Methanol recovery: potential of nanolaminate organic solvent nanofiltration (OSN) membranes.

Researchers have made a significant breakthrough by merging the energy-saving attribute of organic solvent nanofiltration (OSN) with the remarkable solvent permeance and solute rejection of two-dimensional (2D) laminated membranes. This innovative approach brings forth a new era of sustainable and cost-effective separation techniques, presenting a promising solution to the issue of industrial solvents contaminating the environment. This development paves the way for new opportunities in building a sustainable future. Specifically, our mini-review has cast a spotlight on the separation and recovery of methanol-a solvent abundantly used in industrial processes. We systematically evaluated a diverse array of free-standing 2D nanolaminate OSN membranes. The analysis encompasses the assessment of pure methanol permeance, solute rejection capabilities, and the simultaneous evaluation of methanol permeance and solute rejection performance. Notably, this study sheds light on the considerable potential of 2D laminated OSN membranes in revolutionizing separation processes for the industrial use of methanol.

Desalination Potential of Aquaporin-Inspired Functionalization of Carbon Nanotubes: Bridging Between Simulation and Experiment.

Outstanding water/ion selectivity of aquaporins paves the way for bioinspired desalination membranes. Since the amino acid asparagine (Asn) plays a critical role in the fast water conduction of aquaporins through hydrogen bonding interactions, we adapted this feature by functionalizing carbon nanotubes (CNTs) with Asn. We also studied a nonpolar amino acid and carboxylate functional groups for comparison. Computation of the ideal performance of individual CNTs at atomistic scale is a powerful tool for probing the effect of tip-functionalized CNTs on water and ion transport mechanism. Molecular simulation study suggests that steric effects required for ion rejection compromise fast water conductivity; however, an Asn functional group having polarity and hydrogen bonding capability can be used to balance this trade-off to some extent. To test our hypothesis, we incorporated functionalized CNTs (f-CNTs) into the in situ polymerized selective polyamide (PA) layer of thin film nanocomposite membranes and compared their experimental RO desalination performance. The f-CNTs were found to change the separation environment through modification of cross-linking density, thickness, and hydrophilicity of the PA layer. Asn functionalization led to more cross-linked and thinner PA layer while hydrophilicity is improved compared to other functional groups. Accordingly, water permeance is increased by 25% relative to neat PA with a salt rejection above 98%. Starting from the nanomaterial itself and benefiting from molecular simulation, it is possible to design superior membranes suited for practical applications.

Selective adsorption of acidic gases from ternary mixture by acetate- and sulfonate-based ionic liquids at molecular level.

This paper attempts to elucidate the competitive adsorption mechanism of thin films of ionic liquids (ILs) on the surface of porous materials for acidic gases at a molecular level in order to design a proper material for the diminishment of gas emissions. Thin film 1-butyl-3-methylimidazalium ([BMIM]+) cation-based IL systems composed of four different anions such as [CH3CO2]- and [CF3CO2]- (acetate-based), and [CH3SO3]- and [CF3SO3]- (sulfonate-based) are created in contact with the gas phase containing ternary H2S/CO2/CH4:1/25/74 mixture. To define gas adsorption performance at gas-liquid interface and bulk liquid phase, classical molecular dynamics simulations are carried out. Adsorption of acidic gases is governed by the formation of an adsorbed gas layer on the surface of the ionic liquid based on thermodynamics aspects, and then the partial dissolution of gases in the bulk liquid phase is accompanied by the transport of gases. These behaviors are followed by several analysis methods in simulation approaches such as radial distribution function (RDF) of gases around specific atoms of ILs, lateral displacement of gas molecules, radial distance between gas and ILs, interaction energy between gases and ILs, and average number of hydrogen bonding between ions with and without adsorbed gases. Acetate-based ILs performed twice as good in CO2 adsorption capacity than sulfonate-based ILs. However, the one having -CF3 group in acetate-based ILs has short CO2 retention time and high CH4 adsorption capacity, diminishing the H2S+CO2/CH4 adsorption selectivity. High CO2 adsorption performance of acetate-based ILs is related to their strong anion-cation interaction and less hydrogen-bonding ability between cation tail and anion, which is the source for free space between anion and cation. Those with high adsorption capacities and long retention times are those that can ensure that CO2 molecules are coordinated in these free volumes between cation tails and anions. Therefore, here, the effect of different parameters on the CO2 and H2S adsorption over CH4 is revealed via atomistic design, and the importance of selection of suitable anions in IL for identifying potential nanocomposite adsorbent materials for acidic gas removal is highlighted.

Metallicity-Dependent Ultrafast Water Transport in Carbon Nanotubes.

Carbon nanotubes (CNTs) with hydrophobic and atomically smooth inner channels are promising for building ultrahigh-flux nanofluidic platforms for energy harvesting, health monitoring, and water purification. Conventional wisdom is that nanoconfinement effects determine water transport in CNTs. Here, using full-atomistic molecular dynamics simulations, it is shown that water transport behavior in CNTs strongly correlates with the electronic properties of single-walled CNTs (metallic (met) vs semiconducting (s/c)), which is as dominant as the effect of nanoconfinement. Three pairs of CNTs (i.e., (8,8)met , 10.85 Å vs (9,7)s/c , 10.88 Å; (9,8)s/c , 11.53 Å vs (10,7)met , 11.59 Å; and (9,9)met , 12.20 Å vs (10,8)s/c , 12.23 Å) are used to investigate the roles of diameter and metallicity. Specifically, the (9,8)s/c can restrict the hydrogen-bonding-mediated structuring of water and give the highest reduction in carbon-water interaction energy, providing an extraordinarily high water flux, around 250 times that of the commercial reverse osmosis membranes and approximately fourfold higher than the flux of the state-of-the-art boron nitrate nanotubes. Further, the high performance of (9,8)s/c is also reproducible when embedded in lipid bilayers as synthetic high-water flux porins. Given the increasing availability of high-purity CNTs, these findings provide valuable guides for realizing novel CNT-enhanced nanofluidic systems.

Large-Scale Computational Screening of Metal Organic Framework (MOF) Membranes and MOF-Based Polymer Membranes for H2/N2 Separations.

Several thousands of metal organic frameworks (MOFs) have been reported to date, but the information on H2/N2 separation performances of MOF membranes is currently very limited in the literature. We report the first large-scale computational screening study that combines state-of-the-art molecular simulations, grand canonical Monte Carlo (GCMC) and molecular dynamics (MD), to predict H2 permeability and H2/N2 selectivity of 3765 different types of MOF membranes. Results showed that MOF membranes offer very high H2 permeabilities, 2.5 × 103 to 1.7 × 106 Barrer, and moderate H2/N2 membrane selectivities up to 7. The top 20 MOF membranes that exceed the polymeric membranes' upper bound for H2/N2 separation were identified based on the results of initial screening performed at infinite dilution condition. Molecular simulations were then carried out considering binary H2/N2 and quaternary H2/N2/CO2/CO mixtures to evaluate the separation performance of MOF membranes under industrial operating conditions. Lower H2 permeabilities and higher N2 permeabilities were obtained at binary mixture conditions compared to the ones obtained at infinite dilution due to the absence of multicomponent mixture effects in the latter. Structure-performance relations of MOFs were also explored to provide molecular-level insights into the development of new MOF membranes that can offer both high H2 permeability and high H2/N2 selectivity. Results showed that the most promising MOF membranes generally have large pore sizes (>6 Å) as well as high surface areas (>3500 m2/g) and high pore volumes (>1 cm3/g). We finally examined H2/N2 separation potentials of the mixed matrix membranes (MMMs) in which the best MOF materials identified from our high-throughput screening were used as fillers in various polymers. Results showed that incorporation of MOFs into polymers almost doubles H2 permeabilities and slightly enhances H2/N2 selectivities of polymer membranes, which can advance the current membrane technology for efficient H2 purification.

Simulation of H2/CH4 mixture permeation through MOF membranes using non-equilibrium molecular dynamics.

Grand canonical Monte Carlo (GCMC) simulations are widely used with equilibrium molecular dynamics (EMD) to predict gas adsorption and diffusion in single-crystals of metal-organic frameworks (MOFs). Adsorption and diffusion data obtained from these simulations are then combined to predict gas permeabilities and selectivities of MOF membranes. This GCMC + EMD approach is highly useful to screen a large number of MOFs for a target membrane-based gas separation process. External field non-equilibrium molecular dynamics (NEMD) simulations, on the other hand, can directly compute gas permeation by providing an accurate representation of MOF membranes but they are computationally demanding and require long simulation times. In this work, we performed NEMD simulations to investigate H2/CH4 separation performances of MOF membranes. Both single-component and binary mixture permeabilities of H2 and CH4 were computed using the NEMD approach and results were compared with the predictions of the GCMC + EMD approach and experimental measurements reported in the literature. Our results showed that there is a good agreement between NEMD simulations and experiments for the permeability and selectivity of MOF membranes. NEMD simulations provided the direct observation of the mass transfer resistances on the pore mouth of MOF membranes, which is neglected in the GCMC + EMD approach. Our results suggested that once the very large numbers of MOF materials were screened using the GCMC + EMD approach, more detailed NEMD calculations can be performed for the best membrane candidates to unlock the actual gas transport mechanism before the experimental fabrication of MOF membranes.

High-Throughput Screening of MOF Adsorbents and Membranes for H2 Purification and CO2 Capture.

Metal organic frameworks (MOFs) have emerged as great adsorbent and membrane candidates for separation of CO2/H2 mixtures. The main challenge is the existence of thousands of MOFs, which requires computational screening methods to identify the best materials prior to experimental efforts. In this study, we performed high-throughput computational screening of MOFs to examine their adsorbent and membrane performances for CO2/H2 separation. Grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations were used to compute various adsorbent and membrane performance metrics of 3857 MOFs. CO2/H2 adsorption selectivities of MOFs at pressure swing adsorption (PSA) and vacuum swing adsorption (VSA) conditions were calculated to be in the range of 2.5-25 000 and 2.5-85 000, respectively, outperforming many zeolite adsorbents. Correlations between the ranking of MOF adsorbents at the PSA and VSA conditions were examined. H2/CO2 selectivities and H2 permeabilities of MOF membranes were computed as 2.1 × 10-5-6.3 and 230-1.7 × 106 Barrer, respectively. A high number of MOF membranes was identified to surpass the upper bound defined for polymers due to high gas permeabilities of MOFs. Structure-performance relations revealed that MOFs with narrow pore sizes and low porosities are the best adsorbent materials for separation of CO2 from H2, whereas MOFs with large pore sizes and high porosities are the best membrane materials for selective separation of H2. Our results will guide the selection of MOF adsorbents and membranes for efficient H2 purification and CO2 capture processes.

Database for CO2 Separation Performances of MOFs Based on Computational Materials Screening.

Metal-organic frameworks (MOFs) are potential adsorbents for CO2 capture. Because thousands of MOFs exist, computational studies become very useful in identifying the top performing materials for target applications in a time-effective manner. In this study, molecular simulations were performed to screen the MOF database to identify the best materials for CO2 separation from flue gas (CO2/N2) and landfill gas (CO2/CH4) under realistic operating conditions. We validated the accuracy of our computational approach by comparing the simulation results for the CO2 uptakes, CO2/N2 and CO2/CH4 selectivities of various types of MOFs with the available experimental data. Binary CO2/N2 and CO2/CH4 mixture adsorption data were then calculated for the entire MOF database. These data were then used to predict selectivity, working capacity, regenerability, and separation potential of MOFs. The top performing MOF adsorbents that can separate CO2/N2 and CO2/CH4 with high performance were identified. Molecular simulations for the adsorption of a ternary CO2/N2/CH4 mixture were performed for these top materials to provide a more realistic performance assessment of MOF adsorbents. The structure-performance analysis showed that MOFs with Δ Qst0 > 30 kJ/mol, 3.8 Å < pore-limiting diameter < 5 Å, 5 Å < largest cavity diameter < 7.5 Å, 0.5 < ϕ < 0.75, surface area < 1000 m2/g, and ρ > 1 g/cm3 are the best candidates for selective separation of CO2 from flue gas and landfill gas. This information will be very useful to design novel MOFs exhibiting high CO2 separation potentials. Finally, an online, freely accessible database https://cosmoserc.ku.edu.tr was established, for the first time in the literature, which reports all of the computed adsorbent metrics of 3816 MOFs for CO2/N2, CO2/CH4, and CO2/N2/CH4 separations in addition to various structural properties of MOFs.

Solvation of a Cellulose Microfibril in Imidazolium Acetate Ionic Liquids: Effect of a Cosolvent.

The solvation and the onset of dissolution of a cellulose I(ß) microcrystal in ionic liquid media are studied by molecular simulation. Ionic liquids can dissolve large amounts of cellulose, which can later be regenerated from solution, but their high viscosity is an inconvenience. Hydrogen bonding between the anion of the ionic liquid and cellulose is the main aspect determining dissolution. Here we try to elucidate the role of a molecular cosolvent, dimethyl sulfoxide (DMSO), which is an aprotic polar compound, in the system composed of cellulose and the ionic liquid 1-butyl-3-methylimidazolium acetate. We calculated quantities related to specific interactions (mainly hydrogen bonds), conformations, and the structure of local solvation environments, both for a solvated oligomer chain of cellulose and for a model microfibril composed of 36 chains in the I(ß) crystal structure. We compare two solvent systems: the pure ionic liquid and a mixed solvent with an equimolar composition in ionic liquid and DMSO. All entities are represented by detailed all-atom, fully flexible force fields. The main conclusions are that DMSO behaves as an "innocent" cosolvent, lowering the viscosity and accelerating mass transport in the system, but without interacting specifically with cellulose or disrupting the interactions between cellulose with the anions of the ionic liquid. An understanding of solvation in mixed solvents composed of ionic liquids and molecular compounds can enable the design of high-performance media for the use of biomass materials.