Imidazolium group prompted alkaline anion-exchange membrane with high performance for efficient electrochemical CO_(2) conversion

Development of high-performance hydroxide-conductive membranes is a focus research subject owing to promising applications in electrochemical reduction of CO_(2)(eCO_(2)RR).However,few satisfactory membranes have been developed to maximize the performance of CO_(2) electrolyzers,despite its role as the core in regulating ion transport and preventing product crossover or fuel loss.Herein,we report the synthesis of alkaline anion-exchange membranes fabricated by poly(vinyl-alcohol)(PVA)and poly[(3-methyl-1-vinylimidazoliummethylsulfate)-co-(1-vinylpyrrolidone)](PQ44)for use in CO_(2) electrolysis.Owing to the unique imidazolium ring structure coupled with a three-dimensional semiinterpenetrating porous internal architecture,the PVA/PQ44-OH-membranes provide a high hydroxide conductivity(21.47 mS cm^(-1)),preferable mechanical property and thermal stability.In particular,the eCO_(2)RR used PVA/PQ44-OH^(-) as electrolyte membrane realized a charming Faradaic efficiency(88%)and partial current density(29 mA cm^(-2))at0.96 VRHE and,delivered the excellent durability over 20 h electrolysis in 0.5 mol L^(-1) KHCO_(3) electrolyte.Notably,it can even enable an ultrahigh current density beyond 100 mA cm^(-2) at^(-1).11 VRHE when the electrolyte was KOH instead,and produced the FEHCOOof 85%at a low potential of0.81 VRHE,superior to both commercial alkaline A201 and acidic Nafion117 membrane.

Synthesis and characterization of quaternized poly(phthalazinone ether sulfone ketone)for anion-exchange membrane

Chloromethylated poly（phthalazinone ether sulfone ketone） （CMPPESK） was prepared from poly（phthalazinone ether sulfone ketone） （PPESK） using chloromethyl octyl ethers （CMOE） with lower toxicity as chloromethylated regent. CMPPESK was soluble in N-methyl-2-pyrrolidone （NMP）, N,N-dimethylacetamide （DMAc） and chloroform. Quaternized poly（phthalazinone ether sulfone ketone） （QAPPESK） was prepared from CMPPESK by quaternization. QAPPESK had excellent solvent resistance, which was only partly soluble in sulfuric acid （98%） and swollen in N,N-dimethylformamide （DMF）. The vanadium redox flow battery （V-RFB） using QAPPESK anion-exchange membrane had better performance with 88.3% of overall energy efficiency.

A RAPID METHOD TO DETERMINE DIFFUSION COEFFICIENTS OF COUNTER-IONS IN AN ION-EXCHANGE MEMBRANE

1 INTRODUCTIONRapid and precise methods to obtain the diffusion coefficients of counter-ions are im-portant for the characterization of ion exchange membranes.Many theoreticaldescriptions of ion transport in ion exchange membranes have been developed by usingthe principles of irreversible thermodynamics,or the Nernst-Planck equations.Fick’s law can also be used for the description of the transport of ions with equaldiffusivity.However,for counter-ions of different diffusivities,Nerst-Planck

FREE ALKALI RECOVERY FROM NaOH LEACHING LIQUOR OF TUNGSTEN ORE BY ELECTROLYSIS WITH ION-EXCHANGE MEMBRANE

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Transport Properties of Novel Hybrid Cation-Exchange Membranes on the Base of MF-4SC and Halloysite Nanotubes

The diffusion permeability through new hybrid materials based on a Nafion-type membrane (MF- 4SC) and nanotubes of halloysite is investigated using the Nernst-Planck approach. A method of quantitative evaluation of physicochemical parameters (averaged and individual diffusion coefficients and averaged distribution coefficients of ion pairs in the membrane) of system “electrolyte solution—ion-exchange membrane—water”, which was proposed earlier, is further developed. The parameters of hybrid membranes on the base of MF-4SC and nanotubes of halloysite (5% wt and 8% wt) are obtained from experimental data on diffusion permeability of NaCl solutions using theoretical calculations. New model of three-layer membrane system can be used for refining calculated results with taking into account both diffusive layers. It is shown that adding of halloysite nanotubes into the membrane volume noticeably affects exchange capacity as well as structural and transport characteristics of original perfluorinated membranes. Hybrid membranes on the base of MF-4SC and halloysite nanotubes can be used in fuel cells and catalysis.

Phosphate removal from aqueous solution by Donnan dialysis with anion-exchange membrane

The removal of phosphate from aqueous solution by Donnan dialysis with anion-exchange membrane was investigated.The results show that phosphate could be removed from aqueous solution without supplying external high pressure or electrical potential.Under the conditions of influent phosphate of 2.0 mg/L,counterion(Cl-)concentration of 0.1 mol/L,stirring speed of 500 r/min and phase temperature of 298 K,the removal of phosphate achieves 70.0%.Decreasing counterion concentration has little influence on the removal of phosphate,but phosphate amount in anion-exchange membrane increases significantly.With the increase of stirring speed and phase temperature,the removal efficiency of phosphate greatly is improved.Existing forms of phosphate in aqueous solution affected transport of phosphate and only strong acidic pH of feed solution(pH=3.0)decreases the removal of phosphate.Transport of phosphate is also accompanied by change of pH value of feed solution.In consequence,it might be a promise potential process for phosphate advanced wastewater treatment,especially in the area where high salted nature water can be utilized.

Advancing ion-exchange membranes to ion-selective membranes:principles,status,and opportunities

Ion-exchange membranes(IEMs)are utilized in numerous established,emergent,and emerging applications for water,energy,and the environment.This article reviews the five different types of IEM selectivity,namely charge,valence,specific ion,ion/solvent,and ion/uncharged solute selectivities.Technological pathways to advance the selectivities through the sorption and migration mechanisms of transport in IEM are critically analyzed.Because of the underlying principles governing transport,efforts to enhance selectivity by tuning the membrane structural and chemical properties are almost always accompanied by a concomitant decline in permeability of the desired ion.Suppressing the undesired crossover of solvent and neutral species is crucial to realize the practical implementation of several technologies,including bioelectrochemical systems,hypersaline electrodialysis desalination,fuel cells,and redox flow batteries,but the ion/solvent and ion/uncharged solute selectivities are relatively understudied,compared to the ion/ion selectivities.Deepening fundamental understanding of the transport phenomena,specifically the factors underpinning structure-property-performance relationships,will be vital to guide the informed development of more selective IEMs.Innovations in material and membrane design offer opportunities to utilize ion discrimination mechanisms that are radically different from conventional IEMs and potentially depart from the putative permeability-selectivity tradeoff.Advancements in IEM selectivity can contribute to meeting the aqueous separation needs of water,energy,and environmental challenges.

Towards reliable assessment of hydrogen oxidation electrocatalysts for anion-exchange membrane fuel cells

Recent advancement of proton exchange membrane fuel cells has led to commercial sales of fuel-cell cars but market barrier exists because this technology heavily relies on platinum catalyst.Given the permission of adopting platinum-group-metal-free catalysts,anion-exchange membrane fuel cell has received notable attention.However,the sluggish kinetics of anodic hydrogen oxidation reaction(HOR)largely limit the cell efficiency.Although many high-performance HOR catalysts have been reported,there are analytical uncertainties in the literature concerning the assessment of the catalyst activity.Here we determine the origin of false HOR currents in the recorded polarization curves and propose a rigorous approach to eliminate them.We unveil experimentally the uncertainties of obtaining exchange current densities(j0)using Tafel plot from Bulter–Volmer equation and recommend employing the micro-polarization region method.For bulky catalysts that cannot establish a well-defined diffusion layer,we suggest applying external stirring bar to offer certain level of enforced convection and using j0 to compare the activity.

Effects of ion-exchange on the pervaporation performance and microstructure of NaY zeolite membrane

Pervaporation performance of NaY zeolite membranes is improved by ion-exchange with di-valent nitrate salt.Different nitrate salts,including Co(NO_(3))_(2),Mg(NO_(3))_(2),Zn(NO_(3))_(2),Ca(NO_(3))_(2),Cu(NO_(3))_(2),KNO_(3),and AgNO_(3),have great effects on the channel structure and water affinity of the NaY zeolite membrane.When the concentration of nitrate salt,ion-exchange temperature and time are 0.1 mol·L^(-1),50℃and 2 h,the ion-exchange degree order of NaY zeolites is Ag^(+)>K^(+)>Ca^(2+)>Zn^(2+)>>Co^(2+)>Mg^(2+).Especially,Ag^(+)and K^(+)cation exchange degree of NaY zeolites are achieved to 96.54% and 82.77% in this work.BET surface,total pore capacity,pore size distribution and water contact angle of the ion-exchanged NaY zeolites are all disordered by mono-and di-valent cations.Di-valent nitrate salt is favor for increasing the dehydration performance of NaY zeolite membranes by ion-exchange.When the ion-exchange solution is Zn(NO_(3))_(2),the total flux variation and separation factor variation of the NaY membrane(M-5)are -45% and 230% for separation of 10%(mass)H_(2)O/EtOH mixture by pervaporation,and the ion-exchanged membranes showed good reproducibility.

Sustained release of vascular endothelial growth factor A and basic fibroblast growth factor from nanofiber membranes reduces oxygen/glucose deprivation-induced injury to neurovascular units

Upregulation of vascular endothelial growth factor A/basic fibroblast growth factor(VEGFA/b FGF)expression in the penumbra of cerebral ischemia can increase vascular volume,reduce lesion volume,and enhance neural cell proliferation and differentiation,thereby exerting neuroprotective effects.However,the beneficial effects of endogenous VEGFA/b FGF are limited as their expression is only transiently increased.In this study,we generated multilayered nanofiber membranes loaded with VEGFA/b FGF using layer-by-layer self-assembly and electrospinning techniques.We found that a membrane containing 10 layers had an ideal ultrastructure and could efficiently and stably release growth factors for more than 1 month.This 10-layered nanofiber membrane promoted brain microvascular endothelial cell tube formation and proliferation,inhibited neuronal apoptosis,upregulated the expression of tight junction proteins,and improved the viability of various cellular components of neurovascular units under conditions of oxygen/glucose deprivation.Furthermore,this nanofiber membrane decreased the expression of Janus kinase-2/signal transducer and activator of transcription-3(JAK2/STAT3),Bax/Bcl-2,and cleaved caspase-3.Therefore,this nanofiber membrane exhibits a neuroprotective effect on oxygen/glucose-deprived neurovascular units by inhibiting the JAK2/STAT3 pathway.

Elaidic acid leads to mitochondrial dysfunction via mitochondria-associated membranes triggers disruption of mitochondrial calcium fluxes

Elaidic acid(EA)stimulation can lead to endoplasmic reticulum stress(ERS),accompanied by a large release of Ca^(2+),and ultimately the activation of NLRP3 inflammasome in Kupffer cells(KCs).Mitochondrial instability or dysfunction may be the key stimulating factors to activate NLRP3 inflammasome,and sustained Ca^(2+)transfer can result in mitochondrial dysfunction.We focused on KCs to explore the damage to mitochondria by EA.After EA stimulation,cells produced an oxidative stress(OS)response with a significant increase in ROS release.Immunoprecipitation experiments and the addition of inhibitors revealed that the increase in the level of intracellular Ca^(2+)led to Ca^(2+)accumulation in the mitochondrial matrix via mitochondria-associated membranes(MAMs).This was accompanied by a significant release of m ROS,loss of MMP and ATP,and a significant increase in mitochondrial permeability transition pore opening,ultimately leading to mitochondrial instability.These findings confirmed the mechanism that EA induced mitochondrial Ca^(2+)imbalance in KCs via MAM,ultimately leading to mitochondrial dysfunction.Meanwhile,EA induced OS and the decrease of MMP and ATP in rat liver,and significant lesions were found in liver mitochondria.Swelling of the inner mitochondrial cristae and mitochondrial vacuolization occurred,with a marked increase in lipid droplets.

Milk fat globule membrane supplementation protects againstβ-lactoglobul-ininduced food allergy in mice via upregulation of regulatory T cells and enhancement of intestinal barrier in a microbiota-derived short-chain fatty acids manner

Milk fat globule membrane(MFGM),which contains abundant glycoproteins and phospholipids,exerts beneficial effects on intestinal health and immunomodulation.The aim of this study was to evaluate the protective effects and possible underlying mechanisms of MFGM on cow’s milk allergy(CMA)in aβ-lactoglobulin(BLG)-induced allergic mice model.MFGM was supplemented to allergic mice induced by BLG at a dose of 400 mg/kg body weight.Results demonstrated that MFGM alleviated food allergy symptoms,decreased serum levels of lipopolysaccharide,pro-inflammatory cytokines,immunoglobulin(Ig)E,Ig G1,and Th2 cytokines including interleukin(IL)-4,while increased serum levels of Th1 cytokines including interferon-γand regulatory T cells(Tregs)cytokines including IL-10 and transforming growth factor-β.MFGM modulated gut microbiota and enhanced intestinal barrier of BLG-allergic mice,as evidenced by decreased relative abundance of Desulfobacterota,Rikenellaceae,Lachnospiraceae,and Desulfovibrionaceae,while increased relative abundance of Bacteroidetes,Lactobacillaceae and Muribaculaceae,and enhanced expressions of tight junction proteins including Occludin,Claudin-1 and zonula occludens-1.Furthermore,MFGM increased fecal short-chain fatty acids(SCFAs)levels,which elevated G protein-coupled receptor(GPR)43 and GPR109A expressions.The increased expressions of GPR43 and GPR109A induced CD103+dendritic cells accumulation and promoted Tregs differentiation in mesenteric lymph node to a certain extent.In summary,MFGM alleviated CMA in a BLG-induced allergic mice model through enhancing intestinal barrier and promoting Tregs differentiation,which may be correlated with SCFAs-mediated activation of GPRs.These findings suggest that MFGM may be useful as a promising functional ingredient against CMA.

Machine learning for membrane design and discovery

Membrane technologies are becoming increasingly versatile and helpful today for sustainable development.Machine Learning(ML),an essential branch of artificial intelligence(AI),has substantially impacted the research and development norm of new materials for energy and environment.This review provides an overview and perspectives on ML methodologies and their applications in membrane design and dis-covery.A brief overview of membrane technologies isfirst provided with the current bottlenecks and potential solutions.Through an appli-cations-based perspective of AI-aided membrane design and discovery,we further show how ML strategies are applied to the membrane discovery cycle(including membrane material design,membrane application,membrane process design,and knowledge extraction),in various membrane systems,ranging from gas,liquid,and fuel cell separation membranes.Furthermore,the best practices of integrating ML methods and specific application targets in membrane design and discovery are presented with an ideal paradigm proposed.The challenges to be addressed and prospects of AI applications in membrane discovery are also highlighted in the end.

Suppression of current-induced membrane discharge of bipolar membranes by regulating ion crossover transport

Bipolar membranes(BPMs)exhibit the unique capability to regulate the operating environment of electrochemical system through the water dissociation-combination processes.However,the industrial utilization of BPMs is limited by instability and serious energy consumption.The current-induced membrane discharge(CIMD)at high-current conditions has a negative influence on the performance of anion-exchange membranes,but the underlying ion transport mechanisms in the BPMs remain unclear.Here,the CIMD-coupled Poisson-Nernst-Planck(PNP)equations are used to explore the ion transport mechanisms in the BPMs for both reverse bias and forward bias at neutral and acid-base conditions.It is demonstrated that the CIMD effect in the reverse-bias mode can be suppressed by enhancing the diffusive transport of salt counter-ions(Na^(+)and Cl^(−))into the BPMs,and that in the forward-bias mode with acid-base electrolytes can be suppressed by matching the transport rate of water counter-ions(H_(3)O^(+)and OH^(−)).Suppressing the CIMD can promote the water dissociation in the reverse-bias mode,as well as overcome the plateau of limiting current density and reduce the interfacial blockage of salt co-ions(Cl^(−))in the anion-exchange layer in the forward-bias mode with acid-base electrolytes.Our work highlights the importance of regulating ion crossover transport on improving the performance of BPMs.

Regulation of interlayer channels of graphene oxide nanosheets in ultra-thin Pebax mixed-matrix membranes for CO_(2) capture

For the application of carbon capture by membrane process,it is crucial to develop a highly permeable CO_(2)-selective membrane.In this work,we reported an ultra-thin polyether-block-amide(Pebax)mixedmatrix membranes(MMMs)incorporated by graphene oxide(GO),in which the interlayer channels were regulated to optimize the CO_(2)/N_(2) separation performance.Various membrane preparation conditions were systematically investigated on the influence of the membrane structure and separation performance,including the lateral size of GO nanosheets,GO loading,thermal reduction temperature,and time.The results demonstrated that the precisely regulated interlayer channel of GO nanosheets can rapidly provide CO_(2)-selective transport channels due to the synergetic effects of size sieving and preferential adsorption.The GO/Pebax ultra-thin MMMs exhibited CO_(2)/N_(2) selectivity of 72 and CO_(2) permeance of 400 GPU(1 GPU=106 cm^(3)(STP)·cm^(2)·s^(-1)·cmHg^(-1)),providing a promising candidate for CO_(2) capture.

In‑depth proteome characterization of endometrium and extraembryonic membranes during implantation in pig

Background Proteome characterization of the porcine endometrium and extraembryonic membranes is important to understand mother-embryo cross-communication.In this study,the proteome of the endometrium and cho-rioallantoic membrane was characterized in pregnant sows(PS)during early gestation(d 18 and 24 of gestation)and in the endometrium of non-pregnant sows(NPS)during the same days using LC-MS/MS analysis.The UniProtKB database and ClueGO were used to obtain functional Gene Ontology annotations and biological and functional networks,respectively.Results Our analysis yielded 3,254 and 3,457 proteins identified in the endometrium of PS and NPS,respectively;of these,1,753 being common while 1,501 and 1,704 were exclusive to PS and NPS,respectively.In addition,we iden-tified 3,968 proteins in the extraembryonic membranes of PS.Further analyses of function revealed some proteins had relevance for the immune system process and biological adhesion in endometrium while the embryonic chorion displayed abundance of proteins related to cell adhesion and cytoskeletal organization,suggesting they dominated the moment of endometrial remodeling,implantation and adhesion of the lining epithelia.Data are available via Pro-teomeXchange with identifier PXD042565.Conclusion This is the first in-depth proteomic characterization of the endometrium and extraembryonic mem-branes during weeks 3 to 4 of gestation;data that contribute to the molecular understanding of the dynamic environ-ment during this critical period,associated with the majority of pregnancy losses.

Electrifying Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ) for focalized heating in oxygen transport membranes

Industry decarbonization requires the development of highly efficient and flexible technologies relying on renewable energy resources,especially biomass and solar/wind electricity.In the case of pure oxygen production,oxygen transport membranes(OTMs)appear as an alternative technology for the cryogenic distillation of air,the industrially-established process of producing oxygen.Moreover,OTMs could provide oxygen from different sources(air,water,CO_(2),etc.),and they are more flexible in adapting to current processes,producing oxygen at 700^(-1)000℃.Furthermore,OTMs can be integrated into catalytic membrane reactors,providing new pathways for different processes.The first part of this study was focused on electrification on a traditional OTM material(Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)),imposing different electric currents/voltages along a capillary membrane.Thanks to the emerging Joule effect,the membrane-surface temperature and the associated O_(2) permeation flux could be adjusted.Here,the OTM is electrically and locally heated and reaches 900℃on the surface,whereas the surrounding of the membrane was maintained at 650℃.The O_(2)permeation flux reached for the electrified membranes was~3.7 NmL min^(-1)cm^(-2),corresponding to the flux obtained with an OTM non-electrified at 900℃.The influence of depositing a porous Ce_(0.8)Tb_(0.2)O_(2-δ) catalytic/protective layer on the outer membrane surface revealed that lower surface temperatures(830℃)were detected at the same imposed electric power.Finally,the electrification concept was demonstrated in a catalytic membrane reactor(CMR)where the oxidative dehydrogenation of ethane(ODHE)was carried out.ODHE reaction is very sensitive to temperature,and here,we demonstrate an improvement of the ethylene yield by reaching moderate temperatures in the reaction chamber while the O_(2) injection into the reaction can be easily fine-tuned.

Probing the Efficiency of PPMG-Based Composite Electrolytes for Applications of Proton Exchange Membrane Fuel Cell

PPMG-based composite electrolytes were fabricated via the solution method using the polyvinyl alcohol and polyvinylpyrrolidone blend reinforced with various contents of sulfonated inorganic filler.Sulfuric acid was employed as the sulfonating agent to functionalize the external surface of the inorganic filler,i.e.,graphene oxide.The proton conductivities of the newly prepared proton exchange membranes(PEMs)were increased by increasing the temperature and content of sulfonated graphene oxide(SGO),i.e.,ranging from 0.025 S/cm to 0.060 S/cm.The induction of the optimum level of SGO is determined to be an excellent route to enhance ionic conductivity.The single-cell performance test was conducted by sandwiching the newly prepared PEMs between an anode(0.2 mg/cm^(2) Pt/Ru)and a cathode(0.2 mg/cm^(2) Pt)to prepare membrane electrode assemblies,followed by hot pressing under a pressure of approximately 100 kg/cm^(2) at 60℃for 5–10 min.The highest power densities achieved with PPMG PEMs were 14.9 and 35.60 mW/cm^(2) at 25℃and 70℃,respectively,at ambient pressure with 100%relative humidity.Results showed that the newly prepared PEMs exhibit good electrochemical performance.The results indicated that the prepared composite membrane with 6 wt%filler can be used as an alternative membrane for applications of high-performance proton exchange membrane fuel cell.

Review on current development of polybenzimidazole membrane for lithium battery

With the rapid development of portable technology,lithium batteries have emerged as potential candidates for high-performance energy storage systems owing to their high energy density and cycling stability.Among the key components of a lithium battery system,the separator plays a critical role as it directly influences the battery performance benchmark(cycling performance and safety).However,traditional polyolefin separators(polypropylene/polyethylene)are unable to meet the demands of highperformance and safer battery systems due to their poor electrolyte compatibility,thermal runaways,and ultimate growth of dendrites.In contrast,membranes fabricated using polybenzimidazole(PBI)exhibit excellent electrolyte wettability and outstanding thermal dimensional stability,thus holding great potential as separators for high-performance and high-safety batteries.In this paper,we present a comprehensive review of the general requirements for separators,synthesis technology for separators,and research trends focusing PBI membranes in lithium batteries to alleviate the current commercial challenges faced by conventional polyolefin separators.In addition,we discuss the future development direction for PBI battery separators by considering various factors such as production cost,ecological footprint,preparation technology,and battery component compatibility.By exploring these perspectives,we aim to promote the continued application and exploration of PBI-based materials to advance lithium battery technology.

Towards high-performance and robust anion exchange membranes(AEMs)for water electrolysis:Super-acid-catalyzed synthesis of AEMs

The increasing demand for hydrogen energy to address environmental issues and achieve carbon neutrality has elevated interest in green hydrogen production,which does not rely on fossil fuels.Among various hydrogen production technologies,anion exchange membrane water electrolyzer(AEMWE)has emerged as a next-generation technology known for its high hydrogen production efficiency and its ability to use non-metal catalysts.However,this technology faces significant challenges,particularly in terms of the membrane durability and low ionic conductivity.To address these challenges,research efforts have focused on developing membranes with a new backbone structure and anion exchange groups to enhance durability and ionic conductivity.Notably,the super-acid-catalyzed condensation(SACC)synthesis method stands out due to its user convenience,the ability to create high molecular weight(MW)polymers,and the use of oxygen-tolerant organic catalysts.Although the synthesis of anion exchange membranes(AEMs)using the SACC method began in 2015,and despite growing interest in this synthesis approach,there remains a scarcity of review papers focusing on AEMs synthesized using the SACC method.The review covers the basics of SACC synthesis,presents various polymers synthesized using this method,and summarizes the development of these polymers,particularly their building blocks including aryl,ketone,and anion exchange groups.We systematically describe the effects of changes in the molecular structure of each polymer component,conducted by various research groups,on the mechanical properties,conductivity,and operational stability of the membrane.This review will provide insights into the development of AEMs with superior performance and operational stability suitable for water electrolysis applications.