Uniformly Distributed Mixed Matrix Membranes via a Solution Processable Strategy for Propylene/Propane Separation.

Aggregation of filler particles during the formation of mixed matrix membranes is difficult to avoid when filler loadings exceed a 10-15 wt %. Such agglomeration usually leads to poor membrane performance. In this work, using a ZIF-67 metal-organic framework (MOF) as filler along with surface modification of Ag4 tz4 to improve processability and selective olefin adsorption, we demonstrate that highly loaded with a very low agglomeration degree membranes can be synthesized displaying unmatched separation selectivity (39) for C3 H6 /C3 H8 mixtures and high permeability rates (99 Barrer), far surpassing previous reports in the literature. Through molecular dynamics simulation, the enhanced compatibility between ZIF-67 and polymer matrix with adding Ag4 tz4 was proven and the tendency in gas permeability and C3 H6 selectivity in the mixed matrix membranes (MMMs) were well explained. More importantly, the membrane showed a wide range of pressure and temperature resistance, together with remarkable long-term stability (>900 h). The modification method might help solve interface issues in MMMs and can be extended to the fabrication of other fillers to achieve high performance MMMs for gas separation.

Amidoxime modified polymers of intrinsic microporosity/alginate composite hydrogel beads for efficient adsorption of cationic dyes from aqueous solution.

Polymers of intrinsic microporosity (PIM-1) has demonstrated great potential in adsorption and separation fields. In this study, PIM-1 was structured into an applicable and efficient adsorbent using a facile way. PIM-1 was first modified by amidoxime, and then the amidoxime modified PIM-1 (AOPIM-1) was mingled into alginate (Alg) hydrogel to obtain composite hydrogel beads. The AOPIM-1/Alg composite beads were further employed for removal of malachite green (MG) from aqueous solution and the effects of doped ratio, adsorbent dosage, contact time, and initial dye concentration on the MG adsorption performance were systematically investigated. The MG adsorption capacity of pure Alg beads was substantially enhanced after incorporating AOPIM-1. Furthermore, isothermal, kinetic and thermodynamic studies were performed to explore the fundamental adsorption behavior. Both Freundlich isotherm and Langmuir isotherm models can fit the adsorption isotherm data well, and the adsorption kinetics is well described by Pseudo-second-order. The adsorption process is feasible, spontaneous and endothermic. In addition, mixed dyes adsorption measurements indicate that AOPIM-1/Alg beads are highly selective to adsorb cationic dyes from anionic/cationic mixed dyes solution. The regeneration test shows that above 90% of the adsorption capacity of the composite beads can be maintained after 10 cycles of MG adsorption/desorption. These findings point that AOPIM-1/Alg composite hydrogel beads are an efficient, up-and-coming and recyclable adsorbent for cationic dyes adsorption from aqueous solution.

Moderately Crystalline Azine-Linked Covalent Organic Framework Membrane for Ultrafast Molecular Sieving.

Covalent organic frameworks are potential candidates for the preparation of advanced molecular separation membranes due to their porous structure, uniform aperture, and chemical stability. However, the fabrication of continuous COF membranes in a facile and mild manner remains a challenge. Herein, a continuous, defect-free, and flexible azine-linked ACOF-1 membrane was prepared on a hydrolyzed polyacrylonitrile (HPAN) substrate via in situ interfacial polymerization (IP). A moderately crystalline COF ultrathin selective layer enabled ultrafast molecular sieving. The effect of synthesis parameters including precursor concentration, catalyst dosage, and reaction duration on the dye separation performance was investigated. The optimized membrane displayed an ultrahigh water permeance of 142 L m-2 h-1 bar-1 together with favorable rejection (e.g., 99.2% for Congo red and 96.3% for methyl blue). The water permeance is 5-12 times higher than that of reported membranes with similar rejections. In addition, ACOF-1 membranes demonstrate outstanding long-term stability together with organic solvent and extreme pH resistance. Meanwhile, the membrane is suitable for removing dyes from salt solution products owing to their nonselective permeation for hydrated salt ions (<10.6%). The superior performance and the excellent chemical stability render the ACOF-1 membrane a satisfactory system for water purification.

High-Performance Polybenzimidazole Membranes for Helium Extraction from Natural Gas.

Increasing helium use in research and production processes necessitates separation techniques to secure sufficient supply of this noble gas. Energy-efficient helium production from natural gas is still a big challenge. Membrane gas separation technology could play an important role. Herein, a novel poly( p-phenylene benzobisimidazole) (PBDI) polymeric membrane for helium extraction from natural gas with low He abundance is reported. The membranes were fabricated by a facile interfacial polymerization at room temperature. The thin and defect-free membrane structure was manipulated by the confined polymerization of monomers diffusing through the interface between two immiscible liquids. Both He/CH4 selectivity and He permeance are competitive over those of other commercial perfluoropolymers. Even at low He content of 1%, separation performance of the PBDI membrane transcended the current upper bound. The unprecedented selectivity (>1000) together with the excellent stability (∼360 h) endows PBDI membranes with a great potential for energy-efficient industrial recovery and production of this precious He resources from reservoirs with low abundance.

One-Pot Synthesis of High-Flux b-Oriented MFI Zeolite Membranes for Xe Recovery.

We demonstrate that b-oriented MFI (Mobil Five) zeolite membranes can be manufactured by in situ crystallization using an intermediate amorphous SiO2 layer. The improved in-plane growth by using a zeolite growth modifier leads to fusion of independent crystals and eliminates boundary gaps, giving good selectivity in the separation of CO2/Xe mixtures. The fast diffusion of CO2 dominates the overall membrane selectivity toward the CO2/Xe mixture. Because of the straight and short [010] channels, the obtained CO2 permeation fluxes are several orders of magnitude higher than those of carbon molecular sieving membranes and polymeric membranes, opening opportunities for Xe recovery from waste anesthetic gas.

Facile manufacture of porous organic framework membranes for precombustion CO2 capture.

The development of new membranes with high H2 separation performance under industrially relevant conditions (high temperatures and pressures) is of primary importance. For instance, these membranes may facilitate the implementation of energy-efficient precombustion CO2 capture or reduce energy intensity in other industrial processes such as ammonia synthesis. We report a facile synthetic protocol based on interfacial polymerization for the fabrication of supported benzimidazole-linked polymer membranes that display an unprecedented H2/CO2 selectivity (up to 40) at 423 K together with high-pressure resistance and long-term stability (>800 hours in the presence of water vapor).

Molecular-Scale Hybrid Membranes Derived from Metal-Organic Polyhedra for Gas Separation.

The preparation and the performance of mixed matrix membranes based on metal-organic polyhedra (MOPs) are reported. MOP fillers can be dispersed as discrete molecular units (average 9 nm in diameter) when low filler cargos are used. In spite of the low doping amount (1.6 wt %), a large performance enhancement in permeability, aging resistance, and selectivity can be achieved. We rationalize this effect on the basis of the large surface to volume ratio of the filler, which leads to excellent dispersion at low concentrations and thus alters polymer packing. Although membranes based only on the polymer component age quickly with time, the performance of the resulting MOP-containing membranes meets the commercial target for postcombustion CO2 capture for more than 100 days.

Nanosheets of Nonlayered Aluminum Metal-Organic Frameworks through a Surfactant-Assisted Method.

During the last decade, the synthesis and application of metal-organic framework (MOF) nanosheets has received growing interest, showing unique performances for different technological applications. Despite the potential of this type of nanolamellar materials, the synthetic routes developed so far are restricted to MOFs possessing layered structures, limiting further development in this field. Here, a bottom-up surfactant-assisted synthetic approach is presented for the fabrication of nanosheets of various nonlayered MOFs, broadening the scope of MOF nanosheets application. Surfactant-assisted preorganization of the metallic precursor prior to MOF synthesis enables the manufacture of nonlayered Al-containing MOF lamellae. These MOF nanosheets are shown to exhibit a superior performance over other crystal morphologies for both chemical sensing and gas separation. As revealed by electron microscopy and diffraction, this superior performance arises from the shorter diffusion pathway in the MOF nanosheets, whose 1D channels are oriented along the shortest particle dimension.

Enhanced vapour sensing using silicon nanowire devices coated with Pt nanoparticle functionalized porous organic frameworks.

Recently various porous organic frameworks (POFs, crystalline or amorphous materials) have been discovered, and used for a wide range of applications, including molecular separations and catalysis. Silicon nanowires (SiNWs) have been extensively studied for diverse applications, including as transistors, solar cells, lithium ion batteries and sensors. Here we demonstrate the functionalization of SiNW surfaces with POFs and explore its effect on the electrical sensing properties of SiNW-based devices. The surface modification by POFs was easily achieved by polycondensation on amine-modified SiNWs. Platinum nanoparticles were formed in these POFs by impregnation with chloroplatinic acid followed by chemical reduction. The final hybrid system showed highly enhanced sensitivity for methanol vapour detection. We envisage that the integration of SiNWs with POF selector layers, loaded with different metal nanoparticles will open up new avenues, not only in chemical and biosensing, but also in separations and catalysis.

Azine-Linked Covalent Organic Framework (COF)-Based Mixed-Matrix Membranes for CO2 /CH4 Separation.

Mixed-matrix membranes (MMMs) comprising Matrimid and a microporous azine-linked covalent organic frameworks (ACOF-1) were prepared and tested in the separation of CO2 from an equimolar CO2 /CH4 mixture. The COF-based MMMs show a more than doubling of the CO2 permeability upon 16 wt % ACOF-1 loading together with a slight increase in selectivity compared to the bare polymer. These results show the potential of COFs in the preparation of MMMs.

Tunable hydrogen separation in porous graphene membrane: first-principle and molecular dynamic simulation.

First-principle density functional theory (DFT) calculation and molecular dynamic (MD) simulation are employed to investigate the hydrogen purification performance of two-dimensional porous graphene material (PG-ESX). First, the pore size of PG-ES1 (3.2775 Å) is expected to show high selectivity of H2 by DFT calculation. Then MD simulations demonstrate the hydrogen purification process of the PG-ESX membrane. The results indicate that the selectivity of H2 over several other gas molecules that often accompany H2 in industrial steam methane reforming or dehydrogenation of alkanes (such as N2, CO, and CH4) is sensitive to the pore size of the membrane. PG-ES and PG-ES1 membranes both exhibit high selectivity for H2 over other gases, but the permeability of the PG-ES membrane is much lower than the PG-ES1 membrane because of the smaller pore size. The PG-ES2 membrane with bigger pores demonstrates low selectivity for H2 over other gases. Energy barrier and electron density have been used to explain the difference of selectivity and permeability of PG-ESX membranes by DFT calculations. The energy barrier for gas molecules passing through the membrane generally increase with the decreasing of pore sizes or increasing of molecule kinetic diameter, due to the different electron overlap between gas and a membrane. The PG-ES1 membrane is far superior to other carbon membranes and has great potential applications in hydrogen purification, energy clean combustion, and making new concept membrane for gas separation.

Self-assembly of double helical nanostructures inside carbon nanotubes.

We use molecular dynamics (MD) simulations to show that a DNA-like double helix of two poly(acetylene) (PA) chains can form inside single-walled carbon nanotubes (SWNTs). The computational results indicate that SWNTs can activate and guide the self-assembly of polymer chains, allowing them to adopt a helical configuration in a SWNT through the combined action of the van der Waals potential well and the π-π stacking interaction between the polymer and the inner surface of SWNTs. Meanwhile both the SWNT size and polymer chain stiffness determine the outcome of the nanostructure. Furthermore, we also found that water clusters encourage the self-assembly of PA helical structures in the tube. This molecular model may lead to a better understanding of the formation of a double helix biological molecule inside SWNTs. Alternatively, it could form the basis of a novel nanoscale material by utilizing the 'empty' spaces of SWNTs.

Influence of chemical functionalization on the CO2/N2 separation performance of porous graphene membranes.

The separation of CO2 from a mixture of CO2 and N2 using a porous graphene membrane was investigated using molecular dynamics (MD) simulations. The effects of chemical functionalization of the graphene sheet and pore rim on the gas separation performance of porous graphene membranes were examined. It was found that chemical functionalization of the graphene sheet can increase the absorption ability of CO2, while chemical functionalization of the pore rim can significantly improve the selectivity of CO2 over N2. The results show that the porous graphene membrane with all-N modified pore-16 exhibits a higher CO2 selectivity over N2 (∼11) due to the enhanced electrostatic interactions compared to the unmodified graphene membrane. This demonstrates the potential use of functionalized porous graphene as single-atom-thick membrane for CO2 and N2 separation. We provide an effective way to improve the gas separation performance of porous graphene membranes, which may be useful for designing new concept membranes for other gases.