. While the general role of FGs is known, different types of FGs and their configurations are expected to critically affect the formation of clusters and they are yet to be clarified. To this end, we conducted a comprehensive Monte Carlo simulation of water adsorption at 298 K in a functionalized graphitic slit pore as a function of types of FGs (acidic and basic) and their configurations. The adsorption mechanism is derived from the analysis of adsorption/desorption isotherms, isosteric heat, and 2D density and compressibility distributions. Our results show that (1) with the increasing density of FGs, the isotherm switches from Type V to Type I and the precursor used for pore filling shifts from clustering to molecular layering, (2) the intra-rotation of atoms around the Sigma bonds in the FGs plays an important role in clustering when the FGs are in proximity and (3) for a given density of FGs, the configurations (interspacing distribution) of FGs dictate the shape and size of the water clusters, affecting the filling and emptying of water molecules from the confined space, which have practical implications in moisture control by solid adsorbents.

The physisorption mechanism of SO2 on graphitized carbon.

Sulfur dioxide (SO2) in flue gases emitted from fossil fuel power plants dramatically reduces the CO2 capture efficiency via adsorption, which is due to the potential reaction of SO2 with basic functional groups on the adsorbent. Physisorption rather than chemisorption is preferred, because adsorbents can be more easily regenerated by either reducing the pressure or increasing the temperature. Carbon is a suitable adsorbent for SO2 capture and widely used, and therefore it is important to study SO2 adsorption onto carbon with the Monte Carlo simulation to provide microscopic details to demarcate the roles of the basal plane of the graphene layer and the functional groups in adsorption. SO2 is a polar molecule like water, as they both carry partial charges, but they interact differently with functional groups. Instead of 3D-clusters in the case of water, SO2 is localized around the functional groups and spreads over the basal plane to form 2D-molecular layers because of the strong dispersive interactions with graphite. The results indicate that the functional group has a negligible effect on the enhancement of adsorption and its role is to localize 2D-clusters of SO2 molecules. For non-graphitized carbon, we have found that the greater loadings at low pressure compared to the highly graphitized carbon is due to the presence of defects (crevices) on the basal plane surface. Finally, to describe better the experimental data, we have found that the reduction in the interactions between adsorbed molecules in the first layer is because of the repulsion of their dipoles pointing normal to the surface, a phenomenon called surface mediation and is widely used in the description of gas adsorption on surfaces.

A simulation study of the low temperature phase diagram of the methane monolayer on graphite: a test of potential energy functions.

We have used molecular simulation with two intermolecular potential models, TraPPE-UA and TraPPE-EH, the latter of which accounts for the tetrahedral shape, to study the effects of shape on methane adsorption on graphite. Both models give good descriptions of the vapour-liquid equilibria in the bulk phase, but adsorption on graphite is better described by the TraPPE-EH model. Molecular configurations in the monolayer, show the variation with temperature of the registry sites for the carbon and hydrogen atoms of the methane molecules. At temperatures below 70 K, the centre of mass (COM) of the molecules is in registry with the centre of the carbon hexagons. For temperatures above 70 K, a commensurate monolayer is initially formed as at low temperatures, then as the loading is increased the first layer remains in registry, but the COM of the methane molecules in the first layer shifts to the top of the graphite carbon atoms with the C-H bond pointing to carbon atoms in the second shell of a C-hexagon. At temperatures above 93 K, the first adsorbate layer goes through these two commensurate states and then undergoes a transition to an incommensurate solid. Finally, for temperatures greater than 110 K methane behaves like a pseudo spherical molecule.

Atomistic-Scale Energetic Heterogeneity on a Membrane Surface.

Knowing the energetic topology of a surface is important, especially with regard to membrane fouling. In this study, molecular computations were carried out to determine the energetic topology of a polyvinylidene fluoride (PVDF) membrane with different surface wettability and three representative probe molecules (namely argon, carbon dioxide and water) of different sizes and natures. Among the probe molecules, water has the strongest interaction with the PVDF surface, followed by carbon dioxide and then argon. Argon, which only has van der Waals interactions with PVDF, is a good probing molecule to identify crevices and the molecular profile of a surface. Carbon dioxide, which is the largest probing molecule and does not have dipole moment, exhibits similar van der Waals and electrostatic interactions. As for water, the dominant attractive interactions are electrostatics with fluorine atoms of the intrinsically hydrophobic PVDF membrane, but the electrostatic interactions are much stronger for the hydroxyl and carboxyl groups on the hydrophilic PVDF due to strong dipole moment. PVDF only becomes hydrophilic when the interaction energy is approximately doubled when grafted with hydroxyl and carboxyl groups. The energetic heterogeneity and the effect of different probe molecules revealed here are expected to be valuable in guiding membrane modifications to mitigate fouling.

Enantiomeric Separation of Racemic Mixtures Using Chiral-Selective and Organic-Solvent-Resistant Thin-Film Composite Membranes.

Membrane-based chiral separation has emerged as a promising method for the efficient separation of chiral molecules. Ideally, the membranes should be able to achieve good enantioselectivity, while maintaining high stability in harsh solvents. However, engineering membranes for chiral molecular separation in harsh organic solvent environments is still a big challenge. In this study, we fabricated a novel thin-film composite nanofiltration membrane composed of (2-hydroxypropyl)-beta-cyclodextrin (HP-ß-CD) as the chiral selector for the enantiomeric separation of racemic 1-phenylethanol chiral compounds in organic solvents. The fabricated membrane achieved 60-80% enantioselectivity of R-phenylethanol over S-phenylethanol in nonpolar n-hexane. It was found that HP-ß-CD played a critical role in the enantioselective performance, as the membrane without HP-ß-CD showed no chiral selectivity. Molecular docking calculations substantiate the experiments by showing that the average free binding energy of S-phenylethanol with HP-ß-CD is stronger than that of R-phenylethanol, indicating that the complex of S-phenylethanol with HP-ß-CD has a higher thermodynamic stability and greater interaction. Furthermore, the crosslinked network between HP-ß-CD and the polyamide layer conferred the membrane with solvent stability in nonpolar solvents. Moreover, this new membrane exhibited good solvent permeance and a molecular weight cutoff of around 650 g mol-1.

On the growth of argon clusters on a weak adsorbent decorated with patches.

Much attention has been paid to understanding the clustering mechanism of water adsorbed on carbonaceous adsorbents. Adsorbed water forms clusters around strong sites, such as functional groups and surface defects, and these clusters then coalesce if the strong sites are sufficiently close to each other. Simulations of water adsorption are notoriously time consuming because of the slow relaxation of the strongly-directional hydrogen bonds. Our objective in this paper is to gain a better insight into clustering and coalescence of water, without incurring large computing overheads. To this end we have chosen argon as an adsorbate, and a substrate that is a very weak adsorbent for argon. To mimic functional groups, the substrate surface is decorated with strongly adsorbing patches. The adsorbate forms nano-clusters with convex surfaces at pressures greater than the saturation vapour pressure. When these clusters are sufficiently close to each other, they coalescence to form larger fused clusters, and there is a decrease in the equilibrium pressure. The relationship between the radius of curvature of the developed nano-clusters and the equilibrium pressure follows the functional form of the Kelvin equation, but the energy parameterγvM is smaller than the bulk value, implying that the clusters have a smaller cohesive energy.

On the canonical isotherms for bulk fluid, surface adsorption and adsorption in pores: A common thread.

Kinetic Monte Carlo simulated isotherms calculated in the canonical ensemble, at temperatures below the critical temperature, for bulk fluid, surface adsorption and adsorption in a confined space, show a van der Waals (vdW) loop with a vertical phase transition between the rarefied and dense spinodal points at the co-existence chemical potential, µco. Microscopic examination of the state points on this loop reveals features that are common to these systems. At state points with chemical potentials greater than µco the microscopic configurations show clusters, which coalesce to form two co-existing phases along the vertical section of the loop (the coexistence line). As more molecules are added, the dense region expands at the expense of the rarefied region, to the point where the rarefied region becomes spherical (cylindrical for 2D-systems) with a curvature greater than that of the coexisting phases. This results in a decrease of chemical potential from µco to the liquid spinodal point where the rarefied region disappears. With a further increase in loading, the chemical potential and the density increase. The existence of a vdW loop is the microscopic reason for the hysteresis observed in the grand canonical isotherm, where the adsorption and desorption boundaries of the hysteresis loop are first-order transitions, enclosing the vertical section of the vdW loop of the canonical isotherm. However, a first-order transition is rarely observed in experiments where transitions are usually steep, but not vertical. From our extensive simulations, we provide two possible reasons: (1) the finite extent of the system and (2) the existence of high energy sites that localize the clusters. In the first case, the desorption branch, and in the second case the adsorption branch, either comes close to, or collapses onto the coexistence line. When both occur, the hysteresis loop disappears and the isotherm is reversible, as often observed experimentally.

Water adsorption on carbon - A review.

Water adsorption on carbonaceous materials has been studied increasingly in the recent years, not only because of its impact on many industrial processes, but also motivated by a desire to understand, at a fundamental level, the distinctive character of directional interactions between water molecules, and between water molecules and other polar groups, such as the functional groups (FGs) at the surfaces of graphene layers. This paper presents an extensive review of recent experimental and theoretical work on water adsorption on various carbonaceous materials, with the aim of gaining a better understanding of how water adsorption in carbonaceous materials relates to the concentration of FGs, their topology (arrangement of the groups) and the structure of the confined space in porous carbons. Arising from this review we are able to propose mechanisms for water adsorption in carbonaceous materials as the adsorbate density increases. The intricate interplay between the roles of FGs and confinement makes adsorption of water on carbon materials very different from that of other simple molecules.