Proton exchange membrane(PEM)is an integral component in fuel cells which enables proton transport for efficient energy conversion.Sulfonated Polyether Ether Ketone(SPEEK)has emerged as a cost-effective option with no...Proton exchange membrane(PEM)is an integral component in fuel cells which enables proton transport for efficient energy conversion.Sulfonated Polyether Ether Ketone(SPEEK)has emerged as a cost-effective option with non-fluorinated aromatic backbones for Proton Exchange Membrane Fuel Cell(PEMFC)applications,even though it exhibits lower proton conductivity compared to Nafion.This work aims to study the influence of Sulfonated Chitosan(SCS)concentrations on proton conductivity of SPEEK-based PEM at room temperature.SPEEK was synthesized using a sulfonation process with concentrated sulfuric acid at room temperature.SCS was synthesized via reflux of CS and 1.2 M H2SO4 with a ratio of 1:35(w/v)at 90℃ for 30 min.The composite membranes of SPEEK-SCS were formed with four different SCS concentrations,using the solution castingmethod,andDimethyl Sulfoxide(DMSO)was used as a solvent.The composite membranes synthesized include pure SPEEK(S0),SPEEK with 1%SCS(S1),SPEEK with 2%SCS(S2),and SPEEK with 3%SCS(S3).Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD),water uptake,degree of swelling,Ionic exchange capacity(IEC)with Electrochemical impedance spectroscopy(EIS)were used to characterize the composite membranes in terms of composition,crystallinity,water absorption,dimensional changes,number of exchangeable ions in membranes,and proton conductivity,respectively.Notably,S3 had the highest water uptake and the lowest degree of swelling.S2 had the highest proton conductivity among the SPEEK-SCS composite membranes at room temperature with 3.44×10^(−2) Scm^(-1).展开更多
A visible-light induced cascade sulfonation/cyclization reaction of 3-allyl-2-arylquinazolinones employing water as an environmentally friendly solvent was revealed.This transition metal-free protocol,using 9-mesityl-...A visible-light induced cascade sulfonation/cyclization reaction of 3-allyl-2-arylquinazolinones employing water as an environmentally friendly solvent was revealed.This transition metal-free protocol,using 9-mesityl-10-methylacridinium perchlorate as the photocatalyst,represents a masterly tactic for the synthesis of sulfonated dihydroisoquinolino[1,2-b]quinazolinones featuring mild conditions,facile operation,and broad substrate scope.展开更多
Biopolymeric nanocomposites have attracted considerable attention because of their biocompatibility,biodegradability,and unique physicochemical properties.It is essential to manufacture three-dimensional(3D)biocompati...Biopolymeric nanocomposites have attracted considerable attention because of their biocompatibility,biodegradability,and unique physicochemical properties.It is essential to manufacture three-dimensional(3D)biocompatible micro/nanostructures using biopolymeric nanocomposites.Herein,we demonstrate the high-fidelity fabrication of biocompatible 3D features with sub-50 nm resolution using femtosecond laser direct writing(FsLDW)of a biopolymeric nanocomposite composed of egg white and sulfonated graphene(S-graphene).The biopolymer nanocomposite acts as a negative photoresist suitable for water-based lithography.The introduction of S-graphene not only dramatically lowered the laser power threshold but also significantly modulated the morphology of the 3D features constructed by FsLDW.Microstructures with porous,rough,or smooth morphologies were obtained by optimizing the S-graphene concentration and laser scanning speed.The fabricated egg-white/S-graphene microstructures exhibited biocompatibility and environmental degradability.Egg white/S-graphene was also employed to fabricate diffractive gratings with superior optical quality.This study provides a promising method to manufacture biocompatible 3D features with controllable morphology,which has potential applications in biological and photonic fields.展开更多
To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polym...To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.展开更多
To address the cycling stability of zinc-ion batteries resulting from zinc dendrites,this work proposes the utilization of sulfonic groups to modulate the de-solvation and adsorption energy of zinc ions,achieving the ...To address the cycling stability of zinc-ion batteries resulting from zinc dendrites,this work proposes the utilization of sulfonic groups to modulate the de-solvation and adsorption energy of zinc ions,achieving the horizontal growth of zinc dendrites.Using polyacrylamide(PAM)and carboxymethyl cellulose(CMC)composite gels as modification targets,sodium dodecyl sulfate(SDS)provides the sulfonic group,the PAM/CMC/SDS gel electrolyte exhibits a coordination number as low as 0.19 and a desolvation energy reaching up to 2.73 eV.Based on this,the gel electrolyte exhibits a wide operating voltage range of 2.93 V,effectively suppressing both hydrogen and oxygen evolution reactions.More importantly,zinc ions in the PAM/CMC/SDS electrolytes preferentially grow along the zinc(002)plane,characterized by higher adsorption energy,leading to the formation of a uniform and dense zinc deposit,rather than vertical growth on the(100)crystal plane.The successfully induced directional deposition of zinc crystals and mitigation of hydrogen evolution enables the PAM/CMC/SDS gel electrolyte to achieve remarkable cycling stability in Zn||Zn symmetrical cells for up to 2800 h,In addition,the Zn||MnO_(2) asymmetric battery exhibits a specific capacity of 334 mAh g^(-1),accompanied by excellent rate performance,which ensures the reliability and durability of the quasi-solid-state zinc-ion battery based on the gel electrolyte in dynamic practical applications.展开更多
Andrographolide sulfonate(AS)is a sulfonated derivative of andrographolide extracted from Andrographis paniculata(Burm.f.)Nees,and has been approved for several decades in China.The present study aimed to investigate ...Andrographolide sulfonate(AS)is a sulfonated derivative of andrographolide extracted from Andrographis paniculata(Burm.f.)Nees,and has been approved for several decades in China.The present study aimed to investigate the novel therapeutic application and possible mechanisms of AS in the treatment of rheumatoid arthritis.Results indicated that administration of AS by injection or gavage significantly reduced the paw swelling,improved body weights,and attenuated pathological changes in joints of rats with adjuvant-induced arthritis.Additionally,the levels of tumor necrosis factor-alpha(TNF-α),interleukin-6(IL-6),and IL-1β in the serum and ankle joints were reduced.Bioinformatics analysis,along with the spleen index and measurements of IL-17 and IL-10 levels,suggested a potential relationship between AS and Th17 cells under arthritic conditions.In vitro,AS was shown to block Th17 cell differentiation,as evidenced by the reduced percentages of CD4^(+)IL-17A^(+)T cells and decreased expression levels of RORγt,IL-17A,IL-17F,IL-21,and IL-22,without affecting the cell viability and apoptosis.This effect was attributed to the limited glycolysis,as indicated by metabolomics analysis,reduced glucose uptake,and p H measurements.Further investigation revealed that AS might bind to hexokinase2(HK2)to down-regulate the protein levels of HK2 but not glyceraldehyde-3-phosphate dehydrogenase(GAPDH)or pyruvate kinase M2(PKM2),and overexpression of HK2 reversed the inhibition of AS on Th17 cell differentiation.Furthermore,AS impaired the activation of phosphatidylinositol 3-kinase(PI3K)/protein kinase B(AKT)signals in vivo and in vitro,which was abolished by the addition of lactate.In conclusion,AS significantly improved adjuvant-induced arthritis(AIA)in rats by inhibiting glycolysis-mediated activation of PI3K/AKT to restrain Th17 cell differentiation.展开更多
Per-and polyfluoroalkyl substances(PFAS)are persistent environmental contaminants that often show an adverse impact on human health.Rational design of porous adsorbents for selective and reversible removal of PFAS,suc...Per-and polyfluoroalkyl substances(PFAS)are persistent environmental contaminants that often show an adverse impact on human health.Rational design of porous adsorbents for selective and reversible removal of PFAS,such as perfluorooctane sulfonate(PFOS),is imperative and challenging.Herein,a Janus strategy based on an ionic covalent organic framework(iCOF-DGCl)composed of the alternately hydrophobic aromatic domains and hydrophilic guanidinium moieites has been proposed to meet the requirement of high-performance adsorbents.iCOF-DGCl shows fast adsorption kinetics(970.9 mg g^(−1)min^(−1))and ultrahigh uptake capacity(2491 mg g^(−1))toward PFOS,making it one of the most effective materials among the reported PFOS adsorbents.Moreover,the PFOS removal by iCOF-DGCl remains highly selective in the presence of disturbing anions,and the adsorbent could be well recovered for reuse.Mechanism studies have demonstrated that the Janus structure units of iCOF-DGCl form both hydrophobic and electrostatic interactions with the amphiphilic PFOS,thus achieving cooperative adsorption of PFOS.This work provides a facile approach based on Janus structure of COFs adsorbent for wastewater remediation.展开更多
The sulfonated poly(α-methyl styrene-b-isobutylene-b-α-methyl styrene)copolymers(S-ASIBS)with the average molar percentage of sulfonic acid(-SO_(3)H)groups(SP)ranging from 3.6 mol%to 14.3 mol%could be synthesized by...The sulfonated poly(α-methyl styrene-b-isobutylene-b-α-methyl styrene)copolymers(S-ASIBS)with the average molar percentage of sulfonic acid(-SO_(3)H)groups(SP)ranging from 3.6 mol%to 14.3 mol%could be synthesized by sulfonation of ASIBS with acetyl sulfate.The hydrophilic ionic channels were generated for proton exchange membranes(PEMs)by ion aggregation of-SO_(3)H groups and microphase separation between hydrophobic polyisobutylene and hydrophilic sulfonated poly(α-methyl styrene)segments in S-ASIBS.The proton transport ability was improved while oxidative stability was decreased by increasing SP in S-ASIBS.The appropriate SP of about 12.7 mol%in S-ASIBS provides the available PEMs with high proton transport ability,low methanol permeability and good oxidative stability.The absence of active tertiary hydrogen atoms along S-ASIBS copolymer chains avoids their attack by peroxy radicals.The residual rates of weight(RW)and proton conductivity(Rσ)of S-ASIBS-12.7 membrane after oxidation treatment for 916 h were 84.3%and 88.1%respectively,near to those of commercial Nafion 117(RW=87.9%,Rσ=90.3%).The membrane electrode assembly(MEA)could be prepared by using various S-ASIBS as PEMs for direct methanol fuel cell.The single cell with S-ASIBS-12.7 MEA behaves high performance of open circuit voltage(OCV)of 548 mV and peak power density(Pmax)of 36.1 mW·cm^(-2),which is similar to those of Nafion 117(OCV=506 mV,P_(max)=35.6 mW·cm^(-2)).To the best of our knowledge,this is the first example of advanced S-ASIBS membrane with high proton conductivity,excellent fuel barrier property and remarkable oxidative stability for promising PEMs.展开更多
Acidic-and alkalic-hydrolyses are selective in breaking functional bonds and falling off pharmacological moieties of antibiotics in production wastewater in comparison with advanced oxidation processes.Elevating tempe...Acidic-and alkalic-hydrolyses are selective in breaking functional bonds and falling off pharmacological moieties of antibiotics in production wastewater in comparison with advanced oxidation processes.Elevating temperature can accelerate hydrolytic kinetics and improve efficiency.In this work,magnetic sulfonated polypropylene resin(Fe_(3)O_(4)@PS-S)composites were reported for acidic-thermal hydrolysis of tylosin by employing the acidic feature of sulfonic group,the dielectric effect of resin,and the magnetic-loss effect of magnetite under microwave irradiation.As observed,a rapid and complete mitigation 100 mg/L of tylosin was achieved within 15 min by the catalysts.Acidic cleavage of tylosin was fulfilled by sulfonic groups in the composites,and microwave thermal accelerated the hydrolysis reactions due to the dielectric and magnetic-loss effects.Differentiating the dielectric and magnetic-loss effects through electromagnetic analyses indicated that the latter contributed more in converting microwave energy to heat.The interactions under multiple operational conditions were quantitatively fitted using the Behnajady model and visually demonstrated,which indicated that a synergic effect of microwave thermal-and acidichydrolyses contributed to the efficient mitigation of tylosin.The transformation products were identified and the pathways were supposed.Cleaving deoxyaminosugars groups and destructing lactone structures led to reduced antibacterial potential and toxicity reduction.The acute toxicity of tylosin and transformation products to fish,daphnia,and green algae were all classified as non-toxic.This work suggested that this synergistic acid-thermal hydrolytic method is attractive and promising in pretreating tylosin production wastewater in field.展开更多
Reclaimed water for irrigation or hydroponic cultivation provides exposure pathways for per-and polyfluoroalkyl substances(PFAS)to enter the human food chain.This study employed hydroponic methods to investigate the b...Reclaimed water for irrigation or hydroponic cultivation provides exposure pathways for per-and polyfluoroalkyl substances(PFAS)to enter the human food chain.This study employed hydroponic methods to investigate the behavior of legacy PFAS and emerging chlorinated polyfluoroalkyl ether sulfonic acids(Cl-PFESAs)in lettuce grown under environment-related exposure levels and assessed the human exposure risks from consuming contaminated lettuce.Overall,PFAS in lettuce were concentration-dependent,with long-chain PFAS tending to accumulate in roots and short-chain PFAS accumulating more in shoots.The enrichment of PFAS in lettuce was jointly influenced by their chain length and polar functional groups.Specifically,the root concentration factors(RCFs)of PFAS generally increased with increasing chain length,and RCF values of most perfluoroalkanesulfonic acids(PFSAs)were significantly higher than those of perfluoroalkyl carboxylic acids(PFCAs)with the same chain length(p<0.01),while the translocation factors(TFs)exhibited opposite trends.RCF values of perfluorooctane sulfonate(PFOS)and its alternatives,Cl-PFESAs,were ranked as follows:8:2 Cl-PFESA(mean:139)>6:2 Cl-PFESA(28.6)>PFOS(25.7),which was attributed to the increased molecular size and hydrophobicity resulting from the insertion of ether bonds and additional CF2 in 8:2 Cl-PFESA.Notably,TF value of 8:2 Cl-PFESA(mean:0.007)was the smallest among all PFAS,indicating 8:2 Cl-PFESA was difficult to transfer to nutritional compartments.Adults and children would exceed the most conservative health-based reference dose(RfD)by consuming approximately 15.9–148 g and 7.92–74.0 g of contaminated lettuce per day,implying high health risks.展开更多
Photocatalytic technology has been proven to be a simple and effective method for degrading recalcitrant organic pollutants.In this study,a series of Z-scheme heterojunction nanocomposites composed of CeO_(2)and terep...Photocatalytic technology has been proven to be a simple and effective method for degrading recalcitrant organic pollutants.In this study,a series of Z-scheme heterojunction nanocomposites composed of CeO_(2)and terephthalic acid-modified WO_(3) was prepared and further used as photocatalysts for perfluorobutane sulfonate(PFBS)degradation.In this design,terephthalic acid was used as an electron recombination center and heterojunction mediator,which effectively enhances the migration ability of electron-hole pairs and the physicochemical stability of the catalyst.In addition,in situ synthesis of CeO_(2)onto the WO_(3) surface by the coordinate bond between terephthalic acid and Ce ions can avoid CeO_(2)agglomeration.As a result,the CeO_(2)@WO_(3) photocatalyst exhibits excellent PFBS degradation ability(94%for CeO_(2)@WO_(3) vs.19%for CeO_(2)).After the fifth cyclic degradation experiment,the CeO_(2)@WO_(3) photocatalyst still maintains stable degradation efficiency.Furthermore,the reaction mechanism of the PFBS in CeO_(2)@WO_(3) photocatalytic process was analyzed by free radical trapping experiment and liquid chromatography tandem mass spectrometry(LC-MS)technique.This study provides new insights for constructing Z-scheme heterojunction and demonstrates that CeO_(2)@WO_(3) photocatalysts possess a promising prospect for degrading PFBS pollutants.展开更多
Desulfurization of coke oven gas(COG)is a critical step for achieving green and sustainable development in the coking industry.Ammonium binuclear cobalt phthalocyanine sulfonate(PDS),serving as the core catalyst in th...Desulfurization of coke oven gas(COG)is a critical step for achieving green and sustainable development in the coking industry.Ammonium binuclear cobalt phthalocyanine sulfonate(PDS),serving as the core catalyst in the Hydroquinone-PDSFerrous sulfate(HPF)desulfurization process,requires precise concentration monitoring for process optimization.To address the limitations of traditional detection methods,including insufficient sensitivity,cumbersome manual operations,and weak anti-interference capability,this study developed a fully automated analytical system and method based on spectrophotometry,thereby filling a technological gap in automated PDS detection.Systematic performance validation demonstrated that the autoanalyzer exhibits excellent sensitivity and a wide linear range,with results consistent with industrial standard methods.Leveraging a programmable logic controller(PLC),the system achieves end-to-end automation from sample pretreatment to data feedback,overcoming limitations inherent in manual operations such as delayed sample processing and human-induced errors,which significantly enhances the sensitivity and timeliness of PDS concentration monitoring in complex industrial matrices.The proposed method offers triple benefits of environmental friendliness,cost-effectiveness,and social value,providing key technical support for the coking industry.展开更多
Aqueous zinc-ion batteries(AZIBs)have emerged as a promising next-generation energy storage solution due to their high energy density,abundant resources,low cost,and high safety.However,unstable zinc anode caused by s...Aqueous zinc-ion batteries(AZIBs)have emerged as a promising next-generation energy storage solution due to their high energy density,abundant resources,low cost,and high safety.However,unstable zinc anode caused by side reactions and dendritic growth always severely worsens the long-term operation of AZIBs.Herein,a novel 3-cyclobutene sulfone(CS)additive was employed in the aqueous electrolyte to achieve a highly reversible Zn anode.The CS additive can offer strong electronegativity and high binding energy for the coordination with Zn^(2+),which enables its entry into the solvent sheath structure of Zn^(2+)and eliminates the free H_(2)O molecules from the solvated{Zn^(2+)-SO_(4)^(2-)-(H_(2)O)_(5)}.Thus,the occurrence of side reactions and dendritic growth can be effectively inhibited.Accordingly,the Zn anode achieves long cycle-life(1400 h at 1 m A cm^(-2),1 m Ah cm^(-2),and 400 h at 5 m A cm^(-2),5 m Ah cm^(-2))and high average coulombic efficiency(99.5% over 500 cycles at 10 m A cm^(-2),1 m Ah cm^(-2)).Besides,the assembled Zn||NH_(4)V_(4)O_(10)full cell suggests enhanced cycling reversibility(123.8 m Ah g^(-1)over 500 cycles at 2 A g^(-1),84.9 m Ah g^(-1)over 800 cycles at 5 A g^(-1))and improved rate capability(139.1 m Ah g^(-1)at 5 A g^(-1)).This work may exhibit the creative design and deep understanding of sulfone-based electrolyte additives for the achievement of high-performance AZIBs.展开更多
Compared with the most advanced lithium-ion batteries,aqueous zinc-iodine batteries(Zn–I_(2)batteries)have higher theoretical capacity and energy density,thus attracting much attention in energy storage.However,due t...Compared with the most advanced lithium-ion batteries,aqueous zinc-iodine batteries(Zn–I_(2)batteries)have higher theoretical capacity and energy density,thus attracting much attention in energy storage.However,due to several technical issues,the commercialization of Zn–I_(2)batteries is still at a bottleneck,and among them,the“shuttle effect”of polyiodide anions is considered to be a main challenge.In order to minimize the shuttle of polyiodide species within the cathode compartment,we herein synthesize a zinc-ion conductive covalent organic framework(COF),namely DMSBA-Tp-COF,that is used to assemble a composite separator together with commercial glass fiber(GF)substrate and graphene(Gr)by a simple vacuum filtration coating technology.The negatively charged–SO_(3)^(-)ions present in COF coatings enable homogeneous Zn^(2+)flux and simultaneously suppress polyiodides shuttling in the Zn–I_(2)batteries.As a result,the composite Gr@DMSBA-Tp-COF@GF separator endows the corresponding Zn–I_(2)symmetrical cell with excellent long-term cyclic stability with a lifespan over 800 h and high-specific capacity of 3.2 mAh cm^(-2)(at a current density of 20 mA cm^(-2),voltage range of 0.7–1.7 V).This study provides a prospective strategy to rationally design functional COFs separators and accelerate their applications in high energy storage systems.展开更多
High-temperature and high-salt reservoirs are often accompanied by serious gas channeling in gas flooding,which will greatly affect the effect of gas injection development,so in-situ foaming of temperature-resistant a...High-temperature and high-salt reservoirs are often accompanied by serious gas channeling in gas flooding,which will greatly affect the effect of gas injection development,so in-situ foaming of temperature-resistant and salt-resistant foaming agents is commonly used to control gas channeling.The feasibility of the compound system of dodecyl hydroxyl sulfobetaine(HSB12)andα-olefin sulfonate(AOS)as foaming agent for sandstone reservoir was studied at 130℃and 22×10^(4)mg/L.The results showed that the foaming agent(HSB12 and AOS were compounded in a 6:1 mass ratio,in this article,this foaming agent is simply referred to as SA61)had good solubility in 22×10^(4)mg/L simulated formation water.Besides,the foaming volume of SA61 and HSB12 was similar,but the foam decay half-life of SA61was 10-25 times higher than that of HSB12.The foaming performance of SA61 on the surface of quartz sand remained above 90%of that before adsorption.The strong interaction between HSB12 and AOS in the compound system SA61 was demonstrated by surface rheological measurements and NMR studies of surfactants.The results of co re flow test showed that SA61 had better mobility control ability than HSB12under the same surfactant concentration.In addition,SA61 showed a selective mobility reduction in2005.30 and 632.00 mD cores.The above research results can guide the selection and application of foaming agent in clastic reservoir.展开更多
Temperature-sensitive random copolymerized nanohydrogels were prepared via a one-pot polymerization method using N-isopropylacrylamide(NIPAM)and 2-acrylamido-2-methylpropanesulfonic acid(AMPS)as raw materials.Transmis...Temperature-sensitive random copolymerized nanohydrogels were prepared via a one-pot polymerization method using N-isopropylacrylamide(NIPAM)and 2-acrylamido-2-methylpropanesulfonic acid(AMPS)as raw materials.Transmission electron microscopy(TEM)and differential scanning calorimetry(DSC)analyses revealed the partially crystallized porous nanostructure of the gels,which is consistent with the characteristics of porous nanohydrogel materials.The low-molecular-weight polymers exhibited enhancement and sharpening of the end group peaks in Fourier-transform infrared(FTIR),X-ray photoelectron spectroscopy(XPS),and nuclear magnetic resonance hydrogen(^(1)H-NMR)spectra due to the high proportion of small molecules or low-molecular-weight chain segments.In turn,the high-molecular-weight polymers showed pronounced peaks in the main chain segments because of the long-chain effect.Hygroscopicity increased with the molecular weight of the selected polymers,but was inhibited by temperatures below the lower critical solution temperature(LCST).Meanwhile,moisture desorption was faster in low-molecular-weight samples,and the overall moisture desorption rate rose above the LCST value.According to the kinetic analysis,the moisture absorption process conformed to the quasi-primary or quasi-secondary kinetic model,whereas the moisture desorption followed the quasi-secondary model.Moisture cycling experiments showed that the material maintained stable moisture absorption and desorption performance after several cycles,which is essential for long-term cycling.展开更多
Polyethylene oxide(PEO)-based solid polymer electrolytes are considered as promising material for solidstate sodium metallic batteries(SSMBs).However,their poor interfacial stability with high-voltage cathode limits t...Polyethylene oxide(PEO)-based solid polymer electrolytes are considered as promising material for solidstate sodium metallic batteries(SSMBs).However,their poor interfacial stability with high-voltage cathode limits their application in high-energy–density solid-state batteries.Herein,a uniform,sulfur-containing inorganic–organic composite cathode–electrolyte interphase layer was in situ formed by the addition of sodium polyvinyl sulfonate(NaPVS).The 5 wt%NaPVS-Na_(3)V_(2)(PO_(4))_(3)(NVP)|PEOsodium hexauorophosphate(NaPF6)|Na battery shows a higher initial capacity of 111.2 mAh.g^(-1)and an ultra-high capacity retention of 90.5%after 300 cycles.The 5 wt%NaPVS-Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)|PEO-NaPF_(6)|Na battery with the high cutoff voltage of 4.2 V showed a specific discharge capacity of 88.9 mAh.g^(-1)at 0.5C for 100 cycles with a capacity retention of 79%,which is much better than that of the pristine-NVPF(PR-NVPF)|PEO-NaPF_(6)|Na battery(33.2%).The addition of NaPVS not only enhances the diffusion kinetics at the interface but also improves the rate performance and stability of the battery,thus bolstering its viability for high-energy applications.In situ phase tracking further elucidates that NaPVS effectively mitigates self-discharge induced by the oxidative decomposition of PEO at high temperature.This work proposes a general strategy to maintain the structural stability of the cathode–electrolyte interface in PEO-based high-performance SSMBs.展开更多
The growing focus on environmental sustainability has spurred significant interest in plant extracts as eco-friendly alternatives to conventional corrosion inhibitors.This study presents a novel approach to enhance th...The growing focus on environmental sustainability has spurred significant interest in plant extracts as eco-friendly alternatives to conventional corrosion inhibitors.This study presents a novel approach to enhance the corrosion resistance of cold-rolled steel(CRS)by utilizing a combination of sodium dodecylbenzene sulfonate(SDBS)and Camellia oleifera fruit shell extract(CFSE).The inhibition performance of the CFSE/SDBS complex on CRS in 0.50 M sulfamic acid(SA)solution was evaluated through weight loss methods and electrochemical methods.The results demonstrate an impressive inhibition efficiency of 93.2%with 200 mg L^(-1) CFSE and 50 mg L^(-1) SDBS at 20℃,supported by a synergism parameter(S_(θ))exceeding 1.CFSE,SDBS,and the CFSE/SDBS complex act as mixed-type inhibitors,primarily influencing the cathodic reaction.Surface analyses conducted using X-ray photoelectron spectroscopy(XPS)and time of flight secondary ion mass spectrometry(ToF-SIMS)confirm that the active components in CFSE and SDBS can adsorb onto CRS surfaces,creating a robust protective film.Quantum chemical(QC)calculations identify reactive sites in morin(MR),DL-methionine(DL-Met),and lysine(Lys),highlighting heteroatoms and conjugated double bonds as key contributors.Molecular dynamic(MD)simulations reveal that these compounds form an impermeable film on Fe(001)surfaces,effectively reducing the migration rate of corrosive ions(NH_(2)SO_(3)^(-),H_(3)O^(+)).This research challenges conventional compounding methods and offers innovative insights into the development of eco-friendly corrosion inhibitors derived from plant extracts.展开更多
The large-scale commercialization of proton exchange membrane fuel cells(PEMFCs)has been hindered by the high demand of platinum(Pt)in the cathode due to the sluggish kinetics of the oxygen reduction reaction.Reducing...The large-scale commercialization of proton exchange membrane fuel cells(PEMFCs)has been hindered by the high demand of platinum(Pt)in the cathode due to the sluggish kinetics of the oxygen reduction reaction.Reducing the amount of Pt would worsen the problems caused by the adsorption of perfluorinated sulfonic acid(PFSA)ionomers to Pt via the side chains,namely,blocking the active sites of Pt and inducing densely packed layers of fluorocarbon backbones on Pt surface to obstruct local O_(2)transport at the Pt/PFSA interfaces.This work aims at optimizing the Pt/ionomer interface to mitigate the sulfonate adsorption and in the meantime to reduce the local O_(2)transport resistance(R_(local)),by using a porous composite of 1-butyl-3-methylimidazolium hydrogen sulfate ionic liquid(IL)modified MOF-808(BMImHSO_(4)@MOF-808)as additive in cathodic catalyst layer(CCL).Through detailed physical,spectroscopic and electrochemical characterizations,we demonstrate a three-fold optimization mechanism of Pt/ionomer interface structure by BMImHSO_(4)@MOF-808:the unsaturated metal sites in MOF-808 effectively inhibit the sulfonate adsorption on Pt through coordination with the sulfonates of PFSA,thereby improving catalyst utilization;the pores in MOF-808 establish efficient transport channels for gaseous oxygen,significantly reducing R_(local);the IL modification layers facilitate the formation of continuous proton transport networks,increasing proton conductivity.The incorporation of BMImHSO_(4)@MOF-808 in a low-Pt CCL(0.1 mg_(Pt)cm^(-2))yields a peak power density of 1.9 W cm^(-2)for PEMFC under H_(2)-O_(2)condition,and ca.20%increase of power density under H_(2)-air condition as compared with conventional CCL,indicating the prospect of IL-MOF composites as an efficient additive to enhance the performance of PEMFCs.展开更多
文摘Proton exchange membrane(PEM)is an integral component in fuel cells which enables proton transport for efficient energy conversion.Sulfonated Polyether Ether Ketone(SPEEK)has emerged as a cost-effective option with non-fluorinated aromatic backbones for Proton Exchange Membrane Fuel Cell(PEMFC)applications,even though it exhibits lower proton conductivity compared to Nafion.This work aims to study the influence of Sulfonated Chitosan(SCS)concentrations on proton conductivity of SPEEK-based PEM at room temperature.SPEEK was synthesized using a sulfonation process with concentrated sulfuric acid at room temperature.SCS was synthesized via reflux of CS and 1.2 M H2SO4 with a ratio of 1:35(w/v)at 90℃ for 30 min.The composite membranes of SPEEK-SCS were formed with four different SCS concentrations,using the solution castingmethod,andDimethyl Sulfoxide(DMSO)was used as a solvent.The composite membranes synthesized include pure SPEEK(S0),SPEEK with 1%SCS(S1),SPEEK with 2%SCS(S2),and SPEEK with 3%SCS(S3).Fourier transform infrared spectroscopy(FTIR),X-ray diffraction(XRD),water uptake,degree of swelling,Ionic exchange capacity(IEC)with Electrochemical impedance spectroscopy(EIS)were used to characterize the composite membranes in terms of composition,crystallinity,water absorption,dimensional changes,number of exchangeable ions in membranes,and proton conductivity,respectively.Notably,S3 had the highest water uptake and the lowest degree of swelling.S2 had the highest proton conductivity among the SPEEK-SCS composite membranes at room temperature with 3.44×10^(−2) Scm^(-1).
基金funds from Natural Science Foundation of Guangxi Province(Nos.2023GXNSFBA026304,2023GXNSFDA026063)the Guangxi Science and Technology Base and Special Talents(No.Guike AD20159047).
文摘A visible-light induced cascade sulfonation/cyclization reaction of 3-allyl-2-arylquinazolinones employing water as an environmentally friendly solvent was revealed.This transition metal-free protocol,using 9-mesityl-10-methylacridinium perchlorate as the photocatalyst,represents a masterly tactic for the synthesis of sulfonated dihydroisoquinolino[1,2-b]quinazolinones featuring mild conditions,facile operation,and broad substrate scope.
基金financially supported by the National Key Research and Development Program of China(Nos.2024YFB4607402 and 2016YFC1100502)the National Natural Science Foundation of China(Nos.51673208 and 61975213)。
文摘Biopolymeric nanocomposites have attracted considerable attention because of their biocompatibility,biodegradability,and unique physicochemical properties.It is essential to manufacture three-dimensional(3D)biocompatible micro/nanostructures using biopolymeric nanocomposites.Herein,we demonstrate the high-fidelity fabrication of biocompatible 3D features with sub-50 nm resolution using femtosecond laser direct writing(FsLDW)of a biopolymeric nanocomposite composed of egg white and sulfonated graphene(S-graphene).The biopolymer nanocomposite acts as a negative photoresist suitable for water-based lithography.The introduction of S-graphene not only dramatically lowered the laser power threshold but also significantly modulated the morphology of the 3D features constructed by FsLDW.Microstructures with porous,rough,or smooth morphologies were obtained by optimizing the S-graphene concentration and laser scanning speed.The fabricated egg-white/S-graphene microstructures exhibited biocompatibility and environmental degradability.Egg white/S-graphene was also employed to fabricate diffractive gratings with superior optical quality.This study provides a promising method to manufacture biocompatible 3D features with controllable morphology,which has potential applications in biological and photonic fields.
基金the support from the Jiangsu Provincial Senior Talent Program (Dengfeng,Jiangsu University)the support from the National Key R&D Program of China (No.2024YFB3612600)+3 种基金the National Natural Science Foundation of China (Nos.22275098,62288102)Basic Research Program of Jiangsu (No.BK20243057)the Natural Science Research Start-up Foundation of Recruiting Talents of Nanjing University of Posts and Telecommunications (No.NY222097)the National Natural Science Foundation of China (No.62205035)。
文摘To precisely control intrachain π-electron delocalization and interchain interaction simultaneously is the prerequisite to obtain stable and efficient deep-blue light-emitting p-n polymer semiconductors for the polymer light-emitting diodes(PLEDs).Herein,we introduced the steric carbazole-fluorene nanogrid into light-emitting diphenyl sulfone-based p-n polymer semiconductors(PG and PDG) via metal-free C-N coupling polymerization for the fabrication of deep-blue PLEDs.The steric,rigid and twisted configuration between nanogrid and diphenyl sulfone in PG and PDG present the unique characteristic of large steric hindrance interaction to suppress interchain aggregation in solid state.Due to the different length of electron-deficient diphenyl sulfone monomers,PG showed a deep-blue emission with a maximum peak at 428 nm but red-shifted to 480 nm for the PDG films.Interestingly,similar deep-blue emission behavior of PG in diluted non-polar solution and films suggested the extremely weak interchain aggregation.Finally,PLEDs based on PG are fabricated with a stable deep-blue emission of CIE(0.15,0.10),and corresponding EL spectral profile is also completely identical to PL ones of diluted solution,revealed the intrachain emission without obvious interchain excited state,confirmed effectiveness of the steric hindrance functionalization of nanogrid in p-n polymer semiconductor for deep-blue light-emitting organic optoelectronics.
基金the financial support from the National Natural Science Foundation of China(Nos.52125202 and 22078028)the Jiangsu Provincial Science and Technology Plan Project Youth Fund(Nos.BK20230639 and BK20230640)+1 种基金the Changzhou University College Student Innovation and Entrepreneurship Training Program(No.202410292098Y)the Changzhou University College Student Science and Technology Innovation Fund of the School of Petrochemical Engineering.
文摘To address the cycling stability of zinc-ion batteries resulting from zinc dendrites,this work proposes the utilization of sulfonic groups to modulate the de-solvation and adsorption energy of zinc ions,achieving the horizontal growth of zinc dendrites.Using polyacrylamide(PAM)and carboxymethyl cellulose(CMC)composite gels as modification targets,sodium dodecyl sulfate(SDS)provides the sulfonic group,the PAM/CMC/SDS gel electrolyte exhibits a coordination number as low as 0.19 and a desolvation energy reaching up to 2.73 eV.Based on this,the gel electrolyte exhibits a wide operating voltage range of 2.93 V,effectively suppressing both hydrogen and oxygen evolution reactions.More importantly,zinc ions in the PAM/CMC/SDS electrolytes preferentially grow along the zinc(002)plane,characterized by higher adsorption energy,leading to the formation of a uniform and dense zinc deposit,rather than vertical growth on the(100)crystal plane.The successfully induced directional deposition of zinc crystals and mitigation of hydrogen evolution enables the PAM/CMC/SDS gel electrolyte to achieve remarkable cycling stability in Zn||Zn symmetrical cells for up to 2800 h,In addition,the Zn||MnO_(2) asymmetric battery exhibits a specific capacity of 334 mAh g^(-1),accompanied by excellent rate performance,which ensures the reliability and durability of the quasi-solid-state zinc-ion battery based on the gel electrolyte in dynamic practical applications.
基金supported by the project of Central Funds Guiding the Local Science and Technology Development(No.20212ZDD02010)。
文摘Andrographolide sulfonate(AS)is a sulfonated derivative of andrographolide extracted from Andrographis paniculata(Burm.f.)Nees,and has been approved for several decades in China.The present study aimed to investigate the novel therapeutic application and possible mechanisms of AS in the treatment of rheumatoid arthritis.Results indicated that administration of AS by injection or gavage significantly reduced the paw swelling,improved body weights,and attenuated pathological changes in joints of rats with adjuvant-induced arthritis.Additionally,the levels of tumor necrosis factor-alpha(TNF-α),interleukin-6(IL-6),and IL-1β in the serum and ankle joints were reduced.Bioinformatics analysis,along with the spleen index and measurements of IL-17 and IL-10 levels,suggested a potential relationship between AS and Th17 cells under arthritic conditions.In vitro,AS was shown to block Th17 cell differentiation,as evidenced by the reduced percentages of CD4^(+)IL-17A^(+)T cells and decreased expression levels of RORγt,IL-17A,IL-17F,IL-21,and IL-22,without affecting the cell viability and apoptosis.This effect was attributed to the limited glycolysis,as indicated by metabolomics analysis,reduced glucose uptake,and p H measurements.Further investigation revealed that AS might bind to hexokinase2(HK2)to down-regulate the protein levels of HK2 but not glyceraldehyde-3-phosphate dehydrogenase(GAPDH)or pyruvate kinase M2(PKM2),and overexpression of HK2 reversed the inhibition of AS on Th17 cell differentiation.Furthermore,AS impaired the activation of phosphatidylinositol 3-kinase(PI3K)/protein kinase B(AKT)signals in vivo and in vitro,which was abolished by the addition of lactate.In conclusion,AS significantly improved adjuvant-induced arthritis(AIA)in rats by inhibiting glycolysis-mediated activation of PI3K/AKT to restrain Th17 cell differentiation.
基金the financial support from National Key Research and Development Program(2019YFA0210403)National Natural Science Foundation of China(22001178,21975259)+1 种基金Natural Science Foundation of Hebei Province(B2021202077,B2022202039,C20220313)S&T Program of Hebei(236Z4308G).The authors extend their gratitude to Shiyanjia Lab(www.shiyanjia.com)for XPS measurement.
文摘Per-and polyfluoroalkyl substances(PFAS)are persistent environmental contaminants that often show an adverse impact on human health.Rational design of porous adsorbents for selective and reversible removal of PFAS,such as perfluorooctane sulfonate(PFOS),is imperative and challenging.Herein,a Janus strategy based on an ionic covalent organic framework(iCOF-DGCl)composed of the alternately hydrophobic aromatic domains and hydrophilic guanidinium moieites has been proposed to meet the requirement of high-performance adsorbents.iCOF-DGCl shows fast adsorption kinetics(970.9 mg g^(−1)min^(−1))and ultrahigh uptake capacity(2491 mg g^(−1))toward PFOS,making it one of the most effective materials among the reported PFOS adsorbents.Moreover,the PFOS removal by iCOF-DGCl remains highly selective in the presence of disturbing anions,and the adsorbent could be well recovered for reuse.Mechanism studies have demonstrated that the Janus structure units of iCOF-DGCl form both hydrophobic and electrostatic interactions with the amphiphilic PFOS,thus achieving cooperative adsorption of PFOS.This work provides a facile approach based on Janus structure of COFs adsorbent for wastewater remediation.
基金financially supported by the National Natural Science Foundation of China (No. 21774006)
文摘The sulfonated poly(α-methyl styrene-b-isobutylene-b-α-methyl styrene)copolymers(S-ASIBS)with the average molar percentage of sulfonic acid(-SO_(3)H)groups(SP)ranging from 3.6 mol%to 14.3 mol%could be synthesized by sulfonation of ASIBS with acetyl sulfate.The hydrophilic ionic channels were generated for proton exchange membranes(PEMs)by ion aggregation of-SO_(3)H groups and microphase separation between hydrophobic polyisobutylene and hydrophilic sulfonated poly(α-methyl styrene)segments in S-ASIBS.The proton transport ability was improved while oxidative stability was decreased by increasing SP in S-ASIBS.The appropriate SP of about 12.7 mol%in S-ASIBS provides the available PEMs with high proton transport ability,low methanol permeability and good oxidative stability.The absence of active tertiary hydrogen atoms along S-ASIBS copolymer chains avoids their attack by peroxy radicals.The residual rates of weight(RW)and proton conductivity(Rσ)of S-ASIBS-12.7 membrane after oxidation treatment for 916 h were 84.3%and 88.1%respectively,near to those of commercial Nafion 117(RW=87.9%,Rσ=90.3%).The membrane electrode assembly(MEA)could be prepared by using various S-ASIBS as PEMs for direct methanol fuel cell.The single cell with S-ASIBS-12.7 MEA behaves high performance of open circuit voltage(OCV)of 548 mV and peak power density(Pmax)of 36.1 mW·cm^(-2),which is similar to those of Nafion 117(OCV=506 mV,P_(max)=35.6 mW·cm^(-2)).To the best of our knowledge,this is the first example of advanced S-ASIBS membrane with high proton conductivity,excellent fuel barrier property and remarkable oxidative stability for promising PEMs.
基金supported by the National Natural Science Foundation of China(Nos.51978052 and 22306012)the National Key Research and Development Program of China(No.2023YFC3711300)the Guangdong Basic and Applied Basic Research Foundation(No.2022A1515110578).
文摘Acidic-and alkalic-hydrolyses are selective in breaking functional bonds and falling off pharmacological moieties of antibiotics in production wastewater in comparison with advanced oxidation processes.Elevating temperature can accelerate hydrolytic kinetics and improve efficiency.In this work,magnetic sulfonated polypropylene resin(Fe_(3)O_(4)@PS-S)composites were reported for acidic-thermal hydrolysis of tylosin by employing the acidic feature of sulfonic group,the dielectric effect of resin,and the magnetic-loss effect of magnetite under microwave irradiation.As observed,a rapid and complete mitigation 100 mg/L of tylosin was achieved within 15 min by the catalysts.Acidic cleavage of tylosin was fulfilled by sulfonic groups in the composites,and microwave thermal accelerated the hydrolysis reactions due to the dielectric and magnetic-loss effects.Differentiating the dielectric and magnetic-loss effects through electromagnetic analyses indicated that the latter contributed more in converting microwave energy to heat.The interactions under multiple operational conditions were quantitatively fitted using the Behnajady model and visually demonstrated,which indicated that a synergic effect of microwave thermal-and acidichydrolyses contributed to the efficient mitigation of tylosin.The transformation products were identified and the pathways were supposed.Cleaving deoxyaminosugars groups and destructing lactone structures led to reduced antibacterial potential and toxicity reduction.The acute toxicity of tylosin and transformation products to fish,daphnia,and green algae were all classified as non-toxic.This work suggested that this synergistic acid-thermal hydrolytic method is attractive and promising in pretreating tylosin production wastewater in field.
基金supported by the Fundamental Research Funds for Central Non-profit Scientific Institution(No.1610132022015)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB0750200)the National Natural Science Foundation of China(No.22176198).
文摘Reclaimed water for irrigation or hydroponic cultivation provides exposure pathways for per-and polyfluoroalkyl substances(PFAS)to enter the human food chain.This study employed hydroponic methods to investigate the behavior of legacy PFAS and emerging chlorinated polyfluoroalkyl ether sulfonic acids(Cl-PFESAs)in lettuce grown under environment-related exposure levels and assessed the human exposure risks from consuming contaminated lettuce.Overall,PFAS in lettuce were concentration-dependent,with long-chain PFAS tending to accumulate in roots and short-chain PFAS accumulating more in shoots.The enrichment of PFAS in lettuce was jointly influenced by their chain length and polar functional groups.Specifically,the root concentration factors(RCFs)of PFAS generally increased with increasing chain length,and RCF values of most perfluoroalkanesulfonic acids(PFSAs)were significantly higher than those of perfluoroalkyl carboxylic acids(PFCAs)with the same chain length(p<0.01),while the translocation factors(TFs)exhibited opposite trends.RCF values of perfluorooctane sulfonate(PFOS)and its alternatives,Cl-PFESAs,were ranked as follows:8:2 Cl-PFESA(mean:139)>6:2 Cl-PFESA(28.6)>PFOS(25.7),which was attributed to the increased molecular size and hydrophobicity resulting from the insertion of ether bonds and additional CF2 in 8:2 Cl-PFESA.Notably,TF value of 8:2 Cl-PFESA(mean:0.007)was the smallest among all PFAS,indicating 8:2 Cl-PFESA was difficult to transfer to nutritional compartments.Adults and children would exceed the most conservative health-based reference dose(RfD)by consuming approximately 15.9–148 g and 7.92–74.0 g of contaminated lettuce per day,implying high health risks.
基金Project supported by the National Natural Science Foundation of China(52300206)the Natural Science Foundation of Jiangsu Province(BK20230705)+2 种基金Industry-University Research Cooperation Project of Jiangsu Province,China(BY20221227)Natural Science Foundation of the Jiangsu Higher Education Institutions of China(22KJB610014)the Talent-Recruiting Program of Nanjing Institute of Technology(YKJ202124)。
文摘Photocatalytic technology has been proven to be a simple and effective method for degrading recalcitrant organic pollutants.In this study,a series of Z-scheme heterojunction nanocomposites composed of CeO_(2)and terephthalic acid-modified WO_(3) was prepared and further used as photocatalysts for perfluorobutane sulfonate(PFBS)degradation.In this design,terephthalic acid was used as an electron recombination center and heterojunction mediator,which effectively enhances the migration ability of electron-hole pairs and the physicochemical stability of the catalyst.In addition,in situ synthesis of CeO_(2)onto the WO_(3) surface by the coordinate bond between terephthalic acid and Ce ions can avoid CeO_(2)agglomeration.As a result,the CeO_(2)@WO_(3) photocatalyst exhibits excellent PFBS degradation ability(94%for CeO_(2)@WO_(3) vs.19%for CeO_(2)).After the fifth cyclic degradation experiment,the CeO_(2)@WO_(3) photocatalyst still maintains stable degradation efficiency.Furthermore,the reaction mechanism of the PFBS in CeO_(2)@WO_(3) photocatalytic process was analyzed by free radical trapping experiment and liquid chromatography tandem mass spectrometry(LC-MS)technique.This study provides new insights for constructing Z-scheme heterojunction and demonstrates that CeO_(2)@WO_(3) photocatalysts possess a promising prospect for degrading PFBS pollutants.
基金supported by the cross-sectional research project sponsored by Jilin Baoli Science and Technology Co.(2024-2200-0800-0378)
文摘Desulfurization of coke oven gas(COG)is a critical step for achieving green and sustainable development in the coking industry.Ammonium binuclear cobalt phthalocyanine sulfonate(PDS),serving as the core catalyst in the Hydroquinone-PDSFerrous sulfate(HPF)desulfurization process,requires precise concentration monitoring for process optimization.To address the limitations of traditional detection methods,including insufficient sensitivity,cumbersome manual operations,and weak anti-interference capability,this study developed a fully automated analytical system and method based on spectrophotometry,thereby filling a technological gap in automated PDS detection.Systematic performance validation demonstrated that the autoanalyzer exhibits excellent sensitivity and a wide linear range,with results consistent with industrial standard methods.Leveraging a programmable logic controller(PLC),the system achieves end-to-end automation from sample pretreatment to data feedback,overcoming limitations inherent in manual operations such as delayed sample processing and human-induced errors,which significantly enhances the sensitivity and timeliness of PDS concentration monitoring in complex industrial matrices.The proposed method offers triple benefits of environmental friendliness,cost-effectiveness,and social value,providing key technical support for the coking industry.
基金the financial support from the Foshan Talents Special Foundation(BKBS202003)。
文摘Aqueous zinc-ion batteries(AZIBs)have emerged as a promising next-generation energy storage solution due to their high energy density,abundant resources,low cost,and high safety.However,unstable zinc anode caused by side reactions and dendritic growth always severely worsens the long-term operation of AZIBs.Herein,a novel 3-cyclobutene sulfone(CS)additive was employed in the aqueous electrolyte to achieve a highly reversible Zn anode.The CS additive can offer strong electronegativity and high binding energy for the coordination with Zn^(2+),which enables its entry into the solvent sheath structure of Zn^(2+)and eliminates the free H_(2)O molecules from the solvated{Zn^(2+)-SO_(4)^(2-)-(H_(2)O)_(5)}.Thus,the occurrence of side reactions and dendritic growth can be effectively inhibited.Accordingly,the Zn anode achieves long cycle-life(1400 h at 1 m A cm^(-2),1 m Ah cm^(-2),and 400 h at 5 m A cm^(-2),5 m Ah cm^(-2))and high average coulombic efficiency(99.5% over 500 cycles at 10 m A cm^(-2),1 m Ah cm^(-2)).Besides,the assembled Zn||NH_(4)V_(4)O_(10)full cell suggests enhanced cycling reversibility(123.8 m Ah g^(-1)over 500 cycles at 2 A g^(-1),84.9 m Ah g^(-1)over 800 cycles at 5 A g^(-1))and improved rate capability(139.1 m Ah g^(-1)at 5 A g^(-1)).This work may exhibit the creative design and deep understanding of sulfone-based electrolyte additives for the achievement of high-performance AZIBs.
基金financially supported by the National Natural Science Foundation of China(22465012,22105053)the Key Research and Development Project of Hainan Province,China(ZDYF2024GXJS005)the Major Science and Technology Project of Hainan Province,China(ZDKJ202016).
文摘Compared with the most advanced lithium-ion batteries,aqueous zinc-iodine batteries(Zn–I_(2)batteries)have higher theoretical capacity and energy density,thus attracting much attention in energy storage.However,due to several technical issues,the commercialization of Zn–I_(2)batteries is still at a bottleneck,and among them,the“shuttle effect”of polyiodide anions is considered to be a main challenge.In order to minimize the shuttle of polyiodide species within the cathode compartment,we herein synthesize a zinc-ion conductive covalent organic framework(COF),namely DMSBA-Tp-COF,that is used to assemble a composite separator together with commercial glass fiber(GF)substrate and graphene(Gr)by a simple vacuum filtration coating technology.The negatively charged–SO_(3)^(-)ions present in COF coatings enable homogeneous Zn^(2+)flux and simultaneously suppress polyiodides shuttling in the Zn–I_(2)batteries.As a result,the composite Gr@DMSBA-Tp-COF@GF separator endows the corresponding Zn–I_(2)symmetrical cell with excellent long-term cyclic stability with a lifespan over 800 h and high-specific capacity of 3.2 mAh cm^(-2)(at a current density of 20 mA cm^(-2),voltage range of 0.7–1.7 V).This study provides a prospective strategy to rationally design functional COFs separators and accelerate their applications in high energy storage systems.
基金financial support from the Major Scientific and Technological Projects of CNPC(Award No.ZD2019-183-007)。
文摘High-temperature and high-salt reservoirs are often accompanied by serious gas channeling in gas flooding,which will greatly affect the effect of gas injection development,so in-situ foaming of temperature-resistant and salt-resistant foaming agents is commonly used to control gas channeling.The feasibility of the compound system of dodecyl hydroxyl sulfobetaine(HSB12)andα-olefin sulfonate(AOS)as foaming agent for sandstone reservoir was studied at 130℃and 22×10^(4)mg/L.The results showed that the foaming agent(HSB12 and AOS were compounded in a 6:1 mass ratio,in this article,this foaming agent is simply referred to as SA61)had good solubility in 22×10^(4)mg/L simulated formation water.Besides,the foaming volume of SA61 and HSB12 was similar,but the foam decay half-life of SA61was 10-25 times higher than that of HSB12.The foaming performance of SA61 on the surface of quartz sand remained above 90%of that before adsorption.The strong interaction between HSB12 and AOS in the compound system SA61 was demonstrated by surface rheological measurements and NMR studies of surfactants.The results of co re flow test showed that SA61 had better mobility control ability than HSB12under the same surfactant concentration.In addition,SA61 showed a selective mobility reduction in2005.30 and 632.00 mD cores.The above research results can guide the selection and application of foaming agent in clastic reservoir.
文摘Temperature-sensitive random copolymerized nanohydrogels were prepared via a one-pot polymerization method using N-isopropylacrylamide(NIPAM)and 2-acrylamido-2-methylpropanesulfonic acid(AMPS)as raw materials.Transmission electron microscopy(TEM)and differential scanning calorimetry(DSC)analyses revealed the partially crystallized porous nanostructure of the gels,which is consistent with the characteristics of porous nanohydrogel materials.The low-molecular-weight polymers exhibited enhancement and sharpening of the end group peaks in Fourier-transform infrared(FTIR),X-ray photoelectron spectroscopy(XPS),and nuclear magnetic resonance hydrogen(^(1)H-NMR)spectra due to the high proportion of small molecules or low-molecular-weight chain segments.In turn,the high-molecular-weight polymers showed pronounced peaks in the main chain segments because of the long-chain effect.Hygroscopicity increased with the molecular weight of the selected polymers,but was inhibited by temperatures below the lower critical solution temperature(LCST).Meanwhile,moisture desorption was faster in low-molecular-weight samples,and the overall moisture desorption rate rose above the LCST value.According to the kinetic analysis,the moisture absorption process conformed to the quasi-primary or quasi-secondary kinetic model,whereas the moisture desorption followed the quasi-secondary model.Moisture cycling experiments showed that the material maintained stable moisture absorption and desorption performance after several cycles,which is essential for long-term cycling.
基金supported by the Natural Science Foundation of China(No.22109079)the Natural Science Foundation of China(No.21973008)+2 种基金the Natural Science Foundation of China(No.22179010)the National Key R&D Program of China(No.2021YFB2400200)Taishan Scholars of Shandong Province(No.tsqnz20231212)。
文摘Polyethylene oxide(PEO)-based solid polymer electrolytes are considered as promising material for solidstate sodium metallic batteries(SSMBs).However,their poor interfacial stability with high-voltage cathode limits their application in high-energy–density solid-state batteries.Herein,a uniform,sulfur-containing inorganic–organic composite cathode–electrolyte interphase layer was in situ formed by the addition of sodium polyvinyl sulfonate(NaPVS).The 5 wt%NaPVS-Na_(3)V_(2)(PO_(4))_(3)(NVP)|PEOsodium hexauorophosphate(NaPF6)|Na battery shows a higher initial capacity of 111.2 mAh.g^(-1)and an ultra-high capacity retention of 90.5%after 300 cycles.The 5 wt%NaPVS-Na_(3)V_(2)(PO_(4))_(2)F_(3)(NVPF)|PEO-NaPF_(6)|Na battery with the high cutoff voltage of 4.2 V showed a specific discharge capacity of 88.9 mAh.g^(-1)at 0.5C for 100 cycles with a capacity retention of 79%,which is much better than that of the pristine-NVPF(PR-NVPF)|PEO-NaPF_(6)|Na battery(33.2%).The addition of NaPVS not only enhances the diffusion kinetics at the interface but also improves the rate performance and stability of the battery,thus bolstering its viability for high-energy applications.In situ phase tracking further elucidates that NaPVS effectively mitigates self-discharge induced by the oxidative decomposition of PEO at high temperature.This work proposes a general strategy to maintain the structural stability of the cathode–electrolyte interface in PEO-based high-performance SSMBs.
基金financially supported by the National Natural Science Foundation of China(No.52161016)the Joint Key Project of Agricultural Fundamental Research in Yunnan Provincial(No.202101BD070001-017)+2 种基金the Yunnan Provincial Academician Workstation(No.202305AF150009)the Yunnan Province Natural Science Key Foundation(No.202201AS070152)the Special Project of"Leading Talents of Industrial Technology"of Yunnan Ten Thousand Talents Plan(No.80201408).
文摘The growing focus on environmental sustainability has spurred significant interest in plant extracts as eco-friendly alternatives to conventional corrosion inhibitors.This study presents a novel approach to enhance the corrosion resistance of cold-rolled steel(CRS)by utilizing a combination of sodium dodecylbenzene sulfonate(SDBS)and Camellia oleifera fruit shell extract(CFSE).The inhibition performance of the CFSE/SDBS complex on CRS in 0.50 M sulfamic acid(SA)solution was evaluated through weight loss methods and electrochemical methods.The results demonstrate an impressive inhibition efficiency of 93.2%with 200 mg L^(-1) CFSE and 50 mg L^(-1) SDBS at 20℃,supported by a synergism parameter(S_(θ))exceeding 1.CFSE,SDBS,and the CFSE/SDBS complex act as mixed-type inhibitors,primarily influencing the cathodic reaction.Surface analyses conducted using X-ray photoelectron spectroscopy(XPS)and time of flight secondary ion mass spectrometry(ToF-SIMS)confirm that the active components in CFSE and SDBS can adsorb onto CRS surfaces,creating a robust protective film.Quantum chemical(QC)calculations identify reactive sites in morin(MR),DL-methionine(DL-Met),and lysine(Lys),highlighting heteroatoms and conjugated double bonds as key contributors.Molecular dynamic(MD)simulations reveal that these compounds form an impermeable film on Fe(001)surfaces,effectively reducing the migration rate of corrosive ions(NH_(2)SO_(3)^(-),H_(3)O^(+)).This research challenges conventional compounding methods and offers innovative insights into the development of eco-friendly corrosion inhibitors derived from plant extracts.
文摘The large-scale commercialization of proton exchange membrane fuel cells(PEMFCs)has been hindered by the high demand of platinum(Pt)in the cathode due to the sluggish kinetics of the oxygen reduction reaction.Reducing the amount of Pt would worsen the problems caused by the adsorption of perfluorinated sulfonic acid(PFSA)ionomers to Pt via the side chains,namely,blocking the active sites of Pt and inducing densely packed layers of fluorocarbon backbones on Pt surface to obstruct local O_(2)transport at the Pt/PFSA interfaces.This work aims at optimizing the Pt/ionomer interface to mitigate the sulfonate adsorption and in the meantime to reduce the local O_(2)transport resistance(R_(local)),by using a porous composite of 1-butyl-3-methylimidazolium hydrogen sulfate ionic liquid(IL)modified MOF-808(BMImHSO_(4)@MOF-808)as additive in cathodic catalyst layer(CCL).Through detailed physical,spectroscopic and electrochemical characterizations,we demonstrate a three-fold optimization mechanism of Pt/ionomer interface structure by BMImHSO_(4)@MOF-808:the unsaturated metal sites in MOF-808 effectively inhibit the sulfonate adsorption on Pt through coordination with the sulfonates of PFSA,thereby improving catalyst utilization;the pores in MOF-808 establish efficient transport channels for gaseous oxygen,significantly reducing R_(local);the IL modification layers facilitate the formation of continuous proton transport networks,increasing proton conductivity.The incorporation of BMImHSO_(4)@MOF-808 in a low-Pt CCL(0.1 mg_(Pt)cm^(-2))yields a peak power density of 1.9 W cm^(-2)for PEMFC under H_(2)-O_(2)condition,and ca.20%increase of power density under H_(2)-air condition as compared with conventional CCL,indicating the prospect of IL-MOF composites as an efficient additive to enhance the performance of PEMFCs.
