Large-Area Soluble Covalent Organic Framework Oligomer Coating for Organic Solution Nanofiltration Membranes.

Covalent organic frameworks (COFs) are a family of engaging membrane materials for molecular separation, which remain challenging to fabricate in the form of thin-film composite membranes due to slow crystal growth and insoluble powder. Here, an additive approach is presented to construct COF-based thin-film composite membranes in 10 min via COF oligomer coating onto poly(ether ether ketone) (PEEK）ultrafiltration membranes. By the virtue of ultra-thin liquid phase and liquid-solid interface-confined assembly, the COF oligomers are fast stacked up and grow along the interface with the solvent evaporation. Benefiting from the low out-plane resistance of COFs, COF@PEEK composite membranes exhibit high solvent permeances in a negative correlation with solvent viscosity. The well-defined pore structures enable high molecular sieving ability (Mw = 300 g mol-1 ). Besides, the COF@PEEK composite membranes possess excellent mechanical integrities and steadily operate for over 150 h in the condition of high-pressure cross flow. This work not only exemplifies the high-efficiency and scale-up preparation of COF-based thin-film composite membranes but also provides a new strategy for COF membrane processing.

Confined Nano-Channels Incorporated with Multi-Quaternized Cations for Highly Phosphoric Acid Retention HT-PEMs.

Developing a new strategy to retain phosphoric acid (PA) to improve the performance and durability of high-temperature proton exchange membrane fuel cell (HT-PEMFC) remains a challenge. Here, a strategy for ion-restricted catcher microstructure that incorporates PA-doped multi-quaternized poly(fluorene alkylene-co-biphenyl alkylene) (PFBA) bearing confined nanochannels is reported. Dynamic analysis reveals strong interaction between side chains and PA molecules, confirming that the microstructure can improve PA retention. The PFBA linked with triquaternary ammonium side chain (PFBA-tQA) shows the highest PA retention rate of 95%. Its H2/O2 fuel cell operates within 0.6% voltage decay at 160 °C/0% RH, and it also runs over 100 h at 100 °C/49% RH under external humidification. This combination of high PA retention, and chemical and dimensional stability fills a gap in the HT-PEMFC field, which requires strict moisture control at 90-120 °C to prevent acid leaching, simplifying the start-up procedure of HT-PEMFC without preheating.

Bioinspired Under-Liquid Dual Superlyophobic Surface for On-Demand Oil/Water Separation.

Porous membranes with under-liquid dual superlyophobic properties, which are difficult to achieve because of a thermodynamic contradiction, have attracted considerable interest in the field of switchable oil/water separation. Herein, a bioinspired mesh membrane with alternating hydrophilic and hydrophobic chemical patterns on its surface that endows it with superamphiphilic and under-liquid dual superlyophobic properties is fabricated by a simple liquidus modification process. The as-prepared membrane possesses a combination of under-oil superhydrophobic and under-water superoleophobic characteristics in the absence of external stimuli. Moreover, it can effectively perform the on-demand separation of various oil/water systems, including immiscible oil/water mixtures and oil/water emulsions owing to its under-liquid dual superlyophobic properties.

Janus Membranes with Asymmetric Superwettability for High-Performance and Long-Term On-Demand Oil/Water Emulsion Separation.

Current single-function superwettable materials are typically designed for either oil removal or water removal and are constrained by oil density, limiting their widespread applications. Janus membranes with opposite wettability on their two surfaces have recently emerged and present attractive opportunities for on-demand oil/water emulsion separation. Here, a combination strategy is introduced to prepare a Janus membrane with asymmetric superwettability for switchable oil/water emulsion separation. A mussel-inspired asymmetric interface introduction cooperating with the sequence-confined surface modification not only brings about an asymmetric superwettability Janus interface but also guarantees an outstanding stable interface and remarkable chemical stability surfaces. Specifically, the superhydrophilic surface with underwater superoleophobicity can separate surfactant-stabilized oil-in-water emulsions. Conversely, other surface displays opposite superhydrophobicity and superoleophilicity to treat surfactant-stabilized water-in-oil emulsions. Significantly, this superwettable Janus membrane presents superior long-term on-demand oil/water emulsion separation without obvious flux decline and high recovery ability because of its superwettability and superior stability. Furthermore, the asymmetric superwettability enhances the interfacial floatability at air-water interfaces, enabling the design of advanced interfacial materials. The as-prepared superwettable Janus membrane has established a cooperated separation system, overcoming the monotony of conventional superwettable membranes and expanding the application of these specialized membranes to oily wastewater treatment.

Multi-DNA-Modified Double-Network Hydrogel with Customized Microstructure: A Novel System for Living Circulating Tumor Cells Capture and Real-Time Detection.

The precise and effective isolation of living circulating tumor cells (CTCs) from peripheral blood, followed by their real-time monitoring, is crucial for diagnosing cancer patients. In this study, a cell-imprinted double-network (DN) hydrogel modified with circular multi-DNA (CMD), coined the CMD-imprinted hydrogel with fixed cells as templates (CMD-CIDH), was developed. The hydrogel featured a customized surface for proficient capture of viable CTCs and in situ real-time fluorescent detection without subsequent release. The customized surface, constructed using polyacrylamide/chitosan DN hydrogel as the matrix on the cell template, had a dense network structure, thereby ensuring excellent stability and a low degradation rate. Optimal capture efficiencies, recorded at 93 ± 3% for MCF-7 cells and 90 ± 2% for Hela cells, were achieved by grafting the CMD and adjusting the nodule size on the customized surface. The capture efficiency remained significantly high at 67 ± 11% in simulated breast cancer patient experiments even at a minimal concentration of 5 cells mL-1. Furthermore, CMD grafted onto the surface produced a potent fluorescence signature, enabling in situ real-time fluorescent detection of the target cell's growth state even in complex environments. The customized surface is highly efficient for screening CTCs in peripheral blood and has promising potential for setting up the CTCs culture.

Phosphonated Ionomers of Intrinsic Microporosity with Partially Ordered Structure for High-Temperature Proton Exchange Membrane Fuel Cells.

High mass transport resistance within the catalyst layer is one of the major factors restricting the performance and low Pt loadings of proton exchange membrane fuel cells (PEMFCs). To resolve the issue, a novel partially ordered phosphonated ionomer (PIM-P) with both an intrinsic microporous structure and proton-conductive functionality was designed as the catalyst binder to improve the mass transport of electrodes. The rigid and contorted structure of PIM-P limits the free movement of the conformation and the efficient packing of polymer chains, resulting in the formation of a robust gas transmission channel. The phosphonated groups provide sites for stable proton conduction. In particular, by incorporating fluorinated and phosphonated groups strategically on the local side chains, an orderly stacking of molecular chains based on group assembly contributes to the construction of efficient mass transport pathways. The peak power density of the membrane electrode assembly with the PIM-P ionomer is 18-379% greater than that of those with commercial or porous catalyst binders at 160 °C under an H2/O2 condition. This study emphasizes the crucial role of ordered structure in the rapid conduction of polymers with intrinsic microporosity and provides a new idea for increasing mass transport at electrodes from the perspective of structural design instead of complex processes.

Ultrathin films of organic networks as nanofiltration membranes via solution-based molecular layer deposition.

Ultrathin films of organic networks on various substrates were fabricated through the solution-based molecular layer deposition (MLD) technique. The rigid tetrahedral geometries of polyfunctional amine and acyl chloride involved in the reaction ensure the continuity of the polymerization process. A linear increase in film thickness with respect to cycle number was observed by UV-vis adsorption, ellipsometry, and quartz crystal microbalance. The growth rate per MLD cycle is 1.6 nm, which can be controlled at the single molecular level. For the first time, we develop the MLD method on the top of hydrolyzed PAN substrate, resulting in nanofiltration (NF) membranes. The stepwise growth was monitored via attenuated total reflectance infrared studies. The separation performance of the obtained membrane for various solutes was sensitive to the terminated layers and number of cycles. The rejection of NH(2)-terminated membranes follows the order of CaCl(2) > Na(2)SO(4) > NaCl, while the order for COOH-capped surface is Na(2)SO(4) > CaCl(2) > NaCl. The absolute value of zeta potential for the MLD membranes decreases with the addition of deposition layers. The moderate water flux for the resulting membrane is due to the reduced porosity of the support as well as the low roughness and hydrophilicity of the membrane surface. This bottom-up process provides a promising approach for construction of long-term steady NF membranes with nanoscale dimensions.

Microbial diversity in the snow, a moraine lake and a stream in Himalayan glacier.

The microbial diversity and abundance in surface snow at different altitudes (5300 and 5504 m above sea level), a moraine lake and a glacial stream in the Yala Glacier on the southern slope of the Himalayas were investigated through a 16S rRNA gene clone library and flow cytometry approaches. Cell abundance in different habitats changed from 1.1 × 10(4) to 25 × 10(4) cells mL(-1), with the highest abundance in the moraine lake and the lowest abundance in the snow at 5504 m. Microbial communities in the snow were significantly different from those in the moraine lake and stream, although they were similar within snow and within the aquatic habitats. The two snow libraries were both dominated by Cyanobacteria, which accounted for about half of the total, followed by the Alphaproteobacteria and Firmicutes. The moraine lake and stream libraries were dominated by the Bacteroidetes and Betaproteobacteria, followed by the Actinobacteria. The results indicated that snow and water were highly diverse systems even in the same glacier. Microbial communities in the snow on the Yala Glacier were distinctly different from those in the East Rongbuk Glacier on the northern slope of Himalayas. However, microbes in the moraine lakes at two glaciers had similar community features. The snow habitat was easily affected by various environmental factors, while the aquatic habitats were comparatively stable in different glaciers.

Nano-Interlayers Fabricated via Interfacial Azo-Coupling Polymerization: Effect of Pore Properties of Interlayers on Overall Performance of Thin-Film Composite for Nanofiltration.

The supporting layer of nanofiltration membranes is critical to the overall nanofiltration performance. However, conventional supports lack efficient surface porosity, which leads to the limited utilization rate of the polyamide (PA) layer. Herein a double-skin-layer nanofiltration membrane with porous organic polymer nanointerlayers prepared via a two-step interfacial polymerization technique is presented to investigate the effect of the interlayers' pore properties on the performance of the thin-film composite. Nanometer interlayers with different pore sizes are fabricated via interfacial azo-coupling polymerization. The pore properties of the nanointerlayer extremely influence the permeance, where a suitable pore size of 4.22 nm promotes pure water permeance of up to 32.2 L m-2 h-1 bar-1, which is ∼3.8-fold greater than the membrane without an interlayer. However, an interlayer with 0.54 nm pores limits the performance (4.7 L m-2 h-1 bar-1), which is even lower than the unmodified membrane (7.5 L m-2 h-1 bar-1), because of the narrow pores and confined transport mode. However, the confined diffusion rate of amino monomers from the support to interface leads to a thinner PA layer of ∼45 nm and results in high flux. This work provides a facial route for the fabrication of interlayers and facilitate the design of high-performance membrane materials with interlayers.

A high potential biphenol derivative cathode: toward a highly stable air-insensitive aqueous organic flow battery.

Aqueous organic flow batteries have attracted dramatic attention for stationary energy storage due to their resource sustainability and low cost. However, the current reported systems can normally be operated stably under a nitrogen or argon atmosphere due to their poor stability. Herein a stable air-insensitive biphenol derivative cathode, 3,3',5,5'-tetramethylaminemethylene-4,4'-biphenol (TABP), with high solubility (>1.5 mol L-1) and redox potential (0.91 V vs. SHE) is designed and synthesized by a scalable one-step method. Paring with silicotungstic acid (SWO), an SWO/TABP flow battery shows a stable performance of zero capacity decay over 900 cycles under the air atmosphere. Further, an SWO/TABP flow battery manifests a high rate performance with an energy efficiency of 85% at a current density of 60 mA cm-2 and a very high volumetric capacity of more than 47 Ah L-1. This work provides a new and practical option for next-generation practical large-scale energy storage.

High-efficiency Pd nanoparticles loaded porous organic polymers membrane catalytic reactors.

An innovative tactic to prepare porous organic polymer membranes was developed via interfacial azo-coupling polymerization. The membranes possess plentiful anchoring sites for loading Pd nanoparticles, and served as a membrane reactor, which exhibits high-performance catalytic reduction with a flux of 27.3 t m-2 day-1 and good long-term stability due to almost zero Pd leaching.

Ionic-liquid-grafted rigid poly(p-phenylene) microspheres: efficient heterogeneous media for metal scavenging and catalysis.

Novel guanidinium ionic liquid-grafted rigid poly(p-phenylene) (PPPIL) microspheres have been developed for metal scavenging and catalysis. The noble-metal nanoparticles supported on the microspheres surface can be used as efficient heterogeneous catalysts. The combination of nanoparticles and ionic liquid fragments on the microsphere surfaces enhance the activity and durability of the catalyst. The PPPILPd(0) catalyst has been tested in the Suzuki cross-coupling reaction, and exhibits much higher catalytic activity than Pd catalysts supported on porous polymer matrices. The PPPILPd(0) catalyst can be recycled at least for nine runs without any significant loss of activity. The present approach may, therefore, have potential applications in transition-metal-nanocatalyzed reactions.

Assembly of magnetic nanospheres into one-dimensional nanostructured carbon hybrid materials.

The synthesis and characterization of carbon-coated ferromagnetic nanoparticles that organize into 1-D assemblies of micrometer-sized ferromagnetic chains is described. A controlled aromatization and carbonization of glucose under hydrothermal reaction conditions enabled the preparation of carbonaceous surfactants that were used as shells for the coating of ferromagnetic Fe(3)O(4) nanospheres with a uniform size distribution. Under controlled experimental conditions, it was, for the first time, demonstrated that glucose could be employed as the carbon source in the preparation of continuous 1-D carbon nanoparticle chains with magnetic nanosphere inclusions. The functional groups on the carbon surface will facilitate the linkage of functional groups or catalytic species to the surface in future application. The salient feature of the reported method was the assembly of magnetic nanospheres under hydrothermal reaction conditions in the absence of external fields.

Patterned, anti-fouling membrane with controllable wettability for ultrafast oil/water separation and liquid-liquid extraction.

A novel liquid-infused, patterned, porous membrane system with anti-fouling characteristics is prepared via simple co-infusion of oil and water within hydrophobic and superhydrophilic surfaces of a porous membrane, respectively. This membrane simultaneously repels the immiscible water and oil exhibiting excellent interfacial floatability at the oil-water interface as a separator, thus showing promise for use in applications in the immiscible oil/water separation industry and liquid-liquid extraction.

Renewable antibacterial and antifouling polysulfone membranes incorporating a PEO-grafted amphiphilic polymer and N-chloramine functional groups.

Functionalized polysulfone (PSf) membranes with combined antibacterial and antifouling properties were fabricated by incorporating a poly(ethyleneoxide)-grafted (PEO-grafted) amphiliic polymer. Both antifouling and antibacterial groups were easily introduced onto the membrane surfaces through non-solvent induced phase separon process and a simple chlorination process. It was observed that the functionalized membranes were effectivatie in resisting both protein absorption and bacterial adhesion. Furthermore, the functionalized membrane (M3-Cl) showed mostly suppressed irreversible flux decline and a 97% flux recovery ratio after simple washing during the separation process, indicating excellent antifouling properties. Meanwhile, the functionalized PSf membrane exhibited efficient biocidal activity against E. coli and S. aureus. These modified functionalized PSf membranes also displayed outstanding properties in inhibiting the formation of biofilm. Moreover, the antibacterial feature was renewable by a simple process.

A liquid-based Janus porous membrane for convenient liquid-liquid extraction and immiscible oil/water separation.

A novel liquid-based Janus porous membrane system was developed through the simple infusion of water and oil within different surfaces. This generates a stable liquid-infusion interface that repels immiscible organic solvents and water, and itself floats at the oil/water interface as a separator. The developed membrane successfully acts as a simple alternative for high-performance liquid separation.

Janus porous membrane with conical nanoneedle channel for rapid unidirectional water transport.

The pierced nanowire Janus porous membrane prepared in this study possesses piercing conical nanoneedles, which not only form a transport channel to enhance unidirectional water transport, but also reduce the energy barrier of water transport by changing the route of water transport from droplet to film.

Bioinspired superhydrophilic-hydrophobic integrated surface with conical pattern-shape for self-driven fog collection.

It is well recognized by the scientific community that the fog can be deposited and transported on asymmetric surfaces, thus numerous efforts have been made to create such surfaces. However, it is still challenging to design a surface capable of fast deposition and rapid transportation simultaneously. Herein, inspired by the asymmetric structure of cactus spines and the cooperative hydrophilic/hydrophobic regions of desert beetles, a superhydrophilic-hydrophobic integrated conical stainless steel needle (SHCSN) is fabricated by a facile method. This integrated needle surface combines the merits of the fast deposition of fog on hydrophobic region and then rapid transportation on superhydrophilic surface. The droplet average transportation velocity on SHCSN is greater than other types of surfaces because of large Laplace pressure and self-driven phenomenon at its superhydrophilic-hydrophobic boundary. The best fog harvest efficiency was realized by optimizing the length of the hydrophobic region using theoretical modeling and experimental exploration, whereas the robust superhydrophilic needle surface induced the increase of collection time. This SHCSN was realized to be more efficient in fog collection than uniform superhydrophilic, uniform hydrophobic/superhydrophobic needle surfaces.

Facile transformation of hydrophilic cellulose into superhydrophobic cellulose.

Superhydrophobic cellulose-based materials coupled with transparent, stable and nanoscale polymethylsiloxane coating have been successfully achieved by a simple process via chemical vapor deposition, followed by hydrolyzation and polymerization.

Integrated antimicrobial and antifouling ultrafiltration membrane by surface grafting PEO and N-chloramine functional groups.

Ultrafiltration membranes with integrated antimicrobial and antifouling properties were fabricated using an engineering thermoplastic (carboxylated cardopoly(aryl ether ketone, PEK-COOH). Different molecular weights of PEO (Mw: 120, 350, 550) were grafted to the PEK-COOH membrane surface via EDC/NHS methodology. N-chloramine modified membranes then were prepared by simple exposure to dilute sodium hypochlorite solution. The surface grafting processes were all performed in water (i.e. without organic solvent). With this surface modification, the hydrophilicity of membranes improved significantly and the pure water flux increased compared to the unmodified PEK-COOH membrane. Furthermore, the PEO and N-chloramine modified membranes were resistant not only to both protein adsorption and bacterial adhesion, but also to microbial proliferation. The results of this work suggest that PEO and N-chloramine modified membranes are promising as fouling-resistant membranes.