Porous Graphene Oxide/Porous Organic Polymer Hybrid Nanosheets Functionalized Mixed Matrix Membrane for Efficient CO2 Capture.

The computational simulation of porous graphene oxide (PGO) indicated that it has great potential for the preparation of gas separation membranes. However, scaling up the manufacture of multilayer, defect-free porous graphene oxide membrane with consistently sized nanopores is extremely challenging. Here, we prepared layer-by-layer CO2-philic Pebax@1657 membranes that were functionalized by o-hydroxyazo-hierarchical porous organic polymers (o-POPs) and PGO. The d-spacing of pristine PGO could be finely regulated through CO2-philic o-POPs to facilitate the permeability of CO2. In addition, the o-POPs exhibit "N2-phobic, CO2-philic" properties with the phenolic hydroxyl and the azo group. The best of the POP-PGO membrane exhibits that the CO2 permeability and ideal selectivity of CO2/N2 are 232.7 Barrer and 80.7, respectively, and it has surpassed the Robeson's upper bound (2008).

Graphitic carbon nitride (g-C3N4) nanosheets functionalized composite membrane with self-cleaning and antibacterial performance.

Membrane fouling significantly impedes membrane performance and thus short lifespan of the membrane. Membranes that functionalized with photocatalytic activity are deemed as an effective and novel approach to settle membrane fouling. The membranes with self-cleaning and antibacterial performance were fabricated via facilely filtering g-C3N4 nanosheets onto polyacrylonitrile (PAN) porous substrates. The g-C3N4 nanosheets were exfoliated by acid etching and ultrasound treatment, and the exfoliated nanosheets was verified by Fourier transform infrared spectra, Atomic force microscopy and X-ray diffraction. The g-C3N4 nanosheets functionalized composite membranes have a water permeability of 11.70 L m-2 h-1 bar-1 and a good antibacterial activity. In addition, the membranes could be restored their original permeability and their surfaces were close to initial color even after three cycles rejecting dyes and post treatment under irradiation with visible light. Besides, the degradable and antimicrobial mechanisms of the membranes were investigated respectively. These g-C3N4 nanosheets composite membranes with self-cleaning and antimicrobial properties have a potential feasibility in water treatment, and provide an alternative method for fabricating self-cleaning membranes.

Ultraselective Pebax Membranes Enabled by Templated Microphase Separation.

Block copolymer materials have been considered as promising candidates to fabricate gas separation membranes. This microphase separation affects the polymer chain packing density and molecular separation efficiency. Here, we demonstrate a method to template microphase separation within a thin composite Pebax membrane, through the controllable self-assembly of one-dimensional halloysite nanotubes (HNTs) within the thin film via the solution-casting technique. Crystallization of the polyamide component is induced at the HNT surface, guiding subsequent crystal growth around the tubular structure. The resultant composite membrane possesses an ultrahigh selectivity (up to 290) for the CO2/N2 gas pair, together with a moderate CO2 permeability (80.4 barrer), being the highest selectivity recorded for Pebax-based membranes, and it easily surpasses the Robeson upper bound. The templated microphase separation concept is further demonstrated with the nanocomposite hollow fiber gas separation membranes, showing its effectiveness of promoting gas selectivity.

Molecular-Level Hybridization of Nafion with Quantum Dots for Highly Enhanced Proton Conduction.

Nanophase-separated membranes hold promise for fast molecule or ion transfer. However, development and practical application are significantly hindered by both the difficulty of chemical modification and nanophase instability. This can be addressed by organic-inorganic hybridization of functional fillers with a precise distribution in specific nanophase. Here, a molecular-level hybridization for nanophase-separated Nafion using 2-5 nm quantum dots (QDs) as a new smart filler is demonstrated. Two kinds of QDs are prepared and used: hydrophilic polymer-like QDs (PQDs) and hydrophobic graphene oxide QDs (GQDs). Because of selective interactions, QDs offer advantages of matched structural size and automatic recognition with the nanophase. A distinctive synthesis of subordinate-assembly, in which QDs are driven by the self-assembly of Nafion affinity chains, is reported. This results in a precise distribution of QDs in the ionic, or backbone, nanophases of Nafion. The resulting PQDs in the ionic nanophase significantly increase membrane proton conduction and device output-power without loss of mechanical stability. This is difficult to realize with conventional fillers. The GQDs in the backbone nanophase reduce the crystallinity and significantly augment membrane water uptake and swelling capacities.

Nanoscale tailor-made membranes for precise and rapid molecular sieve separation.

The precise and rapid separation of different molecules from aqueous, organic solutions and gas mixtures is critical to many technologies in the context of resource-saving and sustainable development. The strength of membrane-based technologies is well recognized and they are extensively applied as cost-effective, highly efficient separation techniques. Currently, empirical-based approaches, lacking an accurate nanoscale control, are used to prepare the most advanced membranes. In contrast, nanoscale control renders the membrane molecular specificity (sub-2 nm) necessary for efficient and rapid molecular separation. Therefore, as a growing trend in membrane technology, the field of nanoscale tailor-made membranes is highlighted in this review. An in-depth analysis of the latest advances in tailor-made membranes for precise and rapid molecule sieving is given, along with an outlook to future perspectives of such membranes. Special attention is paid to the established processing strategies, as well as the application of molecular dynamics (MD) simulation in nanoporous membrane design. This review will provide useful guidelines for future research in the development of nanoscale tailor-made membranes with a precise and rapid molecular sieve separation property.

Oriented Clay Nanotube Membrane Assembled on Microporous Polymeric Substrates.

Organized arrays of halloysite clay nanotubes have great potential in molecular separation, absorption, and biomedical applications. A highly oriented layer of halloysite on polyacrylonitrile porous membrane was prepared via a facile evaporation-induced method. Scanning electronic microscopy, surface attenuated total reflection Fourier transform infrared spectroscopy, and energy dispersive X-ray spectroscopy mapping indicated formation of the nanoarchitecture-controlled membrane. The well-ordered nanotube coating allowed for the excellent dye rejection (97.7% for reactive black 5) with high salt permeation (86.5% for aqueous NaCl), and thus these membranes were suitable for dye purification or concentration. These well-aligned nanotubes' composite membranes also showed very good fouling resistance against dye accumulation and bovine serum albumin adsorption as compared to the pristine polyacrylonitrile or membrane coated with disordered halloysite layer.

Zeolitic Imidazolate Framework/Graphene Oxide Hybrid Nanosheets Functionalized Thin Film Nanocomposite Membrane for Enhanced Antimicrobial Performance.

Inspired by the rational design concept, a novel antimicrobial agent zeolitic imidazolate framework-8 (ZIF-8)/graphene oxide (GO) was synthesized and utilized as a novel and efficient bactericidal agent to fabricate antimicrobial thin film nanocomposite (TFN) membranes via interfacial polymerization. The resultant hybrid nanosheets not only integrates the merits of both ZIF-8 and GO but also yields a uniform dispersion of ZIF-8 onto GO nanosheets simultaneously, thus effectively eliminating the agglomeration of ZIF-8 in the active layer of membranes. A ZIF-8/GO thin film nanocomposite (TFN-ZG) membrane with typical water permeability (40.63 L m(-2) h(-1) MPa(-1)) allows for efficient bivalent salt removal (rejections of Na2SO4 and MgSO4 were 100% and 77%, respectively). Furthermore, the synthesized ZIF-8/GO nanocomposites were verified to have an optimal antimicrobial activity (MIC,128 µg/mL) in comparison with ZIF-8 and GO separately, which sufficiently endowed the TFN-ZG membrane with excellent antimicrobial activity (84.3% for TFN-ZG3). Besides, the antimicrobial mechanisms of ZIF-8/GO hybrid nanosheets and TFN-ZG membranes were proposed. ZIF-8/GO functionalized membrane with high antimicrobial activity and salt retention denoted its great potential in water desalination, and we suggest that ZIF-8 based crystal may offer a new pathway for the synthesis of a multifunctional bactericide.

Ultrafine MnO2 nanoparticles decorated on graphene oxide as a highly efficient and recyclable catalyst for aerobic oxidation of benzyl alcohol.

The highly active and selective aerobic oxidation of aromatic alcohols over earth-abundant, inexpensive and recyclable catalysts is highly desirable. We fabricated herein MnO2/graphene oxide (GO) composites by a facile in-situ growth approach at room temperature and used them in selective aerobic oxidation of benzyl alcohol to benzaldehyde. TEM, XRD, FTIR, XPS and N2 adsorption/desorption analysis were employed to systematically investigate the morphology, particle size, structure and surface properties of the catalysts. The 96.8% benzyl alcohol conversion and 100% benzaldehyde selectivity over the MnO2/GO (10/100) catalyst with well dispersive ultrafine MnO2 nanoparticles (ca. 3nm) can be obtained within 3h under 383K. Simultaneously, no appreciable loss of activity and selectivity occurred after recycling use up to six times. Due to their significant low cost, excellent catalytic performance, the MnO2/GO composites have huge application prospect in organic synthesis.

Constructing Ionic Liquid-Filled Proton Transfer Channels within Nanocomposite Membrane by Using Functionalized Graphene Oxide.

Herein, nanocomposite membranes are fabricated based on functionalized graphene oxides (FGOs) and sulfonated poly(ether ether ketone) (SPEEK), followed by being impregnated with imidazole-type ionic liquid (IL). The functional groups (acidic group or basic group) on FGOs generate strong interfacial interactions with SPEEK chains and then adjust their motion and stacking. As a result, the nanocomposite membranes possess tunable interfacial domains as determined by its free volume characteristic, which provides regulated location for IL storage. The stored ILs act as hopping sites for water-free proton conduction along the FGO-constructed interfacial channels. The microstructure at SPEEK-FGO interface governs the IL uptake and distribution in nanocomposite membrane. Different from GO and vinyl imidazole functionalized GO (VGO), the presence of acidic (-SO3H) groups confers the p-styrenesulfonic acid functionalized GO (SGO) incorporated nanocomposite membrane loose interface and strong electrostatic attraction with imidazole-type IL, imparting an enhanced IL uptake and anhydrous proton conductivity. Nanocomposite membrane containing 7.5% SGO attains the maximum IL uptake of 73.7% and hence the anhydrous conductivity of 21.9 mS cm(-1) at 150 °C, more than 30 times that of SPEEK control membrane (0.69 mS cm(-1)). In addition, SGOs generate electrostatic attractions to the ILs confined within SGO-SPEEK interface, affording the nanocomposite membrane enhanced IL retention ability.

High flux, positively charged loose nanofiltration membrane by blending with poly (ionic liquid) brushes grafted silica spheres.

Silica spheres modified by poly (ionic liquid) brushes, a novel positively charged nanomaterial is prepared by atom transfer radical polymerization (ATRP). A high flux positively charged loose nanofiltration membrane is fabricated via "blending-phase inversion" method. The morphology structures, hydrophilicity, thermal and mechanical properties, permeation performance of these membranes are investigated in detail. The results reveal that the hybrid membranes have enhanced surface hydrophilicity, water permeability, thermal stability, and mechanical properties. Characterization of membrane separation properties shows that the hybrid membranes possess higher salt permeability and relatively higher rejection for reactive dyes, which may open opportunities for the recycling of reactive dyes wastewater. Moreover, such hybrid membranes have an outstanding operational stability and salts concentration showed little effect on the separation properties.

Continuous fixed bed adsorption of Cu(II) by halloysite nanotube-alginate hybrid beads: an experimental and modelling study.

We used natural resources of halloysite nanotubes and alginate to prepare a novel porous adsorption material of organic-inorganic hybrid beads. The adsorption behaviour of Cu(II) onto the hybrid beads was examined by a continuous fixed bed column adsorption experiment. Meanwhile, the factors affecting the adsorption capacity such as bed height, influent concentration and flow rate were investigated. The adsorption capacity (Q0) reached 74.13 mg/g when the initial inlet concentration was 100 mg/L with a bed height of 12 cm and flow rate of 3 ml/min. The Thomas model and bed-depth service time fitted well with the experimental data. In the regeneration experiment, the hybrid beads retained high adsorption capacity after three adsorption-desorption cycles. Over the whole study, the new hybrid beads showed excellent adsorption and regeneration properties as well as favourable stability.

Enhanced antibacterial activity of silver nanoparticles/halloysite nanotubes/graphene nanocomposites with sandwich-like structure.

A sandwich-like antibacterial reagent (Ag/HNTs/rGO) was constructed through the direct growth of silver nanoparticles on the surface graphene-based HNTs nanosheets. Herein, various nanomaterials were combined by adhesion effect of DOPA after self-polymerization. Ag/HNTs/rGO possess enhanced antibacterial ability against E. coli and S. aureus compared with individual silver nanoparticles, rGO nanosheets or their nanocomposites.

In-situ preparation of NaA zeolite/chitosan porous hybrid beads for removal of ammonium from aqueous solution.

Inorganic/organic hybrid materials play important roles in removal of contaminants from wastewater. Herein, we used the natural materials of halloysite and chitosan to prepare a new adsorbent of NaA zeolite/chitosan porous hybrid beads by in-situ hydrothermal synthesis method. SEM indicated that the porous hybrid beads were composed of 6-8 µm sized cubic NaA zeolite particles congregated together with chitosan. The adsorption behavior of NH4(+) from aqueous solution onto hybrid beads was investigated at different conditions. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms. A maximum adsorption capacity of 47.62 mg/g at 298 K was achieved according to Langmuir model. The regenerated or reused experiments indicated that the adsorption capacity of the hybrid beads could maintain in 90% above after 10 successive adsorption-desorption cycles. The high adsorption and reusable ability implied potential application of the hybrid beads for removing NH4(+) pollutants from wastewater.

Grafting amphiphilic brushes onto halloysite nanotubes via a living RAFT polymerization and their Pickering emulsification behavior.

Amphiphilic brushes of poly(4-vinylpyridine)-block-polystyrene (P4VP-b-PS) and polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) are grafted onto halloysite nanotubes (HNTs) via a surface reversible addition-fragmentation chain transfer (RAFT) living polymerization through anchoring R group in RAFT agent S-1-dodecyl-S'-(R,R'-dimethyl-R″-acetic acid) trithiocarbonates (DDMAT). The characterization of TGA, TEM, and GPC show that amphiphilic brushes are successfully grafted onto HNTs in a living manner. To verify the amphiphilicity of HNTs grafted with block copolymers, their Pickering emulsification behavior in water/soybean oil diphase mixture is studied. The results show that modified HNTs can emulsify water/soybean oil diphase mixture and the emulsification performance is dependent on microstructure of amphiphilic brushes such as hydrophilic/hydrophobic segment size and sequence.

Surface modification of halloysite nanotubes with dopamine for enzyme immobilization.

Halloysite nanotubes (HNTs) have been proposed as a potential support to immobilize enzymes. Improving enzyme loading on HNTs is critical to their practical applications. Herein, we reported a simple method on the preparation of high-enzyme-loading support by modification with dopamine on the surface of HNTs. The modified HNTs were characterized by transmission electron microscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy analyses. The results showed that dopamine could self-polymerize to adhere to the surface of HNTs and form a thin active coating. While the prepared hybrid nanotubes were used to immobilize enzyme of laccase, they exhibited high loading ability of 168.8 mg/g support, which was greatly higher than that on the pristine HNTs (11.6 mg/g support). The immobilized laccase could retain more than 90% initial activity after 30 days of storage and the free laccase only 32%. The immobilized laccase could also maintain more than 90% initial activity after five repeated uses. In addition, the immobilized laccase exhibited a rapid degradation rate and high degradation efficiency for removal of phenol compounds. These advantages indicated that the new hybrid material can be used as a low-cost and effective support to immobilize enzymes.

Preparation and antibacterial property of PES/AgNO3 three-bore hollow fiber ultrafiltration membranes.

In this study, a three-bore polyethersulfone (PES) hollow fiber ultrafiltration (UF) membrane with antibacterial properties was prepared by phase inversion, using PES as the membrane material, N,N-dimethylacetamide (DMAC) as solvent, polyvinylpyrrolidone (PVP) and AgNO3 as additives. The silver particles were detected by X-ray photoelectron spectroscopy. The effect of AgNO3 content on the antibacterial properties and separation performance was studied in detail. The membranes showed good antibacterial activity against Escherichia coli after adding AgNO3 and the antibacterial rate of PES/AgNO3 UF membrane with AgNO3 content of 1 wt% could reach 99.9% after running for 48 hours. Moreover, the bovine serum albumin solution filtration results indicated that the PES/AgNO3 membranes had a certain degree of antifouling performance. Therefore, three-bore PES/AgNO3 membranes have a potential application to reduce both bacterial and organic fouling in water treatment.

Potent antibacterial activity of a novel silver nanoparticle-halloysite nanotube nanocomposite powder.

Halloysite nanotubes (HNTs), natural nanotube, have been developed as a support for loading of antibacterial agents. Firstly, HNTs were modified by silane coupling agent (KH-792). And then, modified HNTs were immersed in silver nitrate solution and a complex reaction between the two amino groups of KH-792 and silver ions formed, leading to large clusters on the surface of HNTs. Finally, these silver containing clusters were converted into silver nanoparticles (Ag NPs) with about 5nm diameter by reduction process. A new antibacterial agent, Ag NPs/HNTs, was characterized by X-ray fluorescence (XRF), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and scanning transmission electron microscopy-energy dispersive X-ray analysis (STEM-EDX). The antibacterial test indicated that Ag NPs/HNTs showed good antibacterial performance against Gram-negative bacteria (Escherichia coli) and Gram-positive bacteria (Staphylococcus aureus).

Antibacterial properties of PES/CuCl(2) three-bore hollow fiber UF membrane.

In this study, a three-bore polyethersulfone (PES) hollow fiber ultrafiltration (UF) membrane with antibacterial properties was prepared by phase inversion, using PES as the membrane material, N,N-dimethylacetamide (DMAC) as solvent, polyvinylpyrrolidone (PVP) and CuCl(2) as additives. The effect of CuCl(2) content on the water flux and rejection was studied and the antibacterial properties of PES hollow fiber UF membrane were also investigated. The water flux results indicated that the hydrophilic properties of PES UF membranes were improved after adding CuCl(2). The rejection of PVA-50000 was expected to drop slightly but remain high above 96%. The membranes showed good antibacterial activity against Escherichia coli (E. coli) after adding CuCl(2) and the antibacterial rate of PES/CuCl(2) UF membranes was close to 100% after running for 48 h. PES hollow fiber UF membranes with antibacterial properties were prepared through the formation of the water-soluble PVP/Cu(2+) complex with spatial network structure, which have good antibacterial and hydrophilic properties. Therefore, this study could provide an effective method for membrane antifouling.

Hierarchical MnO2 nanostructures: synthesis and their application in water treatment.

Hierarchical MnO2 nanostructures were prepared through the reaction between KMnO4 and oleic acid at room temperature in the surfactant-free microemulsion system. The obtained samples were characterized by powder X-ray diffraction, N2 adsorption, scanning electron microscopy, and transmission electron microscopy. The results indicated that the flowerlike nanospheres were three-dimensional (3D) porous microstructures consisting of nanoplates. The surface area of the sample was 171.5 m(2)/g and the distribution of pore diameter lay within the range of 5-15 nm. The prepared hierarchically structured MnO2 showed excellent adsorption capacity and rapid adsorption rate for methylene blue ions in water. The maximum adsorption capacity of methylene blue was as high as 273.9 mg/g and 97.5% of the dye was removed within initial 5 min of contact time. Compared with other adsorbents, the synthesized hierarchical MnO2 nanostructures displayed a faster adsorption rate and higher adsorption capacity, which implied potential application for removing dye pollutants from waste water.

Preparation of three-bore hollow fiber charged nanofiltration membrane for separation of organics and salts.

Three-bore hollow fiber charged nanofiltration (NF) membrane was prepared by interfacial polymerization (IP). The results showed that the flux and rejection of NF membrane prepared in this study increased with the increasing in the operating pressure. The water flux decreased and rejection for obvious dyes increased as the solute concentration increased. The separation factor for mixture of Xylenol orange/NaCl decreased when NaCl concentration in solution increased and could reach to as high as 18. In addition, three-bore hollow fiber charged nanofiltration membrane prepared in this study has excellent stability for strong acid (pH = 3), strong alkali (pH = 11) and high temperature solution (80 °C).