Solvent-Assisted Graphene Exfoliation from Graphite Using Umbrella Sampling Simulations.

We employed molecular dynamics (MD) simulations coupled with umbrella sampling to explore the thermodynamics governing the exfoliation of a single graphene layer from a graphitic substrate in five different solvents such as dimethylacetamide (DMA), N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), cyclohexane (CHX), and water. The substrate was modeled as a stack of three identical graphene layers with the graphene sheet undergoing exfoliation positioned on top of this stack. The initial configurations for each umbrella simulation were generated through steered MD simulations carried out along two distinct coordinates: one parallel and the other perpendicular to the graphene layers. Our analyses revealed a uniform wetting behavior for both the nanosheet and the graphitic substrate in all of the tested solvents. Consistent with experimental observations, the steered simulations confirmed that exfoliation is more favorable along the parallel direction than along the perpendicular one. All non-water solvents exhibit comparable effectiveness in the exfoliation of graphene. The calculated free energies of these solvents in parallel exfoliation consistently fell within the range of 90-100 kJ/mol/nm2. In perpendicular exfoliation, however, the corresponding energies converge to lower values. This difference is attributed to the nonequilibrium nature of the perpendicular exfoliation, primarily caused by the great steering velocity of the graphene sheet immediately after detachment from the substrate. This rapid motion of the nanosheet along the perpendicular coordinate results in an elevated system energy and heating.

Pathway for Water Transport through Breathable Nanocomposite Membranes of PEBAX with Ionic Liquid [C12C1im]Cl.

Water transport through membranes is an attractive topic among the research dedicated to dehydration processes, microenvironment regulation, or more simply, recovery of freshwater. Herein, an atomistic computer simulation is proposed to provide new insights about a water vapor transport mechanism through PEBAX membranes filled with ionic liquid (IL) [C12C1im]Cl. Starting from experimental evidence that indicates an effective increase in water permeation as the IL is added to the polymer matrix (e.g., up to 85·10-3 (g·m)/(m2·day) at 318.15 K for PEBAX@2533 membranes loaded with 70% of IL), molecular dynamics simulations are proposed to explore the key role of IL in water transport inside membranes. The polar region composed of anions and cationic head groups of the IL is demonstrated to serve as the pathway for water transport through the membrane. Water molecules always stay near the pathway, which becomes wider and thus has a larger water-accessible area with increasing IL concentration. Hence, the diffusion coefficients of water molecules and ions increase as the IL concentration increases. The simulation provides useful indications about a microscopic mechanism that regulates the transport of water vapor through a kind of PEBAX/IL membrane, resulting in full agreement with the experimental evidence.

Thin Film Composite Membranes Based on the Polymer of Intrinsic Microporosity PIM-EA(Me2)-TB Blended with Matrimid®5218.

In this work, thin film composite (TFC) membranes were fabricated with the selective layer based on a blend of polyimide Matrimid®5218 and polymer of intrinsic microporosity (PIM) composed of Tröger's base, TB, and dimethylethanoanthracene units, PIM-EA(Me2)-TB. The TFCs were prepared with different ratios of the two polymers and the effect of the PIM content in the blend of the gas transport properties was studied for pure He, H2, O2, N2, CH4, and CO2 using the well-known time lag method. The prepared TFC membranes were further characterized by IR spectroscopy and scanning electron microscopy (SEM). The role of the support properties for the TFC membrane preparation was analysed for four different commercial porous supports (Nanostone Water PV 350, Vladipor Fluoroplast 50, Synder PAN 30 kDa, and Sulzer PAN UF). The Sulzer PAN UF support with a relatively small pore size favoured the formation of a defect-free dense layer. All the TFC membranes supported on Sulzer PAN UF presented a synergistic enhancement in CO2 permeance, and CO2/CH4 and CO2/N2 ideal selectivity. The permeance increased about two orders of magnitude with respect to neat Matrimid, up to ca. 100 GPU, the ideal CO2/CH4 selectivity increased from approximately 10 to 14, and the CO2/N2 selectivity from approximately 20 to 26 compared to the thick dense reference membrane of PIM-EA(Me2)-TB. The TFC membranes exhibited lower CO2 permeances than expected on the basis of their thickness-most likely due to enhanced aging of thin films and to the low surface porosity of the support membrane, but a higher selectivity for the gas pairs CO2/N2, CO2/CH4, O2/N2, and H2/N2.

Tröger's Base Network Polymers of Intrinsic Microporosity (TB-PIMs) with Tunable Pore Size for Heterogeneous Catalysis.

Heterogeneous catalysis plays a pivotal role in the preparation of value-added chemicals, and it works more efficiently when combined with porous materials and supports. Because of that, a detailed assessment of porosity and pore size is essential when evaluating the performance of new heterogeneous catalysts. Herein, we report the synthesis and characterization of a series of novel microporous Tröger's base polymers and copolymers (TB-PIMs) with tunable pore size. The basicity of TB sites is exploited to catalyze the Knoevenagel condensation of benzaldehydes and malononitrile, and the dimension of the pores can be systematically adjusted with an appropriate selection of monomers and comonomers. The tunability of the pore size provides the enhanced accessibility of the catalytic sites for substrates, which leads to a great improvement in conversions, with the best results achieving completion in only 20 min. In addition, it enables the use of large benzaldehydes, which is prevented when using polymers with very small pores, typical of conventional PIMs. The catalytic reaction is more efficient than the corresponding homogeneous counterpart and is ultimately optimized with the addition of a small amount of a solvent, which facilitates the swelling of the pores and leads to a further improvement in the performance and to a better carbon economy. Molecular dynamic modeling of the copolymers' structures is employed to describe the swellability of flexible chains, helping the understanding of the improved performance and demonstrating the great potential of these novel materials.

On the Consistency of the Exfoliation Free Energy of Graphenes by Molecular Simulations.

Monolayer graphene is now produced at significant yields, by liquid phase exfoliation of graphites in solvents. This has increased the interest in molecular simulation studies to give new insights in the field. We use decoupling simulations to compute the exfoliation free energy of graphenes in a liquid environment. Starting from a bilayer graphene configuration, we decouple the Van der Waals interactions of a graphene monolayer in the presence of saline water. Then, we introduce the monolayer back into water by coupling its interactions with water molecules and ions. A different approach to compute the graphene exfoliation free energy is to use umbrella sampling. We apply umbrella sampling after pulling the graphene monolayer on the shear direction up to a distance from a bilayer. We show that the decoupling and umbrella methods give highly consistent free energy results for three bilayer graphene samples with different size. This strongly suggests that the systems in both methods remain closely in equilibrium as we move between the states before and after the exfoliation. Therefore, the amount of nonequilibrium work needed to peel the two layers apart is minimized efficiently.

Optical Analysis of the Internal Void Structure in Polymer Membranes for Gas Separation.

Global warming by greenhouse gas emissions is one of the main threats of our modern society, and efficient CO2 capture processes are needed to solve this problem. Membrane separation processes have been identified among the most promising technologies for CO2 capture, and these require the development of highly efficient membrane materials which, in turn, requires detailed understanding of their operation mechanism. In the last decades, molecular modeling studies have become an extremely powerful tool to understand and anticipate the gas transport properties of polymeric membranes. This work presents a study on the correlation of the structural features of different membrane materials, analyzed by means of molecular dynamics simulation, and their gas diffusivity/selectivity. We propose a simplified method to determine the void size distribution via an automatic image recognition tool, along with a consolidated Connolly probe sensing of space, without the need of demanding computational procedures. Based on a picture of the void shape and width, automatic image recognition tests the dimensions of the void elements, reducing them to ellipses. Comparison of the minor axis of the obtained ellipses with the diameters of the gases yields a qualitative estimation of non-accessible paths in the geometrical arrangement of polymeric chains. A second tool, the Connolly probe sensing of space, gives more details on the complexity of voids. The combination of the two proposed tools can be used for a qualitative and rapid screening of material models and for an estimation of the trend in their diffusivity selectivity. The main differences in the structural features of three different classes of polymers are investigated in this work (glassy polymers, superglassy perfluoropolymers and high free volume polymers of intrinsic microporosity), and the results show how the proposed computationally less demanding analysis can be linked with their selectivities.

Molecular insights on NaCl crystal formation approaching PVDF membranes functionalized with graphene.

Membrane-assisted crystallization is an emerging technology where microporous hydrophobic membranes are used not as selective barriers but to promote the water vapor transfer between phases inducing supersaturation in solution. This has been successfully tested in the crystallization of ionic salts, low molecular weight organic acids and proteins. In this work, molecular dynamics simulations were used to study the crystal nucleation and growth of sodium chloride in contact with hydrophobic polymer surfaces at a supersaturated concentration of salt. A pristine polyvinylidene fluoride (PVDF) surface and PVDF containing different concentrations of graphene platelets were studied. Membrane crystallization tests were performed in parallel, in order to compare the experimental results with the computational ones. Here, with an integrated experimental-computational approach, we demonstrate that graphene-containing membranes assisted the crystal growth of NaCl, speeding up crystal nucleation in comparison with the pristine PVDF membranes. The computational results agreed with the experimental data, allowing the possibility of exploring the behavior of nanomaterials in membrane processes at a microscopic level.

A simulation study on OH-containing polyimide (HPI) and thermally rearranged polybenzoxazoles (TR-PBO): relationship between gas transport properties and free volume morphology.

Recently, high free volume polymer materials have been regarded as high potential candidates for gas transport/separation membranes, since the amount of free volume in polymeric membrane can improve the diffusivity and solubility of gas molecules. In this study, we focused on how local changes in polymer structure can affect the performance of a membrane at the molecular level. The transport behavior was theoretically analyzed, and then the differences in the amount and morphology of free volume were characterized. Finally, we suggested how the "evolution of microcavities" affects the gas transport properties of hydroxyl-containing polyimide (HPI) and thermally rearranged (TR) polymers. In particular, using image analysis, we intuitively demonstrate the morphological difference between HPI and TR polymers that have been indirectly explained by experimental analyses using a wide-angle X-ray diffractometer (WAXD) and positron annihilation laser spectroscopy (PALS). Solubility results using the grand canonical Monte Carlo (GCMC) method showed marginal improvement in thermally rearranged polybenzoxazoles (TR-PBOs) from its precursor HPI, which is in good agreement with the experimental tendency. Moreover, higher diffusivities but lower selectivities of TR-PBO models compared with those of HPI models were observed, as reported experimentally. The difference in gas transport abilities between HPIs and TR-PBOs originates from the difference in their diffusion behavior, and this is strongly related to the free volume amount and morphology of polymeric materials. In addition to the higher amount of total free volume in TR-PBO, our image analysis revealed that TR-PBO has a higher amount of interconnected "hourglass-shaped free volume elements", which consist of larger and more elongated cavities with bottlenecks than the HPI model. In particular, the bottleneck diameters in the TR-PBO models are wider than those in the HPI models, enabling the larger gas molecules to diffuse through the cavities faster. However, the narrower and smaller bottleneck diameters in the HPI model can induce better selectivity for large gas molecules.

Thermal treatment effect on the structure and property change between hydroxy-containing polyimides (HPIs) and thermally rearranged polybenzoxazole (TR-PBO).

In this study, we report on the effect of thermal treatment on polyimide precursors (HPIs) and on the resulting thermally rearranged polybenzoxazole (TR-PBO) polymer membranes as investigated through the use of molecular dynamics (MD) simulations. For this purpose, we have first analyzed the structures of hydroxy-containing polyimides before thermal treatment and those of the thermally rearranged polybenzoxazoles after the thermal treatment, according to their temperature conditions. As expected, HPIs and TR-PBOs always show very limited motion of their polymer chains, indicated by the radius of gyration, due to their well-known thermal stability. In particular, the very rigid and stiff PBO linkages did not undergo significant change in their torsional angle distribution. On the other hand, in regards to intrachain movement, HPI chains were significantly affected by temperature. Their conformational changes were notably observed, which affected the distances between possible reaction sites, oxygen atoms in hydroxyl groups, and carbon atoms in the imido-ring. The free volume analysis, performed on both polymers and during thermal treatment, indicates that HPIs have a unimodal distribution of free volume areas, which partially coalesce in larger areas having, however, a relatively narrow size. Further, TR-PBO shows a bimodal cavity distribution, and after thermal treatment and TR reaction, the free volume structures in TR-PBO are maintained. The cavity size distributions determined by simulation were also consistent with free volume distributions determined by positron annihilation lifetime spectroscopy.

Pure and Modified Co-Poly(amide-12-b-ethylene oxide) Membranes for Gas Separation Studied by Molecular Investigations.

This paper deals with a theoretical investigation of gas transport properties in a pure and modified PEBAX block copolymer membrane with N-ethyl-o/p-toluene sulfonamide (KET) as additive molecules. Molecular dynamics simulations using COMPASS force field, Gusev-Suter Transition State Theory (TST) and Monte Carlo methods were used. Bulk models of PEBAX and PEBAX/KET in different copolymer/additive compositions were assembled and analyzed to evaluate gas permeability and morphology to characterize structure-performance relationships.

Physicochemical characterization of solute retention in solvent resistant nanofiltration: the effect of solute size, polarity, dipole moment, and solubility parameter.

Growing interest in nanofiltration for solvent purification requires a fundamental understanding of the physicochemical mechanisms of solute retention in organic solvent nanofiltration. In this study, the retention of a similar series of azo dyes with approximately similar molar mass (around 350 Da) by four nanofiltration membranes was studied. The membranes used are commercially available polymeric nanofiltration membranes with molecular weight cutoff between 150 and 300 Da (DuraMem150, StarMem122, NF270 and Desal-Dk). In order to correlate the retention with the size of the molecules, which is assumed to be one of the main factors that determines the retention, use was made of different parameters for the molecular size: molar mass, the Stokes diameter, the equivalent molar diameter, and the cavity surface in methanol and ethanol. All parameters were calculated by using molecular dynamics simulations. For each size parameter, the correlation with retention in nanofiltration experiments was calculated. For the StarMem122 membrane, zero retentions were observed due to the swelling of the membrane and pore size enlargement in methanol and ethanol. For the three other membranes, a fairly good correlation of the retention with the size could only be observed if the size difference between compounds is sufficiently large. Two other factors were studied by using molecular dynamics, i.e., the polarity of the molecule and the electron density of the molecule. The importance of these factors depends on the structure of the molecule as well as the functional groups of the polymer. A very good correlation has been observed for retention of dyes versus their dipole moment. Finally, the effect of solubility parameters of dyes on their retention did not show any significant effect.