Reversibly Cross-Linked Isoporous Membranes Fabricated by the Recyclable Block Copolymer with Pendent Dithiolane Groups.

The reversible formation and cleavage of disulfide bonds under physical/chemical stimuli make it a valuable motif in constructing dynamically cross-linked materials. In the present work, the block copolymer bearing pendent dithiolanes was synthesized and fabricated into isoporous membranes by the combination of self-assembly and nonsolvent-induced phase separation strategy. The cross-linking within the membrane was realized by the thiol-initiated ring-opening cascades of cyclic disulfides. Successful formation of disulfide bond networks within the isoporous membranes was proved by the Raman spectra, UV-vis diffuse reflectance spectroscopy, differential scanning calorimetry, and rheological analysis. The cross-linking in membranes was further demonstrated by the notably improved toughness and obviously enhanced swelling resistance to acid/alkaline solution as well as organic solvents. Importantly, the cross-linked isoporous membranes were fully dissolvable in solution containing dithiothreitol, which enabled the complete cleavage of disulfide bonds and successful recovery of the block copolymer that was able to be repeatedly fabricated into isoporous membranes with pore sizes identical to membranes prepared from the freshly synthesized copolymer. Our results indicate that dynamically cross-linked isoporous membranes with improved durability and good recyclability can be custom-made by simply incorporating active dithiolane moieties into self-assembling block copolymers.

Recent developments in polymeric nano-based separation membranes.

Polymeric nanomaterials, which have tuneable chemical structures, versatile functionalities, and good compatibility with polymeric matrices, have attracted increasing interest from researchers for the construction of polymeric nano-based separation membranes. With their distinctive nanofeatures, polymeric nano-based membranes show great promise in overcoming bottlenecks in polymer membranes, namely, the trade-off between permeability and selectivity, low stability, and fouling issues. Accordingly, recent studies have focused on tuning the structures and tailoring the surface properties of polymeric nano-based membranes via exploitation of membrane fabrication techniques and surface modification strategies, with the objective of pushing the performance of polymeric nano-based membranes to a new level. In this review, first, the approaches for fabricating polymeric nano-based mixed matrix membranes and homogeneous membranes are summarized, such as surface coating, phase inversion, interfacial polymerization, and self-assembly methods. Next, the manipulation strategies of membrane surface properties, namely, the hydrophilicity/hydrophobicity, charge characteristics, and surface roughness, and interior microstructural properties, namely, the pore size and content, channel construction and regulation, are comprehensively discussed. Subsequently, the separation performances of liquid ions/molecules and gas molecules through polymeric nano-based membranes are systematically reported. Finally, we conclude this review with an overview of various unsolved scientific and technical challenges that are associated with new opportunities in the development of advanced polymeric nano-based membranes.

Superfast Water Transport Zwitterionic Polymeric Nanofluidic Membrane Reinforced by Metal-Organic Frameworks.

Nanofluidics derived from low-dimensional nanosheets and protein nanochannels are crucial for advanced catalysis, sensing, and separation. However, polymer nanofluidics is halted by complicated preparation and miniaturized sizes. This work reports the bottom-up synthesis of modular nanofluidics by confined growth of ultrathin metal-organic frameworks (MOFs) in a polymer membrane consisting of zwitterionic dopamine nanoparticles (ZNPs). The confined growth of the MOFs on the ZNPs reduces the chain entanglement between the ZNPs, leading to stiff interfacial channels enhancing the nanofluidic transport of water molecules through the membrane. As such, the water permeability and solute selectivity of MOF@ZNPM are one magnitude improved, leading to a record-high performance among all polymer nanofiltration membranes. Both the experimental work and the molecular dynamics simulations confirm that the water transport is shifted from high-friction-resistance conventional viscous flow to ultrafast nanofluidic flow as a result of rigid and continuous nanochannels in MOF@ZNPM.

Modification of Polyamide-Urethane (PAUt) Thin Film Composite Membrane for Improving the Reverse Osmosis Performance.

In the current study, the poly (amide-urethane) (PAUt) membranes were successfully fabricated by interfacial polymerization of m-phenylenediamine (MPD) and 5-choroformyloxyisophaloyl chloride (CFIC) on the polysulfone substrates. Two modification methods based on layer-by-layer assembly were applied to modify the PAUt membrane surface to achieve antifouling property: 1. Chitosan (CS) was directly self-assembled on the PAUt membrane (i.e., PAUt-CS); and 2. polydimethyl diallyl ammonium chloride (PDDA), polystyrene sulfonate (PSS), and CS were successively self-assembled on the membrane surface (i.e., PAUt-PDDA/PSS/CS). The resultant membranes were symmetrically characterized by Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR), X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM) and Contact Angle Meter (CAM), respectively. The results indicated that the modified membranes had much smoother and more hydrophilic surfaces as compared to the nascent PAUt membrane. Meanwhile, the modified membranes exhibited better reverse osmosis performance in terms of water permeability and salt rejection. After the modified membranes were fouled by lake water, the PAUt-PDDA/PSS/CS membrane presented the best antifouling performance among the three types of membranes. Combining the reverse osmosis performance with the anti-fouling property obviously, the PAUt-PDDA/PSS/CS membrane behaved as a promising candidate to be used in real applications.

Modification of PSf/SPSf Blended Porous Support for Improving the Reverse Osmosis Performance of Aromatic Polyamide Thin Film Composite Membranes.

In this study, modification of polysulfone (PSf)/sulfonated polysulfone (SPSf) blended porous ultrafiltration (UF) support membranes was proposed to improve the reverse osmosis (RO) performance of aromatic polyamide thin film composite (TFC) membranes. The synergistic effects of solvent, polymer concentration, and SPSf doping content in the casting solution were investigated systematically on the properties of both porous supports and RO membranes. SEM and AFM were combined to characterize the physical properties of the membranes, including surface pore natures (porosity, mean pore radius), surface morphology, and section structure. A contact angle meter was used to analyze the membrane surface hydrophilicity. Permeate experiments were carried out to evaluate the separation performances of the membranes. The results showed that the PSf/SPSf blended porous support modified with 6 wt % SPSf in the presence of DMF and 14 wt % PSf had higher porosity, bigger pore diameter, and a rougher and more hydrophilic surface, which was more beneficial for fabrication of a polyamide TFC membrane with favorable reverse osmosis performance. This modified PSf/SPSf support endowed the RO membrane with a more hydrophilic surface, higher water flux (about 1.2 times), as well as a slight increase in salt rejection than the nascent PSf support. In a word, this work provides a new facile method to improve the separation performance of polyamide TFC RO membranes via the modification of conventional PSf porous support with SPSf.

Modification of polyamide TFC nanofiltration membrane for improving separation and antifouling properties.

In this work, a dendrimer trimesoyl amide amine (TMAAM) monomer was proposed to be used as a key functional monomer to modify the conventional aromatic polyamide thin-film composite (TFC) nanofiltration (NF) membrane, and a new kind of TMAAM-based semi-aromatic polyamide composite NF membrane was thus prepared by interfacial polymerization. The effects of the PIP/TMAAM ratio (PIP = piperazine) on the membrane chemical structure, surface properties and separation performances were investigated systematically. With the increase in TMAAM content loaded in the membrane, the water flux strongly increased but the salt rejection decreased only slightly. When the PIP/TMAAM ratio was 1, the membrane NF-2 exhibited a smoother and more hydrophilic surface, as a result of which it displayed an optimum separation performance for different valent salts. In addition, the TMAAM modified TFC membrane presented an extremely high rejection to negatively charged dye molecules and high permeation for monovalent salts, leading to good prospects for dye/salt separation application. Moreover, both the water flux and salt rejection of the TMAAM-based membrane were stable in a long-term running process, and the membrane showed a favourable anti-fouling property and efficient cleaning recovery. Therefore, this work provides a new type of semi-aromatic polyamide composite NF membrane fabricated by a facile and straightforward method via interfacial polymerization with high hydrophilicity, good stability and strong anti-fouling property.

Modification of poly(amide-urethane-imide) (PAUI) thin film composite reverse osmosis membrane with nano-silver particles.

A novel reverse osmosis (RO) composite membrane, poly(amide-urethane-imide@Ag) (PAUI@Ag), was prepared on a polysulfone supporting film through two-step interfacial polymerization. First, in the 1st interfacial polymerization procedure, a new tri-functional crosslinking agent with -OCOCl and -COCl groups, 5-choroformyloxyisophaloyl chloride (CFIC), was reacted with 4-methyl-phenylenediamine (MMPD) without curing treatment to obtain the poly(amide-urethane) base membrane with a CFIC-MMPD precursor separation layer. And then N,N'-dimethyl-m-phenylenediamine (DMMPD) with nano-Ag particle dispersion was introduced onto the base membrane to further construct a CFIC-DMMPD modified ultrathin separation layer via the 2nd interfacial polymerization. Thus, the PAUI@Ag RO membrane with poly(amide-urethane-imide) bi-layer skin was obtained. The membrane was characterized for the chemical composition of separation layer, the membrane cross-section structure and the membrane surface morphology. Permeation experiment was employed to evaluate the PAUI@Ag membrane performance including salt rejection rate and water flux. The results revealed that the PAUI@Ag membrane composed the highly cross-linked separation layer with entire ridges and valleys, small surface roughness, and well dispersed nano-Ag particles. Upon exposure of the membranes to high concentration of free chlorine solutions, the PAUI@Ag RO membrane showed a slightly less chlorine-resistant property compared with the nascent PAUI RO membrane, but was still superior to the conventional polyamide MPD-TMC RO membrane, meanwhile it processed higher anti-biofouling property.

Recent Advances in the Fabrication of Membranes Containing "Ion Pairs" for Nanofiltration Processes.

In the face of serious environmental pollution and water scarcity problems, the membrane separation technique, especially high efficiency, low energy consumption, and environmental friendly nanofiltration, has been quickly developed. Separation membranes with high permeability, good selectivity, and strong antifouling properties are critical for water treatment and green chemical processing. In recent years, researchers have paid more and more attention to the development of high performance nanofiltration membranes containing "ion pairs". In this review, the effects of "ion pairs" characteristics, such as the super-hydrophilicity, controllable charge character, and antifouling property, on nanofiltration performances are discussed. A systematic survey was carried out on the various approaches and multiple regulation factors in the fabrication of polyelectrolyte complex membranes, zwitterionic membranes, and charged mosaic membranes, respectively. The mass transport behavior and antifouling mechanism of the membranes with "ion pairs" are also discussed. Finally, we present a brief perspective on the future development of advanced nanofiltration membranes with "ion pairs".

High-Flux Positively Charged Nanocomposite Nanofiltration Membranes Filled with Poly(dopamine) Modified Multiwall Carbon Nanotubes.

The poor dispensability of pristine carbon nanotubes in water impedes their implications in thin-film nanocomposite membranes for crucial utilities such as water purification. In this work, high-flux positively charged nanocomposite nanofiltration membranes were exploited by uniformly embedding poly(dopamine) modified multiwall carbon nanotubes (PDA-MWCNTs) in polyamide thin-film composite membranes. With poly(dopamine) modification, fine dispersion of MWCNTs in polyethyleneimine (PEI) aqueous solutions was achieved, which was interracially polymerized with trimesoyl chloride (TMC) n-hexane solutions to prepare nanocomposite membranes. The compatibility and interactions between modified MWCNTs and polyamide matrix were enhanced, attributed to the poly(dopamine) coatings on MWCNT surfaces, leading to significantly improved water permeability. At optimized conditions, pure water permeability of the PEI/PDA-MWCNTs/TMC nanofiltration membrane (M-4) was 15.32 L m(-2) h(-1) bar(-1), which was ∼1.6 times increased compared with that of pristine PEI/TMC membranes. Salt rejection of M-4 to different multivalent cations decreased in the sequence ZnCl2 (93.0%) > MgCl2 (91.5%) > CuCl2 (90.5%) ≈ CaCl2, which is well-suited for water softening and heavy metal ion removal.

Synergistic strengthening of polyelectrolyte complex membranes by functionalized carbon nanotubes and metal ions.

Hydrophilic polymers have garnered much attention due to their critical roles in various applications such as molecular separation membranes, bio-interfaces, and surface engineering. However, a long-standing problem is that their mechanical properties usually deteriorate at high relative humidity (RH). Through the simultaneous incorporation of functionalized carbon nanotubes and copper ions (Cu(2+)), this study introduces a facile method to fabricate high strength polyelectrolyte complex nanohybrid membranes resistant to high RH (90%). For example, the tensile strength of the nanohybrid membranes is 55 MPa at 90% RH (80% of the original value at 30% RH). These results are explained by copper ions depressing the swelling degree of the membrane, and functionalized carbon nanotubes promoting stress transfer between the polymer matrix and them. The nanohybrid membranes are efficient in separating water/alcohol mixtures containing relatively high water content (up to 30 wt%), whereas common hydrophilic polymer membranes usually suffer from excessive swelling under this condition.

Preparation and properties of PEC nanocomposite membranes with carboxymethyl cellulose and modified silica.

Carboxymethyl cellulose (CMC)-modified silica nanocomposites were prepared via in situ incorporation of modified silica during the ionic complexation between CMC and poly(2-methacryloyloxy ethyl trimethylammonium chloride) (PDMC). Ionic bonds were introduced between the poly(2-acrylamido-2-methylproanesulfonic acid) modified silica (SiO2-PAMPS) and the polyelectrolyte complex (PEC) matrix. The PEC nanocomposites (PECNs) and their membranes (PECNMs) were characterized with Fourier transform-infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and tensile testing. PECNM containing 5 wt.% SiO2-PAMPS showed a tensile strength of 68 MPa and elongation at break of 7.1%, which were 1.9 and 2.6 times as high as those of pristine PEC membranes, respectively. Moreover, the pervaporation performance of as-prepared PECNMs was evaluated with dehydration of 10 wt.% aqueous isopropanol mixtures, and the PECNMs exhibited a flux of 2,400 gm(-2)h(-1) with a high separation factor of 4491 at 70°C.

Study on degradation of methyl orange using pelagite as photocatalyst.

Pelagite of East Pacific Ocean as a low-price, very high reserve photocatalyst, has been successfully used for the first time to realize total degradation and decoloration of methyl orange within 120 min through photocatalysis. The photocatalysis and degradation performance of pelagite for methyl orange under the effect of various factors has been studied. Results show that pelagite has satisfactory photocatalysis effect in degradation of organic compounds.

Surface modification of phenolphthalein poly(ether sulfone) ultrafiltration membranes by blending with acrylonitrile-based copolymer containing ionic groups for imparting surface electrical properties.

Asymmetric ultrafiltration membranes were fabricated from the blends of phenolphthalein polyethersulfone (PES-C) and acrylonitrile copolymers containing charged groups, poly(acrylonitrile-co-acrylamido methylpropane sulfonic acid) (PAN-co-AMPS). From the surface analysis by XPS and ATR-FTIR, it was found that the charged groups tend to accumulate onto the membrane surface. This result indicated that membrane surface modification for imparting surface electrical properties could be carried out by blending charged polymer. Furthermore, with the help of a relatively novel method to measure membrane conduction, the true zeta potentials calculated on the basis of the streaming potential measurements were used to reflect the charge state of membrane surface. In addition, it was noteworthy that, from the profiles of zeta potential versus pH curves and the magnitude of zeta potentials, the determination of zeta potential was dependent not only on the electrical properties of membrane surface but also on its hydrophilicity. At last, based on a relatively elaborate study on the electrostatic interaction between the membrane surface and protein, it was found that these charged membranes could meet different demands of membrane applications, such as resisting protein fouling or protein separation, through adjusting solution pH value.

[Advances on CO2 fixation by microalgae].

The greenhouse effect, which is believed to occur primarily as a result of the accumulation of carbon dioxide in the atmosphere, has become one of the major environmental concerns and received worldwide attention. In this paper, algae species screening and cultivation for efficient CO2 fixation are reviewed. The related dissolved inorganic carbon (DIC) utilization form and CO2 concentration mechanism (CCM) in the process of CO2 fixation by microalgae are analyzed. Four objectives of the highly effective photobioreactor design and operation are discussed, and the advances on CO2 mitigation technology with integration of microalgae (enzyme) and membrane bioreactor are also briefly introduced. In response to elevated CO2 concentration, much attention needs to be paid to the construction of transgenic microalgae with higher performance in CO2 fixation based on the further ascertainment of the related mechanism, and the development of effective CO2 biofixation system integrated with other kinds of advanced technology, such as membrane immobilization and separation.

Remove volatile organic compounds (VOCs) with membrane separation techniques.

Membrane separation, a new technology for removing VOCs including pervaporation, vapor permeation, membrane contactor, and membrane bioreactor was presented. Comparing with traditional techniques, these special techniques are an efficient and energy-saving technology. Vapor permeation can be applied to recovery of organic solvents from exhaust streams. Membrane contactor could be used for removing or recovering VOCs from air or wastewater. Pervaporation and vapor permeation are viable methods for removing VOCs from wastewater to yield a VOC concentrate which could either be destroyed by conventional means, or be recycled for reuse.