Water-selective hybrid membranes with improved interfacial compatibility from mussel-inspired dopamine-modified alginate and covalent organic frameworks

Hybrid membranes combining the merits of both polymer matrices and fillers have drawn extensive attention. The rational design of polymer–filler interface in hybrid membranes is vitally important for reducing the occurrence of void defects. Herein, imine-type covalent organic frameworks(COFs) were selected as the fillers due to their totally organic nature and multi-functionalities. Mussel-inspired dopamine-modified sodium alginate(Alg DA) was synthesized as the polymer matrix. The dopamine modification significantly improves the Alg DA–COF compatibility,which enhances the COF content up to 50 wt% in the hybrid membranes. The improved interfacial compatibility enhances the membrane separation selectivity. Accordingly, when utilized for dehydration of ethanol/water mixed solution(water concentration of 10 wt%), the hybrid membrane reveals high water concentration of ~98.7 wt% in permeate, and stable permeation flux larger than 1500 g·m-2·h-1. This work might afford useful insights for fabricating hybrid membranes with high separation selectivity by optimizing the polymer–filler interface.

Reducing active layer thickness of polyamide composite membranes using a covalent organic framework interlayer in interfacial polymerization

Polyamide(PA)-based thin-film composite membranes exhibit enormous potential in water purification,owing to their facile fabrication,decent performance and desirable stability.However,the thick PA active layer with high transport resistance from the conventional interfacial polymerization hampers their applications.The controllable fabrication of a thin PA active layer is essential for high separation efficiency but still challenging.Herein,a covalent organic framework TpPa-1 interlayer was firstly deposited on a polyethersulfone(PES)substrate to reduce the thickness of PA active layer in interfacial polymerization.The abundant pores of TpPa-1 increase the local concentration of amine monomers by adsorbing piperazine molecules,while hydrogen bonds between hydrophilic groups of TpPa-1 and piperazine molecules slow down their diffusion rate.Arising from those synergetic effects,the PA active layer is effectively reduced from 200 nm to 120 nm.By optimizing TpPa-1 interlayer and PA active layer,the water flux of resultant membranes can reach 171.35 L·m^-2·h^-1·MPa^-1,which increased by 125.4%compared with PA/PES membranes,while the rejection rates of sodium sulfate and dyes solution remained more than 90%and 99%,respectively.Our strategy may stimulate rational design of ultrathin PA-based nanofiltration membranes with high performances.

Research progress on the substrate for metal-organic framework(MOF) membrane growth for separation

During the last decade, metal-organic frameworks(MOFs) have been applied in various fields due to their unique chemical and functional advantages. One of the widespread research hotspots is MOF-based membranes for separations, specifically continuous defect-free MOF membranes, which are usually grown on porous substrates. The substrate not only serves as the MOF layer support but also has a great influence on the membrane fabrication process and the final separation performance of the resultant membrane. In this review, we mainly introduce the progress focused on the substrates for MOF membranes fabrication. The substrate modifications and seeding methods aimed at synthesizing highquality MOF membranes are also summarized systematically.

An efficient strategy for the preparation of MIL-53(Al)-NH_(2)membranes with high ion selectivity and desalination performance

The efficient extraction of sodium(Na^(+))and lithium(Li^(+))from seawater and salt lakes is increasingly demanding due to their great application value in chemical industries.However,coexisting cations such as divalent calcium(Ca^(2+))and magnesium(Mg^(2+))ions are at the subnanometer scale in diameter,similar to target monovalent ions,making ion separation a great challenge.Here,we propose a simple and fast secondary growth method for the preparation of MIL-53(Al)-NH_(2)membranes on the surface of anodic aluminum oxide.Such membranes contain angstrom-scale(~7Å)channels for the entrance of small monovalent ions and water molecules,endowing the selectivities for monovalent cations over divalent cations and water over salt molecules.The resulting high-connectivity MIL-53(Al)-NH_(2)membranes exhibit excellent ion separation performance(a selectivity of 121.42 for Na^(+)/Ca^(2+)and 93.81 for Li^(+)/Mg^(2+))and desalination performance(a water/salt selectivity of up to 5196).This work highlights metal–organic framework membranes as potential candidates for realizing ion separation and desalination in liquid treatment.

Quasi-solid electrolyte membranes with percolated metal–organic frameworks for practical lithium-metal batteries

High-energy Li-metal batteries (LMBs) suffer from short cycle life and safety issues due to severe parasitic reactions and dendrite growth of Li metal anode (LMA) in liquid electrolytes [1–3].It is generally believed that replacing liquid electrolytes with solidstate electrolytes (SSEs) would be a feasible approach for practical LMBs [4,5]. Conventional SSEs including ceramic and polymer electrolytes have been studied for decades.

In-situ incorporation of halloysite nanotubes with 2D zeolitic imidazolate framework-L based membrane for dye/salt separation

Layered assembled membranes of 2D leaf-like zeolitic imidazolate frameworks(ZIF-L)nanosheets have received great attention in the field of water treatment due to the porous structure and excellent antibacterial ability,but the dense accumulation on the membrane surface and the low permeate flux greatly hinder their application.Herein,we synthesized m HNTs(modified halloysite nanotubes)/ZIF-L nanocomposites on modified m HNTs by in situ growth method.Interestingly,due to the different size of m HNTs and ZIF-L,m HNTs were packed in ZIF-L nanosheets.The hollow m HNTs provided additional transport channels for water molecules,and the accumulation of the ZIF-L nanosheets was decreased after assembling m HNTs/ZIF-L nanocomposites into membrane by filtration.The prepared m HNTs/ZIF-L membrane presented high permeate flux(59.6 L·m^(-2)·h^(-1)),which is 2-4 times of the ZIF-L membranes(14.8 L·m^(-2)·h^(-1)).Moreover,m HNTs/ZIF-L membranes are intrinsically antimicrobial,which exhibit extremely high bacterial resistance.We provide a controllable strategy to improve 2D ZIF-L assembles,and develops novel membranes using 2D package structure as building units.

Self-assembled Cyclodextrin Metal-Organic Frameworks on Graphene Oxide as Filter Membrane for Tracelevel Naringin Pre-enrichment before Analysis

A green,renewable composite was designed and fabricated based on self-assembly of cyclodextrin metal-organic framework(CD-MOF)on graphene oxide(GO).Then,the GO@CD-MOF was embedded in 0.45μm PTFE membrane to produce a dual-functional membrane which could carry out sample enrichment by capturing naringin molecules.The membrane filter was further improved by investigating the effects of the experimental parameters including amount of GO@CD-MOF,enrichment time and elution solvent on enrichment efficiency of naringin.Further,the present method had been successfully applied to citrus sample and obtained satisfied recovery value(79.7%-100.3%).Moreover,the extraction of naringin can be achieved for 2 min,and GO@CD-MOF loaded membrane can be reused at least for 5 times.The results demonstrate that the fabrication of the novel filter membrane based on GO@CD-MOF is a fast,simple and reliable,and possesses great potential in the determination of naringin from real samples by dual-function of separation and enrichment.

Enhanced permeation performance of polyether-polyamide block copolymer membranes through incorporating ZIF-8 nanocrystals

Membrane-based CO_2 separation is a promising alternative in terms of energy and environmental issues to other conventional techniques. Polyether-polyamide block copolymer(Pebax) membranes are promising for CO_2 separation because of their excellent selectivity, but limited by their moderate gas permeability. In this study,fresh-prepared zeolitic imidazolate framework-8(ZIF-8) nanocrystals were integrated into the Pebax?1657matrices to form mixed matrix membranes. The resulting membrane exhibits significantly improved CO_2permeability(as high as 300% increase), without the sacrifice of the selectivity, to the pristine polymer membrane. Several physical characterization techniques were employed to confirm the good interfacial interaction between ZIF-8 fillers and Pebax matrices. The effect of added ZIF-8 fillers on the transport mechanism through MMMs is also explored. Mixed-gas permeation for both CO_2/N_2 and CO_2/CH_4 was also evaluated. The separation performance for CO_2/CH_4 mixtures on the ZIF-8/Pebax MMMs is very close to the Roberson upper bound, and thus is technologically attractive for purification of natural gas.

Engineering Leaf-Like UiO-66-SO3H Membranes for Selective Transport of Cations

Metal–organic frameworks(MOFs)with angstrom-sized pores are promising functional nanomaterials for the fabrication of cation permselective membranes(MOF-CPMs).However,only a few research reports show successful preparation of the MOF-CPMs with good cation separation performance due to several inherent problems in MOFs,such as arduous selfassembly,poor water resistance,and tedious fabrication strategies.Besides,low cation permeation flux due to the absence of the cation permeation assisting functionalities in MOFs is another big issue,which limits their widespread use in membrane technology.Therefore,it is necessary to fabricate functional MOF-CPMs using simplistic strategies to improve cation permeation.In this context,we report a facile in situ smart growth strategy to successfully produce ultrathin(<600 nm)and leaflike UiO-66-SO3H membranes at the surface of anodic alumina oxide.The physicochemical characterizations confirm that sulfonated angstrom-sized ion transport channels exist in the as-prepared UiO-66-SO3H membranes,which accelerate the cation permeation(~3×faster than non-functionalized UiO-66 membrane)and achieve a high ion selectivity(Na^+/Mg^2+>140).The outstanding cation separation performance validates the importance of introducing sulfonic acid groups in MOF-CPMs.

Design and synthesis of Al-MOF/PPSU mixed matrix membrane with pollution resistance

To enhance the performance of the polyphenylene sulfone(PPSU) membrane,a novel mixed matrix membrane with hydrophilicity and antifouling properties was prepared.Using PPSU as the ba sic membrane material,polyvinyl pyrrolidone(PVP) as the porogen,N-Methyl pyrrolidone(NMP) as the solvent,and MOF-CAU-1(Al_(4)(OH)_(2)(OCH_(3))_4(H_2 N-BDC)_(3)·xH_(2) O) as the filler,PPSU/CAU-1 mixed matrix membrane(MMM) was prepared by an immersion precipitation and phase transformation technique.By changing the amount of MOF-CAU-1,the properties and performance of the MMM membrane were investigated in terms of hydrophilicity,pore morphology,surface roughness,and dye removal.The results show that the highest pure water flux of the mixed reached 47.9 L·m^(-2)·h^(-1), when the CAU-1 addition amount was 1.0 wt%, which was 23% higher than that of the pure PPSU membrane.Both the rejection rate and the antifouling performance of the MMM membrane also noticeably improved.

Aqueous Two-Phase Interfacial Assembly of COF Membranes for Water Desalination

Aqueous two-phase system features with ultralow interfacial tension and thick interfacial region,affording unique confined space for membrane assembly.Here,for the first time,an aqueous two-phase interfacial assembly method is proposed to fabricate covalent organic framework(COF)membranes.The aqueous solution containing polyethylene glycol and dextran undergoes segregated phase separation into two water-rich phases.By respectively distributing aldehyde and amine monomers into two aqueous phases,a series of COF membranes are fabricated at water-water interface.The resultant membranes exhibit high NaCl rejection of 93.0-93.6% and water permeance reaching 1.7-3.7 L m^(−2) h^(−1) bar^(−1),superior to most water desalination membranes.Interestingly,the interfacial tension is found to have pronounced effect on membrane structures.The appropriate interfacial tension range(0.1-1.0 mN m^(−1))leads to the tight and intact COF membranes.Furthermore,the method is extended to the fabrication of other COF and metal-organic polymer membranes.This work is the first exploitation of fabricating membranes in all-aqueous system,confering a green and generic method for advanced membrane manufacturing.

Engineering HOF‑Based Mixed‑Matrix Membranes for Efficient CO_(2) Separation

Hydrogen-bonded organic frameworks(HOFs)have emerged as a new class of crystalline porous materials,and their application in membrane technology needs to be explored.Herein,for the first time,we demonstrated the utilization of HOF-based mixed-matrix membrane for CO_(2) separation.HOF-21,a unique metallo-hydrogen-bonded organic framework material,was designed and processed into nanofillers via amine modulator,uniformly dispersing with Pebax polymer.Featured with the mix-bonded framework,HOF-21 possessed moderate pore size of 0.35 nm and displayed excellent stability under humid feed gas.The chemical functions of multiple binding sites and continuous hydrogen-bonded network jointly facilitated the mass transport of CO_(2).The resulting HOF-21 mixed-matrix membrane exhibited a permeability above 750 Barrer,a selectivity of~40 for CO_(2)/CH_(4) and~60 for CO_(2)/N_(2),surpassing the 2008 Robeson upper bound.This work enlarges the family of mixed-matrix membranes and lays the foundation for HOF membrane development.

Silk nanofibril as nanobinder for preparing COF nanosheet-based proton exchange membrane

Two-dimensional covalent organic framework nanosheets(CONs)with ultrathin thickness and porous crystalline nature show substantial potential as novel membrane materials.However,bringing CONs materials into flexible membrane form is a monumental challenge due to the limitation of weak interactions among CONs.Herein,one-dimensional silk nanofibrils(SNFs)from silkworm cocoon are designed as the nanobinder to link sulfonated CON(SCON)into robust SCON-based membrane through vacuum-filtration method.Ultrathin and large lateral-sized SCONs are synthesized via bottom-up interface-confined synthesis approach.Benefiting from high length-diameter ratio of SNF and rich functional groups in both SNF and SCON,two-dimensional(2D)SCONs are effectively connected together by physical entanglement and strong H-bond interactions.The resultant SCON/SNF membrane displays dense structure,high mechanical integrity and good stability.Importantly,the rigid porous nanochannels of SCON,high-concentration-SO3H groups insides the pores and H-bonds at SCON-SNF interfaces impart SCON/SNF membrane high-rate proton transfer pathways.Consequently,a superior proton conductivity of 365 mS cm^(-1)is achieved at 80C and 100%RH by SCON/SNF membrane.This work offers a promising approach for connecting 2D CON materials into flexible membrane as high-performance solid electrolyte for hydrogen fuel cell and may be applied in membrane-related other fields.

Bimetallic ZIFs-derived electrospun carbon nanofiber membrane as bifunctional oxygen electrocatalyst for rechargeable zinc-air battery

The recharged zinc-air battery(ZAB) has drawn significant attention owing to increasing requirement for energy conversion and storage devices.Fabricating the efficient bifunctional oxygen catalyst using a convenient strategy is vitally important for the rechargeable ZAB.In this study,the bimetallic ZIFs-containing electrospun(ES) carbon nanofibers membrane with hierarchically porous structure was prepared by coaxial electrospinning and carbonization process,which was expected to be a bifunctional electrocatalyst for ZABs.Owing to the formed dual single-atomic sites of Co-N_(4) and Zn-N_(4),the obtained ES-Co/ZnCNZIFexhibited the preferable performance toward oxygen reduction reaction(ORR) with E1/2of 0.857 V and JLof 5.52 mA cm^(-2),which were more than Pt/C.Meanwhile,it exhibited a marked oxygen evolution reaction(OER) property with overpotential of 462 mV due to the agglomerated metallic Co nanoparticles.Furthermore,the ZAB based on the ES-Co/Zn-CNZIFcarbon nanofibers membranes delivered peak power density of 215 mW cm^(-2),specific capacity of 802.6 mA h g^(-1),and exceptional cycling stability,far larger than Pt/C+RuO_(2)-based ZABs.A solid-state ZAB based on ES-Co/Zn-CNZIFshowed better flexibility and stability with different bending angles.

Screening and design of COF-based mixed-matrix membrane for CH_(4)/N_(2) separation

Membrane separation is a high-efficiency,energy-saving,and environment-friendly separation technology.Covalent organic framework(COF)-based mixed-matrix membranes(MMMs)have broad application prospects in gas separation and are expected to provide new solutions for coal-bed methane purification.Herein,a high-throughput screening method is used to calculate and evaluate COF-based MMMs for CH_(4)/N_(2) separation.General design rules are proposed from thermodynamic and kinetic points of view using the computation-ready,experimental COFs.From our database containing 471,671 generated COFs,5 COF membrane materials were screened with excellent membrane selectivities,which were then used as the filler of MMMs for separation performance evaluation.Among them,BAR-NAP-Benzene_CF_(3) combined with polydimethylsiloxane and styrene-b-butadiene-b-styrene show high CH_(4) permeability of 4.43×10^(-13) mol·m·s^(-1)·Pa^(-1)·m^(-2) and high CH_(4)/N_(2) selectivity of 9.54,respectively.The obtained results may provide reasonable information for the design of COF-based membranes for the efficient separation of CH_(4)/N_(2).

Molecular dynamics simulation of small gas molecule permeation through CAU-1 membrane

CAU-1 is one of aluminum-based amine-functionalized Metal-Organic Frameworks(MOFs).Gas permeation and separation behaviors through CAU-1 membrane were simulated by the dual-control plane nonequilibrium molecular dynamics(DCP-NEMD)method.The thickness of membrane was 3.55 nm.Gases CO_(2),N_(2),CH_(4),H_(2),He,Kr and Xe were chosen for the calculation in both single component and binary mixtures.The permeation process was calculated in grand canonical(μVT)ensemble with periodic boundary conditions(PBC)in x-and y-directions at different temperatures.The calculated permeance of H_(2),CH_(4),N_(2),CO_(2) and Kr decreased with increasing temperature in both single and binary system,while that of Xe with kinetic molecule of 0.41 nm increased with increasing temperature.It shows Xe permeation is governed by activated diffusion.The simulated separation factors of CO_(2)/N_(2) and CO_(2)/CH_(4) of 4.2 and 1.3 respectively were lower than the experimental ones when only considering van der Waals interaction.Further consideration of electrostatic potential leads to improved calculation CO_(2)/N_(2) and CO_(2)/CH_(4) separation factor of 23.0 and 12.9 respectively that were consistent with the experimental ones of 26.2 and 14.8.It suggests the necessity of considering the Coulomb interactions between CO_(2) and NH_(2)-on the pore wall of CAU-1 for permeation of CO_(2).For H_(2)/N_(2) and H_(2)/CH_(4) the ideal selectivities also keep consistent with our experimental results.Interestingly,the simulated separation factor for noble Kr/Xe reaches infinite,predicting that CAU-1 membrane possesses potential separation properties for radioactive Kr/Xe.

Computational exploration of H_2S/CH_4 mixture separation using acid-functionalized UiO-66(Zr) membrane and composites

A computational study was firstly performed in this work to examine the applicability of an acid-functionalized metal-organic framework(MOF), Ui O-66(Zr)-(COOH)2, in membrane-based H2S/CH4 separation. The results show that this MOF could be potentially interesting when being used as the pure membrane material for the separation of the mixture with low H2 S concentration. Further, the performance of 10 different mixed matrix membranes(MMMs) on the basis of the MOF was predicted by combing the molecular simulation data and the Maxwell permeation model. The results indicate that using this MOF as filler particles in MMMs can signi ficantly enhance the permeation performance of pure polymers. The findings obtained in this work may be helpful in facilitating the application of this promising MOF for practical desulfurization process of fuel gas.

Regulatable pervaporation performance of Zn-MOFs/polydimethylsiloxane mixed matrix pervaporation membranes

Pervaporation(PV)is an emerging separation technique for liquid mixture.Mixed matrix membranes(MMMs)often demonstrate trade-off relationship between separation factor and flux.In this study,by changing the organic linkers(2-methyl imidazolate,imidazole-2-carboxaldehyde,2-ethyl imidazolate),ZIF-8,ZIF-90 and MAF-6 were prepared and filled in polydimethylsiloxane(PDMS)membranes for dealcoholization of 5%(mass)n-butanol solution,and the membranes properties and pervaporation performances were adjusted.Compared with the pure PDMS membrane,the addition of ZIF-8 resulted in a 9%increase in flux(1136 g·m^(-2)·h^(-1))and a 22.5%increase in separation factor(28.3),displaying antitrade-off effect.For the MAF-6/PDMS MMMs(2.0%mass loading),the pervaporation separation index(PSI)and separation factor were 32347 g·m^(-2)·h^(-1) and 58.6 respectively(increased by 34%and 154%in contrast with that of the pure PDMS membrane),and the corresponding permeation flux was 552 g·m^(-2)·h^(-1),presenting great potential in the removal butanol from water.It was deduced that the large aperture size combined with moderate hydrophobicity of metal–organic frameworks(MOFs)favor the concurrent increase in permeability and selectivity.

Reconstructing proton channels via Zr-MOFs realizes highly ion-selective and proton-conductive SPEEK-based hybrid membrane for vanadium flow battery

There is an urgent need to break through the trade-off between proton conductivity and ion selectivity of proton exchange membrane(PEM)in vanadium flow battery(VFB).Proton channels in PEM are the key to controlling the ion sieving and proton conductivity in VFB.Herein,two types of proton channels are reconstructed in the hybrid membrane via introducing modified Zr-MOFs(IM-UIO-66-AS)into SPEEK matrix.Internal proton channels in IM-UIO-66-AS and interfacial proton channels between grafted imidazole groups on Zr-MOFs and SPEEK greatly improve the conductivity of the IM-UIO-66-AS/SPEEK hybrid membrane.More importantly,both reconstructed proton channels block the vanadium-ion permeation to realize enhanced ion selectivity according to the size sieving and Donnan exclusion effects,respectively.Moreover,the hybrid membrane exhibits good mechanical property and dimensional stability.Benefiting from such rational design,a VFB loading with the optimized membrane exhibits enhanced voltage efficiency of 79.9%and outstanding energy efficiency of 79.6%at 200 m A cm^(-2),and keeps a notable cycle stability for 300 cycles in the long-term cycling test.Therefore,this study provides inspiration for preparing next-generation PEMs with high ion selectivity and proton conductivity for VFB application.

Solvent-Less Vapor-Phase Fabrication of Membranes for Sustainable Separation Processes

Sustainable processes for purifying water,capturing carbon,producing biofuels,operating fuel cells,and performing energy-efficient industrial separations will require next-generation membranes.Solvent-less fabrication for membranes not only eliminates potential environmental issues with organic solvents,but also solves the swelling problems that occur with delicate polymer substrates.Furthermore,the activation procedures often required for synthesizing microporous materials such as metal–organic frameworks(MOFs)can be reduced when solvent-less vapor-phase approaches are employed.This perspective covers several vacuum deposition processes,including initiated chemical vapor deposition(iCVD),initiated plasma-enhanced chemical vapor deposition(iPECVD),solvent-less vapor deposition followed by in situ polymerization(SLIP),atomic layer deposition(ALD),and molecular layer deposition(MLD).These solvent-less vapor-phase methods are powerful in creating ultrathin selective layers for thin-film composite membranes and advantageous in conformally coating nanoscale pores for the precise modification of pore size and internal functionalities.The resulting membranes have shown promising performance for gas separation,nanofiltration,desalination,and water/oil separation.Further development of novel membrane materials and the scaling up of high-throughput reactors for solvent-less vapor-phase processes are necessary in order to make a real impact on the chemical industry in the future.