Polyamide-based membranes with structural homogeneity for ultrafast molecular sieving.

Thin-film composite membranes formed by conventional interfacial polymerization generally suffer from the depth heterogeneity of the polyamide layer, i.e., nonuniformly distributed free volume pores, leading to the inefficient permselectivity. Here, we demonstrate a facile and versatile approach to tune the nanoscale homogeneity of polyamide-based thin-film composite membranes via inorganic salt-mediated interfacial polymerization process. Molecular dynamics simulations and various characterization techniques elucidate in detail the underlying molecular mechanism by which the salt addition confines and regulates the diffusion of amine monomers to the water-oil interface and thus tunes the nanoscale homogeneity of the polyamide layer. The resulting thin-film composite membranes with thin, smooth, dense, and structurally homogeneous polyamide layers demonstrate a permeance increment of ~20-435% and/or solute rejection enhancement of ~10-170% as well as improved antifouling property for efficient reverse/forward osmosis and nanofiltration separations. This work sheds light on the tunability of the polyamide layer homogeneity via salt-regulated interfacial polymerization process.

Novel Cellulose Triacetate (CTA)/Cellulose Diacetate (CDA) Blend Membranes Enhanced by Amine Functionalized ZIF-8 for CO2 Separation.

Currently, cellulose acetate (CA) membranes dominate membrane-based CO2 separation for natural gas purification due to their economical and green nature. However, their lower CO2 permeability and ease of plasticization are the drawbacks. To overcome these weaknesses, we have developed high-performance mixed matrix membranes (MMMs) consisting of cellulose triacetate (CTA), cellulose diacetate (CDA), and amine functionalized zeolitic imidazolate frameworks (NH2-ZIF-8) for CO2 separation. The NH2-ZIF-8 was chosen as a filler because (1) its pore size is between the kinetic diameters of CO2 and CH4 and (2) the NH2 groups attached on the surface of NH2-ZIF-8 have good affinity with CO2 molecules. The incorporation of NH2-ZIF-8 in the CTA/CDA blend matrix improved both the gas separation performance and plasticization resistance. The optimized membrane containing 15 wt.% of NH2-ZIF-8 had a CO2 permeability of 11.33 Barrer at 35 °C under the trans-membrane pressure of 5 bar. This is 2-fold higher than the pristine membrane, while showing a superior CO2/CH4 selectivity of 33. In addition, the former had 106% higher CO2 plasticization resistance of up to about 21 bar and an impressive mixed gas CO2/CH4 selectivity of about 40. Therefore, the newly fabricated MMMs based on the CTA/CDA blend may have great potential for CO2 separation in the natural gas industry.

Can Composite Janus Membranes with an Ultrathin Dense Hydrophilic Layer Resist Wetting in Membrane Distillation?

Tackling membrane wetting is an ongoing challenge for large-scale applications of membrane distillation (MD). Herein, composite Janus MD membranes comprising an ultrathin dense hydrophilic layer are developed by layer-by-layer assembling cationic polyethyleneimine and anionic poly(sodium 4-styrenesulfonate) polyelectrolytes on a hydrophobic polyvinylidene fluoride substrate. Using surfactant-containing saline water as the feed with low surface tension, experiments reveal that the number of polyelectrolyte layers, rather than surface wettability or surface charge, determines the anti-wetting performance of the composite Janus membranes. More deposited layers yield higher wetting resistance. With the aid of positron annihilation spectroscopy, this study, for the first time, demonstrates the origin of the excellent wetting resistance of the composite Janus membranes. The effective pore size of the polyelectrolyte multilayer decreases with an increase in the number of the deposited layer. The membrane with an ultrathin hydrophilic multilayer of 48 nm has a sufficiently small pore size to sieve out surfactant molecules from the feed solution via a size exclusion mechanism, thus protecting the hydrophobic substrate from being wetted by the low-surface-tension feed water. This study may pave the way for developing next-generation anti-wetting Janus membranes for robust membrane distillation.

A solution-processable and ultra-permeable conjugated microporous thermoset for selective hydrogen separation.

The synthesis of a polymer that combines the processability of plastics with the extreme rigidity of cross-linked organic networks is highly attractive for molecular sieving applications. However, cross-linked networks are typically insoluble or infusible, preventing them from being processed as plastics. Here, we report a solution-processable conjugated microporous thermoset with permanent pores of ~0.4 nm, prepared by a simple heating process. When employed as a two-dimensional molecular sieving membrane for hydrogen separation, the membrane exhibits ultrahigh permeability with good selectivity for H2 over CO2, O2, N2, CH4, C3H6 and C3H8. The combined processability, structural rigidity and easy feasibility make this polymeric membrane promising for large-scale hydrogen separations of commercial and environmental relevance.

Molecularly tunable thin-film nanocomposite membranes with enhanced molecular sieving for organic solvent forward osmosis.

Thin-film nanocomposites (TFN) functionalized with tunable molecular-sieving nanomaterials have been employed to tailor membranes, with an enhanced permeability and selectivity. Herein, water-soluble hollow cup-like macrocyclic molecules, sulfothiacalix[4]arene (STCAss) and sulfocalix[4]arene (SCA), are ionically bonded into the polyamide network to engineer the molecular-sieving properties of TFN membranes for organic solvent forward osmosis (OSFO). Introducing both STCAss and SCA into the polyamide network not only increases the free volume, but also reduces the thickness of the TFN layers. Combining with their molecularly tunable size of the lower cavities, both STCAss and SCA enable the TFN membranes to size exclusively reject the draw solutes, but only STCAss-functionalized membrane has an ethanol flux doubling the pristine one under the FO and PRO modes in OSFO processes; leading the functionalized polyamide network with remarkable improvements in OSFO performance. This study may provide insights to molecularly functionalize TFN membranes using multifunctional nano-fillers for sustainable separations.

Emerging thin-film nanocomposite (TFN) membranes for reverse osmosis: A review.

Thin-film composite (TFC) membranes are the heart of reverse osmosis (RO) processes for desalination and water reuse. In recent years, nanomaterials with high permeability, selectivity and chemical resistance, and low fouling tendency have begun to emerge and be applied in many other fields. This has stimulated the research on novel RO membranes consisting of nanomaterials (non-porous and porous) in their selective layers. Encouraging results have been demonstrated. Herein, the state-of-the-art developments of polyamide thin-film nanocomposite (TFN) membranes for RO processes are summarized since the concept of TFN was introduced in 2007. While it is obvious that nanomaterials could impart exclusive properties, it should also be noted that significant challenges still exist for research and commercialization of TFN membranes, such as selection of proper nanomaterials, prevention of leaching of nanoparticles, and performance and cost analysis before large-scale RO membrane manufacturing. Future research directions are outlined to offer insights for the fabrication of much advanced TFN membranes with optimal interface morphology and separation performance.

Advanced Porous Materials in Mixed Matrix Membranes.

Membrane technology has gained great interest in industrial separation processing over the past few decades owing to its high energy efficiency, small capital investment, environmentally benign characteristics, and the continuous operation process. Among various types of membranes, mixed matrix membranes (MMMs) combining the merits of the polymer matrix and inorganic/organic fillers have been extensively investigated. With the rapid development of chemistry and materials science, recent studies have shifted toward the design and application of advanced porous materials as promising fillers to boost the separation performance of MMMs. Here, first a comprehensive overview is provided on the choices of advanced porous materials recently adopted in MMMs, including metal-organic frameworks, porous organic frameworks, and porous molecular compounds. Novel trends in MMMs induced by these advanced porous fillers are discussed in detail, followed by a summary of applying these MMMs for gas and liquid separations. Finally, a concise conclusion and current challenges toward the industrial implementation of MMMs are outlined, hoping to provide guidance for the design of high-performance membranes to meet the urgent needs of clean energy and environmental sustainability.

Green Layer-by-Layer Method for the Preparation of Polyacrylonitrile-Supported Zinc Benzene-1,4-dicarboxylic Acid Membranes.

Ultrafiltration-level polyacrylonitrile (PAN) flat sheet membranes were chemically modified through cross-linking and hydrolysis to provide a suitable surface for the growth of a selective layer composed of a Zn benzene-1,4-dicarboxylic acid (Zn(BDC)) metal-organic framework (MOF). Unlike typical membrane modification methods or conventional MOF synthesis procedures, deionized (DI) water was the only solvent used for each of the modification steps. To better understand the layer-by-layer MOF growth process, several MOF growth conditions were also studied, including the effects of solution concentration, growth temperature, membrane immersion time and the number of layers. Subsequently, organic solvent nanofiltration (OSN) was used to test the effectiveness of the modifications and compare the performances of the fabricated membranes. With the appropriate combination of the MOF growth conditions, the layer-by-layer method was used to produce an OSN membrane with an isopropanol permeance of 2.39 L m-2 h-1 bar-1 and an 86 % rejection of the dye Brilliant Blue R (Mw 825.97 g mol-1 ).

Precise Molecular Sieving Architectures with Janus Pathways for Both Polar and Nonpolar Molecules.

Precise molecular sieving architectures with Janus superhighways are constructed via a molecularly engineered interfacial reaction between cyclodextrin (CD) and trimesoyl chloride (TMC). Interestingly, the CD/TMC nanofilms constructed with both hydrophobic inner cavities and hydrophilic channels exhibit exceptionally high permeances for both polar and nonpolar solvents. The precise molecular sieving functions are determined by the type of CD building blocks and the inner cavities of intrinsic 3D hollow bowls. Positron annihilation spectroscopy (PAS) confirms that a larger inner CD cavity tends to generate a larger free volume and higher microporosity. Based on the rejection ratio of various dyes, the estimated molecular weight cutoff of CD/TMC nanofilms follows the trend of α-CD/TMC (320 Da) <ß-CD/TMC (400 Da) <γ-CD/TMC (550 Da), which is in strict accordance with the orders of their free volumes measured by PAS and inner cavity sizes of α-CD <ß-CD <γ-CD. This kind of novel CD/TMC molecular sieving membrane with intrinsic microporosity containing tunable pore size and sharp pore-size distribution can effectively discriminate molecules with different 3D sizes.

Molecularly Tuned Free Volume of Vapor Cross-Linked 6FDA-Durene/ZIF-71 MMMs for H2 /CO2 Separation at 150 °C.

The H2 /CO2 separation properties of di/triamine vapor cross-linked mixed matrix membranes with molecularly tuned free-volume at 150 °C are reported. Free-volume is molecularly tuned by altering the degree of chain-motion using cross-linkers with different chain lengths. A more restricted degree of chain-motion is achieved in the cross-linked network and the resultant membrane has a higher H2 /CO2 selectivity at 150 °C.