Indispensable gutter layers in thin-film composite membranes for carbon capture

Industrial thin-film composite(TFC)membranes achieve superior gas separation properties from high-performance selective layer materials,while the success of membrane technology relies on high-performance gutter layers to achieve production scalability and low-cost manufacturing.However,the current literature predominantly focuses on the design of polymer architectures to obtain high permeability and selectivity,while the art of fabricating gutter layers is usually safeguarded by industrial manufacturers and appears lackluster to academic researchers.This is the first report aiming to provide a comprehensive and critical review of state-of-the-art gutter layer materials and their design and modification to enable TFC membranes with superior separation performance.We first elucidate the importance of the gutter layer on membrane performance through modeling and experimental results.Then various gutter layer materials used to obtain high-performance composite membranes are critically reviewed,and the strategies to improve their compatibility with the selective layer are highlighted,such as oxygen plasma treatment,polydopamine deposition,and surface grafting.Finally,we present the opportunities of the gutter layer design for practical applications.

Outstanding proton conductivity over wide temperature and humidity ranges and enhanced mechanical, thermal stabilities for surface-modified MIL-101-Cr-NH_(2)/Nafion composite membranes

High-performance proton exchange membranes are of great importance for fuel cells.Here,we have synthesized polycarboxylate plasticizer modified MIL-101-Cr-NH_(2)(PCP-MCN),a kind of hybrid metal-organic framework,which exhibits a superior proton conductivity.PCP-MCN nanoparticles are used as additives to fabricate PCP-MCN/Nafion composite membranes.Microstructures and characteristics of PCP-MCN and these membranes have been extensively investigated.Significant enhancement in proton conduction for PCP-MCN around 55℃ is interestingly found due to the thermal motion of the PCP molecular chains.Robust mechanical properties and higher thermal decomposition temperature of the composite membranes are directly ascribed to strong intermolecular interactions between PCP-MCN and Nafion side chains,i.e.,the formation of substantial acid–base pairs(-SO_(3)^(-)…^(+)H–NH-),which further improves compatibility between additive and Nafion matrix.At the same humidity and temperature condition,the water uptake of composite membranes significantly increases due to the incorporation of porous additives with abundant functional groups and thus less crystallinity degree in comparison to pristine Nafion.Proton conductivity(σ)over wide ranges of humidities(30-100%RH at 25℃)and temperatures(30-98℃ at 100%RH)for prepared membranes is measured.The s in PCPMCN/Nafion composite membranes is remarkably enhanced,i.e.0.245 S/cm for PCP-MCN-3wt.%/Nafion is twice that of Nafion membrane at 98℃ and 100%RH,because of the establishment of well-interconnected proton transport ionic water channels and perhaps faster protonation–deprotonation processes.The composite membranes possess weak humidity-dependence of proton transport and higher water uptake due to excellent water retention ability of PCP-MCN.In particular,when 3 wt.%PCP-MCN was added to Nafion,the power density of a single-cell fabricated with this composite membrane reaches impressively 0.480,1.098 W/cm^(2) under 40%RH,100%RH at 60℃,respectively,guaranteeing it to be a promising proton exchange membrane.

Pervaporation Separation of Butanol-Water Mixtures Using Polydimethylsiloxane/Ceramic Composite Membrane

Pervaporation has attracted considerable interest owing to its potential application in recovering biobutanol from biomass acetone-butanol-ethanol (ABE) fermentation broth. In this study, butanol was recovered from its aqueous solution using a polydimethylsiloxane (PDMS)/ceramic composite pervaporation membrane. The effects of operating temperature, feed concentration, feed flow rate and operating time on the membrane pervaporation performance were investigated. It was found that with the increase of temperature or butanol concentration in the feed, the total flux through the membrane increased while the separation factor decreased slightly. As the feed flow rate increased, the total flux increased gradually while the separation factor changed little. At 40°C and 1% (by mass) butanol in the feed, the total flux and separation factor of the membrane reached 457.4 g·m?2·h?1 and 26.1, respectively. The membrane with high flux is suitable for recovering butanol from ABE fermentation broth.

Solvent Recovery from Soybean Oil/Hexane Miscella by PDMS Composite Membrane

Traditional solvent recovery in the extraction step of edible oil processing is distillation,which consumes large amounts of energy.If the distillation is replaced by membrane process,the energy consumption can be reduced greatly.In this work,two kinds of membrane,PDMS(polydimethylsiloxane) composite membrane and Zeolite filled PDMS membrane were prepared,in which asymmetric microporous PVDF(polyvinylidenefluoride) membrane prepared with phase inversion method was functioned as the microporous supporting layer in the flat-plate composite membrane.The different function compositions of the PDMS/PVDF composite membranes were characterized by reflection Fourier transform infrared(FTIR) spectroscopy.The surface and section of PDMS/PVDF composite membranes were investigated by scanning electron microscope(SEM).The PDMS NF(nanofiltration) membranes were then applied in the recovery of hexane from soybean oil/hexane miscellas(1:3,mass ratio).The effects of pressure(0.5-1.5 MPa),cross-linking temperature and PDMS layer thickness on membrane performances were investigated.The results indicated that both two kinds of NF membranes were promising for solvent recovery,and zeolite filled in PDMS NF membrane could enhance the separation performance.

Ceramic Supported PDMS and PEGDA Composite Membranes for CO2 Separation

Composite membranes have attracted increasing attentions owing to their potential applications for CO2 separation. In this work, ceramic supported polydimethylsiloxane （PDMS） and poly （ethylene glycol） diacrylate （PEGDA） composite membranes were prepared. The microstructure and physicochemical properties of the compos- ite membranes were characterized. Preparation conditions were systematically optimized. The gas separation performance of the as-prepared membranes was studied by pure gas and binary gas permeation measurement of CO〉 N2 and H〉 Experiments showed that PDMS, as silicone rubber, exhibited larger permeance and lower separation factors. Conversely, PEGDA composite membrane presented smaller gas permeance but higher ideal selectivity for CO2/N2. Compared to the performance of those membranes using polymeric supports or freestanding membranes, the two kinds of ceramic supported composite membranes exhibited higher gas permeance and acceptable selectivity. Therefore, the ceramic supported composite membrane can be expected as a candidate for CO2 separation from light gases.

Fouling-resistant Composite Membranes for Separation of Oil-in-water Microemulsions

Fouling-resistant ceramic-supported polymer composite membranes were developed for removal of oil-in-water （O/W） mieroemulsions. The composite membranes were featured with an asymmetric three-layer structure, i.e., a porous ceramic membrane substrate, a polyvinylidene fluoride （PVDF） ultrafiltration sub-layer, and a polyamide/polyvinyl alcohol （PVA） composite thin top-layer. The PVDF polymer was east onto the tubular porous ceramic membranes with an immersion precipitation method, and the polyamide/PVA composite thin top-layer was fabricated with an inteffaeial polymerization method. The effects of the sub-layer composition and the recipe in the inteffaeial polymerization for fabricating the top-layer on the structure and performance of composite membranes were systematically investigated. The prepared composite membranes showed a good performance for treating the O/W microemulsions with a mean diameter of about 2.41μm. At the operating pressure of 0.4MPa, the hydraulic permeability remained steadily about 190L·m^-2·h^-1, the oil concentration in the permeate was less than 1.6mg·L^-1, and the oil rejection coefficient was always higher than 98.5% throughout the operation from the beginning.

Polymer/Ceramic Composite Membranes and Their Application in Pervaporation Process

Pervaporation(PV),as an environmental friendly and energy-saving separation technology,has been received increasing attention in recent years.This article reviews the preparation and application of macroporous ceramic-supported polymer composite pervaporation membranes.The separation materials of polymer/ceramic composite membranes presented here include hydrophobic polydimethylsiloxane(PDMS) and hydrophilic poly(vinyl alcohol)(PVA),chitosan(CS) and polyelectrolytes.The effects of ceramic support treatment,polymer solution properties,interfacial adhesion and incorporating or blending modification on the membrane structure and PV performance are discussed.Two in-situ characterization methods developed for polymer/ceramic composite membranes are also covered in the discussion.The applications of these composite membranes in pervaporation process are summarized as well,which contain the bio-fuels recovery,gasoline desulfuration and PV coupled proc-ess using PDMS/ceramic composite membrane,and dehydration of alcohols and esters using ceramic-supported PVA or PVA-CS composite membrane.Finally,a brief conclusion remark on polymer/ceramic composite mem-branes is given and possible future research is outlined.

Proton-Exchange Sulfonated Poly （ether ether ketone） （SPEEK）/SiOx-S Composite Membranes in Direct Methanol Fuel Cells

A sulfonated poly（ether ether ketone） （SPEEK） membrane with a fairly high degree of sulfonation （DS） can swell excessively and even dissolve at high temperature. To solve these problems, insolvable functionalized silica powder with sulfonic acid groups （SiOx-S） was added into the SPEEK matrix （DS = 55.1%） to prepare SPEEK/ SiOx-S composite membranes. The decrease in both the swelling degree and the methanol permeability of the membranes was a dose-dependent result of addition of the SiOx-S powder. Pure SPEEK membrane swelled 52.6% at 80℃, whereas the SPEEK/SiOx-S （15%, by mass） membrane swelled only 27.3% at the same temperature. From room temperature to 80℃, all SPEEK/SPEEK/SiOx-S composite membranes had methanol permeability of about one order of magnitude lower than that ofNafion115. Compared with pure SPEEK membranes, the addition of the SiOx-S powder not only leads to higher proton conductivity, but also increases the dimensional stability at higher temperatures, and greater proton conductivity can be achieved at higher temperature. The SPEEK/SiO4-S （20%, by mass） membrane could withstand temperature up to 145℃, at which in 100% relative humidity （RH） its proton conductivity exceeded slightly that of Nafion 1 15 membrane and reached 0.17 S·cm^-1, while pure SPEEK membrane dissolved at 90℃. The SPEEK/SiOx-S composite membranes are promising for use in direct methanol fuel cells because of their good dimensional stability, high proton conductivity, and low methanol permeability.

Separation of Sulfur/Gasoline Mixture with Polydimethylsiloxane/ Polyetherimide Composite Membranes by Pervaporatlon

Worldwide environment has resulted in a limit on the sulfur content of gasoline.It is urgent to investigate the desulfurization of gasoline.The polydimethylsiloxane(PDMS)/polyetherimide(PEI)composite membranes were prepared by casting a PDMS solution onto porous PEI substrates and characterized by scanning electron microscope(SEM).The membranes were used for sulfur removal from gasoline by pervaporation.The effects of feed temperature,sulfur content in the feed and PDMS layer thickness on membrane performance were investigated,and an activation energy of permeation was obtained.Experimental results indicated that higher feed temperature yielded higher total flux and lower sulfur enrichment factor.The total flux varied little with the increase of sulfur content in the feed,but the sulfur enrichment factor first increased with the amount of thiophene added into the gasoline,and then the variation was little.The increase of PDMS layer thickness resulted in a smaller flux but a larger sulfur enrichment factor.The result indicates that the PDMS/PEI composite membranes are promising for desulfurization by pervaporation.

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.

Novel polybenzimidazole/graphitic carbon nitride nanosheets composite membrane for the application of acid-alkaline amphoteric water electrolysis

It is a great challenge to develop membrane materials with high performance and long durability for acidalkaline amphoteric water electrolysis.Hence,the graphitic carbon nitride(g-C_(3)N_(4))nanosheets were compounded with the(2,2'-m-phenylene)-5,5'-benzimidazole(m-PBI)matrix for the preparation of m-PBI/g-C_(3)N_(4) composite membranes.The synthesis of g-C_(3)N_(4) nanosheets and m-PBI matrix have been confirmed by X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscoy(TEM)and ^(1)H nuclear magnetic resonance spectra(^(1)H NMR),respectively.The fourier transform infrared spectroscopy(FT-IR)and SEM of the composite membranes showed the g-C_(3)N_(4) nanosheets were well dispersed in the m-PBI/g-C_(3)N_(4) composite membrane.The mechanical properties test exhibited the good mechanical strength,and the TGA curves of m-PBI showed the high thermal stability of composite membranes.Besides,the m-PBI/g-C_(3)N_(4) composite membrane showed excellent proton and hydroxide ion conductivity,which was higher than pure m-PBI and Nafion 115 membrane.The acid-alkaline amphoteric water electrolysis test showed m-PBI/1%g-C_(3)N_(4) composite membrane has the best performance with a current density of 800 mA cm^(-2) at cell voltage of 1.98 V at 20℃.It showed that m-PBI/g-C_(3)N_(4) composite membrane has a good application prospect for acid-alkaline amphoteric water electrolysis.

Integral PVA-PES Composite Membranes by Surface Segregation Method for Pervaporation Dehydration of Ethanol

A facile surface segregation method was utilized to fabricate poly（vinyl alcohol）-polyethersulfone （PVA-PES） composite membranes. PVA and PES were first dissolved in dimethyl sulfoxide （DMSO）, then casted on a glass plate and immersed in a coagulation bath. During the phase inversion process in coagulation bath, PVA spontaneously segregated to the polymer solution/coagulation bath interface. The enriched PVA on the surface was further crosslinked by glutaraldehyde. Scanning electron microscopy （SEM）, X-ray photoelectron spectroscopy （XPS） and energy dispersive spectrometer （EDS） confirmed the integral and asymmetric membrane structure with a dense PVA-enriched surface and a porous PES-enriched support, as well as the surface enrichment of PVA. The coverage fraction of the membrane surtace by PVA reacned up to 86.8% when me PVA content m me membrane recipe was 16.7% （by mass）. The water contact angle decreased with the increase of PVA content. The effect of coagulation bath type on membrane structure was analyzed. The membrane pervaporation performance was evaluated by varying the PVA content, the annealing temperature, feed concentration and operation temperature. The membrane exhibited a fairly good ethanol dehydration capacity and long-term operational stability.

Enhancing Structural Stability and Pervaporation Performance of Composite Membranes by Coating Gelatin onto Hydrophilically Modified Support Layer

The interfacial compatibility of composite membrane is an important factor to its structural stability, andseparation performance. In this study, poly （ether sulfone） （PES） support layer was first hydrophilically modified with poly（vinyl alcohol） （PVA） via surface segregation during the phase inversion process. Gelatin （GE） was then cast on the PVA-modified PES support layer as the active layer followed by crosslinking to fabricate composite membranes for ethanol dehydration. The enrichment of PVA on the surface of support layer improved interfacial compatibility of the as-prepared GE/PVA-PES composite membrane. The water contact angle measurement and X-ray photoelectron spectroscopy （XPS） data confirmed the surface segregation of PVA with a surface coverage density of -80%. T-peel test showed that the maxima/force to separate the support layer and the active layer was enhanced by 3 times compared with the GE/PES membrane. The effects of PVA content in the support layer, crosslinking of GE active layer and operating parameters on the pervaporative dehydration performance were investigated. The operational stability of the composite membrane was tested by immersing the membrane in ethanol aqueous solution for a period of time. Stable pervaporation performance for dehydration of 90% ethanol solution was obtained for GE/PVA-PES membrane with a separation factor of -60 and a permeation flux of -1910 g.m^-2.h1 without peeling over 28 days immersion.

TiO2-incorporated polyelectrolyte composite membrane with transformable hydrophilicity/hydrophobicity for nanofiltration separation

The wettability of the membrane surface has shown obvious influent on the separation performance of the membrane.In this work,a hydrophilic PDA-[PDDA/TiO2]+Cl-membrane was prepared by a one-step codeposition of poly(diallyldimethylammonium chloride)(PDDA)polyelectrolyte solution containing positively charged TiO2@PDDA nanoparticles with the assistance of dopamine(DA).Such positively charged membrane can be transformed into a hydrophobic membrane PDA-[PDDA/TiO2]+PFO-via the counterion exchange between Cl-and PFO-(perfluorooctanoate).The transformation between hydrophilicity and hydrophobicity is reversible.For both hydrophilic and hydrophobic membranes,the nanofiltration performances were respectively investigated by the aqueous solution and ethanol solution of dyes including methyl blue(MB),Congo red(CR)and Evans blue(EB),and as well metal salt aqueous solution.The consecutive running stability and anti-fouling performance of both hydrophilic and hydrophobic membranes were explored.The results revealed that both membranes showed high nanofiltration performances for retention of dyes in(non)aqueous solution.For the hydrophilic membrane,the rejection of salts in a sequence is MgSO4>Na2SO4>MgCl2>NaCl.Moreover,both of the hydrophilic and hydrophobic membranes showed high stability and antifouling property.

Preparation of defect free ceramic/Ti composite membranes by surface modification and in situ oxidation

Al2O3 ceramic powder was applied to modify the large pores defects on the surface of the porous metal Ti support,in situ oxidation method was a convenient method to prepare defect free ceramic/Ti composite membranes on this basis.In situ oxidation conditions experimental results show that the best condition for preparing the TiO2-Al2O3/Ti composite membrane is under 800°C for 2 h,and the microstructure and pore sizes of the TiO2-Al2O3/Ti composite membranes are affected obviously.The thickness and composition of the TiO2/Ti composite membranes are determined by SEM and XRD completely.The pore size distribution of the composite membrane is measured by bubble pressure method,the most probable aperture is about 3.12μm,while the average pore size of defect free TiO2-Al2O3/Ti is about 3.23μm.After ultrasonic treatment,the slight weight change of membranes reveals no observable change,which indicates that TiO2-Al2O3/Ti composite membranes maintain a good stability.

A novel CHS/ALG bi-layer composite membrane with sustained antimicrobial efficacy used as wound dressing

A membrane composed of an alginate（ALG） layer and a chitosan（CHS） layer with sustained antimicrobial efficacy was prepared.Ciprofloxacin HC1（CIP） was incorporated into the ALG layer.Morphological feature of the composite membrane was analyzed by scanning electron microscopy（SEM）.Water uptake capacity,in vitro drug release,and in vitro antimicrobial activity were evaluated.The composite membrane exhibited perfect binding characteristic between the two layers.The water uptake capacity of all the membranes was above 800%.The CIP could release from the composite membranes for 48 h.The membrane could control the bacterial growth persistently.The results suggested that this CHS/ALG composite membrane incorporated with CIP had the potential for wound dressing application.

Innovative hydrophobic/hydrophilic perfluoropolyether(PFPE)/polyvinylidene fluoride(PVDF)composite membrane for vacuum membrane distillation

Though membrane distillation(MD)has gained more and more attention in the field of desalination,the wetting phenomenon was still a non-negligible problem.In this work,a method combined dip-coating and UV in situ polymerization for preparing hydrophobic/hydrophilic perfluoropolyether(PFPE)/polyvinylidene fluoride composite membranes.This composite membrane consisted of a top thin hydrophobic coating layer and hydrophilic substrate membrane.In terms of anti-wetting properties,contact angle and liquid entry pressure of all composite membranes(except for those based on 0.45μm)exceeded 160°and 0.3 MPa,respectively.In particular,the desalination performance was tested in vacuum membrane distillation tests by feeding 3.5%(mass)saline solution(NaCl)at 60℃.The composite membranes with larger support pore size and lower PFPE content had higher membrane distillation flux.And for stability tests(testing the 0.22μm membrane coated by 5%(mass)PFPE),the highest MD flux29.08 kg·m^(-2)·h^(-1) and stable salt rejection(over 99.99%)during the period.Except that,the effects of coating material concentration and pore sizes of substrate membrane were also investigated for surface morphology and topography,porosity,mechanical strength and pore size characteristics.This work provided a simple and effective alternative to prepare excellent hydrophobic composite membranes for MD applications.

SEPARATION OF PROPANE FROM PROPANE/NITROGEN MIXTURES USING PDMS COMPOSITE MEMBRANES BY VAPOR PERMEATION

This study deals with polydimethylsiloxane(PDMS)/polyvinylidene fluoride(PVDF) composite membranes for propane separation from propane/nitrogen mixtures,which is relevant to the recovery of propane in petroleum and chemical industry.The surface and cross-section morphology of PDMS/PVDF composite membranes was observed by scanning electron microscope(SEM).The surface morphology of PDMS/PVDF composite membranes is very dense.There are three layers,the thin dense top layer,finger-like porous middle layer and s...

Preparation and characterization of a composite membrane based on the asphaltene component of coal

Asphaltene-ceramic composite membranes were fabricated from ceramic supports and an asphaltene component, which was obtained from the separation of coal to give a kind of new carbonaceous precursor material. Using SEM and thermogravimetric analysis to measure the microstructure and properties of the asphaltene component allowed the porosity, permeability, and retention ratios to be determined. The results show that the asphaltene component can be regarded as a good carbon membrane precursor material because of its high carbon content and strong bonding capacity. When ceramic supports are impregnated with asphaltene colloid the asphaltene easily combines with the support surface and forms a good carbonaceous film after carbonization. Little of the asphaltene component permeates into the internal pores of the ceramic support. Although the number of coats applied to the substrate had little affect on the porosity of the asphaltene-ceramic composite membranes the permeability varied depend- ing upon the number of times the substrate was treated. The way bubbles escape from the film, and the phenomenon of coalescence, as affected by different film thicknesses also seem closely related to the number of coats. A composite membrane carbonized at a final temperature of 600℃ is relatively dense and the permeability of Fe（OH）3 colloid through it is very low. A membrane fired at 800℃ is porous and its permeability and retention of Fe（OH）3 colloid are 88 L/（m2 h MPa） and 85.3%, respectively when the trans-membrane pressure is 0.22 MPa.

Permeation Characteristics of Light Hydrocarbons Through Poly（amide-6-β-ethylene oxide） Multilayer Composite Membranes

In this paper, poly(amide-6-β-ethylene oxide) (PEBA1657) copolymer was used to prepare multilayer polyetherimide (PEI)/polydimethylsiloxane (PDMS)/PEBA1657/PDMS composite membranes by dip-coating method. Permeation behaviors of ethylene, ethane, propylene, propane, n-butane, methane and nitrogen through the multilayer composite membranes were investigated over a range of operating temperature and pressure. The permeances of light hydrocarbons through PEI/PDMS/PEBA1657/PDMS composite membranes increase with their increasing condensability, and the olefins are more permeable than their corresponding paraffins. For light hydrocarbons, the gas permeances increase significantly as temperature increasing. When the transmembrane pressure difference increases, the gas permeance increases moderately due to plasticization effect, while their apparent activation energies for permeation decrease.