Simultaneous spray self-assembly of highly loaded ZIF-8-PDMS nanohybrid membranes exhibiting exceptionally high biobutanol-permselective pervaporation.

The ability to obtain a maximum loading of inorganic nanoparticles while maintaining uniform dispersion in the polymer is the key to the fabrication of mixed-matrix membranes with high pervaporation performance in bioalcohol recovery from aqueous solution. Herein, we report the simultaneous spray self-assembly of a zeolitic imidazolate framework (ZIF)-polymer suspension and a cross-linker/catalyst solution as a method for the fabrication of a well-dispersed ZIF-8-PDMS nanohybrid membrane with an extremely high loading. The ZIF-8-PDMS membrane showed excellent biobutanol-permselective pervaporation performance. When the ZIF-8 loading was increased to 40 wt%, the total flux and separation factor could reach 4846.2 g m(-2) h(-1) and 81.6, respectively, in the recovery of n-butanol from 1.0 wt% aqueous solution (80 °C). This new method is expected to have serious implications for the preparation of defect-free mixed-matrix membranes for many applications.

Coordination-driven in†situ self-assembly strategy for the preparation of metal-organic framework hybrid membranes.

Metal-organic frameworks (MOFs) have emerged as porous solids of a superior type for the fabrication of membranes. However, it is still challenging to prepare a uniformly dispersed robust MOF hybrid membrane. Herein, we propose a simple and powerful strategy, namely, coordination-driven in situ self-assembly, for the fabrication of MOF hybrid membranes. On the basis of the coordination interactions between metal ions and ligands and/or the functional groups of the organic polymer, this method was confirmed to be feasible for the production of a stable membrane with greatly improved MOF-particle dispersion in and compatibility with the polymer, thus providing outstanding separation ability. As an experimental proof of concept, a high-quality ZIF-8/PSS membrane was fabricated that showed excellent performance in the nanofiltration and separation of dyes from water.

Surface-modification of poly(dimethylsiloxane) membrane with self-assembled monolayers for alcohol permselective pervaporation.

The use of self-assembled monolayers (SAMs) has recently been recognized as an effective way to tailor the surface properties of films used in various applications. However, application of SAMs in the preparation of separation membranes remains unexplored. In the present study, surface-modified poly(dimethylsiloxane) (PDMS) membranes were prepared using SAMs to fabricate a membrane for use in pervaporation separation of ethanol/water mixtures. A cross-linked PDMS/polysulfone (PSf) composite membrane was transformed by introducing hydroxyl functionalities on the PDMS surface through a UV/ozone conversion process. (Tridecafluoroctyl)triethoxysilane was allowed to be adsorbed on the resulting Si-OH substrate to increase the hydrophobicity of the membrane. Results from Fourier transform infrared spectroscopy, scanning electron microscopy, energy-dispersive X-ray spectrometry, atomic force microscopy, and contact angle analyses suggest that the fluoroalkylsilane monolayer was successfully formed on the modified PDMS/PSf membrane treated by 60 min UV/ozone exposure. The newly SAM-modified membrane exhibited a separation factor of 13.1 and a permeate flux of 412.9 g/(m(2) h), which are higher than those obtained from PDMS membranes.

Effects of external electric field on film growth, morphology, and nanostructure of polyelectrolyte and nanohybrid multilayers onto insulating substrates.

Electric-field-enhanced layer-by-layer (LbL) assembly of polyelectrolyte and nanohybrid multilayers onto insulating rigid substrates was successfully accomplished using two independent capacitor cells. The influence of external electric field on the multilayer formation was intensively investigated by UV-vis adsorption spectrometry, profilometry, atomic force microscopy, and small-angle X-ray diffraction. This approach was also attempted as a means of fabricating selective layer on flat sheet polymeric porous substrates to obtain the dense composite membranes with high pervaporation performance.

Graphene oxide membranes with stable porous structure for ultrafast water transport.

The robustness of carbon nanomaterials and their potential for ultrahigh permeability has drawn substantial interest for separation processes. However, graphene oxide membranes (GOms) have demonstrated limited viability due to instabilities in their microstructure that lead to failure under cross-flow conditions and applied hydraulic pressure. Here we present a highly stable and ultrapermeable zeolitic imidazolate framework-8 (ZIF-8)-nanocrystal-hybridized GOm that is prepared by ice templating and subsequent in situ crystallization of ZIF-8 at the nanosheet edges. The selective growth of ZIF-8 in the microporous defects enlarges the interlayer spacings while also imparting mechanical integrity to the laminate framework, thus producing a stable microstructure capable of maintaining a water permeability of 60 l m-2 h-1 bar-1 (30-fold higher than GOm) for 180 h. Furthermore, the mitigation of microporous defects via ZIF-8 growth increased the permselectivity of methyl blue molecules sixfold. Low-field nuclear magnetic resonance was employed to characterize the porous structure of our membranes and confirm the tailored growth of ZIF-8. Our technique for tuning the membrane microstructure opens opportunities for developing next-generation nanofiltration membranes.

Construction of metal-ligand-coordinated multilayers and their selective separation behavior.

In this article, a layer-by-layer (LbL)-assembled coordination multilayer on planar and 3D substrates was explored by the alternate deposition of a transition-metal-containing polyelectrolyte and a ligand-containing polymer via the formation of complexes. The metal-ligand coordination between the building blocks of Co(2+)-exchanged poly(styrene sulfonate) (PSS) and poly(4-vinyl pyridine) (P4 VP) has been demonstrated using UV-vis, FTIR, and XPS. The film thickness, structure, and morphology as well as the wettability as a function of bilayer number have been systematically investigated by profilometry, SEM, AFM, and contact angle analyzers. For the purpose of separation applications, the metal-ligand-coordinated multilayer was assembled on both flat sheet and hollow fiber polymeric porous substrates using a dynamic pressure-driven LbL technique. It was demonstrated that the LbL-assembled PSS(Co)(1/2)/P4 VP multilayer membrane had high dehydration performance with respect to different solvent-water mixtures; it also had aromatic compound permselectivity from aromatic-aliphatic hydrocarbons and water-softening capacity. Meanwhile, the successful assembly of multilayers on hollow fibers indicates that the dynamic pressure-driven LbL technique is a unique approach to the construction of multilayers on porous 3-D substrates. Therefore, the metal-ligand-coordinated self-assembly could emerge as a powerful technique for the preparation of a range of separation membranes in different types of modules.

Microphase Diffusion-Controlled Interfacial Polymerization for an Ultrahigh Permeability Nanofiltration Membrane.

The key to improving nanofiltration membrane permeance is reducing its thickness while maintaining high rejection. Herein, a 25 nm thick ultrathin polyamide layer was prepared by a microphase diffusion-controlled interfacial polymerization (MDC-IP) of poly(ethyleneimine) and trimesoyl chloride, which is much thinner than the conventional interfacial polymerization (CIP) polyamide layer. A new formation mechanism for such an ultrathin layer is presented, which included a microphase interfacial reaction and eliminated loose layers due to the confinement of microphase diffusion and the termination of stepwise diffusion. Moreover, the polyamide layer was post-cross-linked to form a stable dual-cross-linked interwoven structure. Such a membrane showed an ultrahigh permeance of 1246 kg/(m2 h MPa), which was 23 times that of CIP membranes. MDC-IP could efficiently control the microinterface between two immiscible phases, which provided a facile way to regulate the membrane at nanoscale.

One-Step Assembly of Molecular Separation Membranes by Direct Atomizing Oligomers.

Polymeric membranes are important materials for efficient sieving of targeted components at the molecular level and have made significant advancement in many industrial applications such as biofuel production, water purification, fuel combustion, and carbon dioxide capture. Although their separation efficiencies have been widely investigated, lack of more efficient, greener, and lower-cost membrane fabrication mechanisms is still a major hurdle for mass production, because the conventional membrane-making process is always time-consuming, highly inefficient, and consumes a large amount of organic solvents. Herein we report a one-step assembly concept capable of directly processing low-viscosity oligomers into polymer-based molecular separation membranes in an ultrafast and green manner. This process was implemented by alternate atomizing-depositing of low-viscosity oligomers and reaction auxiliary agents onto a rotating support and followed by an ultrafast interfacial reaction under solvent-free conditions. Without the need for dissolution processing of polymer, solvent evaporation, and any post-treatments, the whole technological process could be accomplished within a few seconds/minutes, which is 2-3 orders of magnitude faster than conventional solution-coating technologies. The universality of this facile approach has also been demonstrated by successfully producing various defect-free polymeric membranes and homodispersed nanohybrid membranes with excellent and stable performance for bioalcohol production and recovery of different trace organics from dilute solutions.

Natural organic matter fouling behaviors on superwetting nanofiltration membranes.

Nanofiltration has been widely recognized as a promising technology for the removal of micro-molecular organic components from natural water. Natural organic matter (NOM), a very important precursor of disinfection by-products, is currently considered as the major cause of membrane fouling. It is necessary to develop a membrane with both high NOM rejection and anti-NOM fouling properties. In this study, both superhydrophilic and superhydrophobic nanofiltration membranes for NOM removal have been fabricated. The fouling behavior of NOM on superwetting nanofiltration membranes has been extensively investigated by using humic acid (HA) as the model foulant. The extended Derjaguin-Landau-Verwey-Overbeek approach and nanoindentor scratch tests suggested that the superhydrophilic membrane had the strongest repulsion force to HA due to the highest positive total interaction energy (ΔG(TOT)) value and the lowest critical load. Excitation emission matrix analyses of natural water also indicated that the superhydrophilic membrane showed resistance to fouling by hydrophobic substances and therefore high removal thereof. Conversely, the superhydrophobic membrane showed resistance to fouling by hydrophilic substances and therefore high removal capacity. Long-term operation suggested that the superhydrophilic membrane had high stability due to its anti-NOM fouling capacity. Based on the different anti-fouling properties of the studied superwetting membranes, a combination of superhydrophilic and superhydrophobic membranes was examined to further improve the removal of both hydrophobic and hydrophilic pollutants. With a combination of superhydrophilic and superhydrophobic membranes, the NOM rejection (RUV254) and DOC removal rates (RDOC) could be increased to 83.6% and 73.3%, respectively.

Nanoconfined Zeolitic Imidazolate Framework Membranes with Composite Layers of Nearly Zero Thickness.

The key to preparing dense composite membranes is reducing the thickness of the composite layer with stable separation performance. Herein, we report a nanoconfined composite membrane prepared by in situ growth of Zeolitic Imidazolate Framework (ZIF) nanocrystals in the nanoporous layer of the substrate via a fine-tuning contra-diffusion method. The thickness of the composite layer on the membrane surface was nearly zero. The formed ZIF nanoconfined composite membranes showed state-of-art flux and high stability in removing dyes from water. This new strategy is expected to offer great opportunities for the potential practical application of polymer-supported metal-organic framework (MOF) composite membranes.

Oriented Nano-Microstructure-Assisted Controllable Fabrication of Metal-Organic Framework Membranes on Nickel Foam.

Oriented nano-microstructure-assisted controllable fabrication, a facile and versatile preparation strategy, is developed to fabricate metal-organic framework (MOF) membranes. With this method, several MOF membranes with tailored structures are prepared, including HKUST-1 (with 3D pores) and M3 (HCOO)6 (with 1D pores; M = Co, Mn, and Mg) membranes, which demonstrate good performances in gas separations.

[A new species of the genus Phenylobacterium for the degradation of LAS (linear alkylbenzene sulfonate)].

A strain GZ6 that can biodegrade LAS (Linear Alkylbenzene Sulphonate) is identified. It is aerobic gram-negative rod or short-rod (0.5 to 0.8 by 1.0 to 2.0 Mm). It is mobile with a single polar flagellum. Optimum growth occurred at 30 degrees C and pH7.0. It is catalase positive, urease positive, and arginine decarboxylase positive. All the other physiological and biochemical tests performed were negative. It utilizes the xenobiotic compounds chloridazon, antipyrin and LAS as sole carbon sources. Most sugars, alcohols, and carboxylic acids are not utilized. It has Q-10 as the major quinone. The main cell fatty acids are Sum7, C16:0 and Sum4. The DNA G + C mol % content is 70.10. A phylogenic tree was constructed on the basis of 16S rDNA sequences. It showed that the previously known member of the genus Phenylobacterium, Phenylobacterium mobile DSM1986T, is the nearest neighbor to strain GZ6. The level of binary sequence similarity between them is 97.49%. And the DNA-DNA relatedness is 40%. These genetic analysis and their morphological difference show that they are different species of Phenylobacterium. A new species, Phenylobacterium mobile sp. nov., has been proposed.

Low-temperature synthesis of anatase TiO2 nanoparticles with tunable surface charges for enhancing photocatalytic activity.

In this work, the positively or negatively charged anatase TiO2 nanoparticles were synthesized via a low temperature precipitation-peptization process (LTPPP) in the presence of poly(ethyleneimine) (PEI) and poly(sodium4- styrenesulfonate) (PSS). X-ray diffraction (XRD) pattern and high-resolution transmission electron microscope (HRTEM) confirmed the anatase crystalline phase. The charges of the prepared TiO2, PEI-TiO2 and PSS-TiO2 nanoparticles were investigated by zeta potentials. The results showed that the zeta potentials of PEI-TiO2 nanoparticles can be tuned from +39.47 mV to +95.46 mV, and that of PSS-TiO2 nanoparticles can be adjusted from -56.63 mV to -119.32 mV. In comparison with TiO2, PSS-TiO2 exhibited dramatic adsorption and degradation of dye molecules, while the PEI modified TiO2 nanoparticles showed lower photocatalytic activity. The photocatalytic performances of these charged nanoparticles were elucidated by the results of UV-vis diffuse reflectance spectra (DRS) and the photoluminescence (PL) spectra, which indicated that the PSS-TiO2 nanoparticles showed a lower recombination rate of electron-hole pairs than TiO2 and PEI-TiO2.

Hybrid membranes of metal-organic molecule nanocages for aromatic/aliphatic hydrocarbon separation by pervaporation.

Hybrid membranes composed of porous metal-organic molecule nanocages as fillers embedded in a hyperbranched polymer (Boltorn W3000) were fabricated, which exhibit excellent pervaporation separation performances towards aromatic/aliphatic hydrocarbons. The unique nature of the molecule-based fillers and their good dispersion and compatibility in/with the polymer are responsible for the good membrane properties.

[Degradation pathway of 17alpha-ethynylestradiol by Sphingobacterium sp. JCR5].

A bacterial strain, JCR5, which degrades 17alpha-ethynylestradiol (EE2), was isolated from activated sludge of wastewater treatment plant treating wastewater from pharmacy factory mainly producing contraceptive medicine in Beijing, China. Based on its morphology, physiology biochemical properties and 16S rDNA sequence analysis, this strain was identified as Sphingobacteriumn sp. JCR5. Strain JCR5 can grow on EE2 as sole carbon and energy source. The degradation process for EE2 with initial concentration of 30 mg x L(-1) was studied, and the result indicated that the degradation rate of EE2 within 10 days was 87%. Experiments of different substrates showed that strain JCR5 can grow on many substrates other than EE2 such as several steroidal estrogens (estrone, 17beta-estradiol, estriol and mestranol), the intermediates in contraceptive medicine processing and some aromatic compounds. Mass spectrum analysis demonstrated that EE2 was oxygenized to estrone (E1) firstly, and 2-hydroxy-2,4-dienevaleric acid and 2-hydroxy-2,4-diene-1, 6-dioic acid were the main catabolic intermediates during EE2 degradation. The former adopted a pathway that was analogical to the pathway of the previously reported testosterone-degrading Comamnonas testosteroni TA441, and the latter was a metabolite with a different cleavage position of 3-hydroxy-4,5-9, 10-disecoestrane-1(10), 2-diene-5,9, 17- trione-4-oic acid from the former.

[Isolation, identification of 17alpha-ethynylestradiol-degrading strain and its degradation characteristics].

A bacterial strain that degrades 17alpha-ethynylestradiol (EE2) was isolated from activated sludge of wastewater treatment plant treating wastewater from pharmacy factory mainly producing contraceptive medicine in Beijing, China. Based on its morphology, physiological and biochemical characters, as well as 16S rDNA sequence analysis, this strain was identified as Sphingobacterium sp. JCR5. Strain JCR5 can use EE2 as sole carbon and energy source for growth. The optimal temperature and pH for strain JCR5 utilizing EE2 was 25 approximately 40 degrees C and 7 approximately 9, respectively. Metal ions such as Ni2+, Mn2+, Cu2+ and Fe3+ promote growth of strain JCR5, and some metal ions such as Zn2+, Ag+, Pb2+, Ca2+ and Al3+ inhibit its growth. The degradation process for EE2 with initial concentration of 30mg x L(-1) indicated that the degradation rate of EE2 by strain JCR5 within 10 days was 87%.

[The application of nanofiltration membrane in the concentration and separation of lincomycin wastewater].

Two spiral nanofiltration membranes, MPS-44 (1.4 m2) and DLNF2-30 (0.24 m2), were connected in series to test the concentration process of lincomycin wastewater. Results indicated when the water inflow concentration was about 200 mg/L, the lincomycin concentration can reach 2000 mg/L after being concentrated for about 10-20 times. Such concentration can reach the demand of reuse, and the concentrating time was 60-70 h. During the concentration process, the CODCr retention was always above 80%, and the lincomycin retention was always over 90%, and the lincomycin recycle rate was over 90%.