An Efficient Extraction-Free Method for Oxidative Desulfurization of Model Fuels Employing Cross-Linked Polyionic Liquid Phosphotungstate Catalysts

An efficient extraction-free oxidative desulfurization(ODS)process using a series of cross-linked polyionic liquid phosphotungstate(CLPIL-PW)catalysts is reported.The cross-linked PILs were prepared with DVB and 1-n-alkyl-3-vinyl imidazole hydrobromide(alkyl=ethyl,butyl,octyl,dodecyl),and were then assembled with phosphotungstic acid(H_(3)PW_(12)O_(40))to form the catalysts.The CLPIL-PWs have been applied to the oxidative removal of dibenzothiophene(DBT)from model oil with H_(2)O_(2) as an oxidant.The effects of ionic liquid(IL)cationic species,varying the DVB/IL molar ratio in the polymerization process,and varying operating conditions were investigated.The CLPIL-PWs were characterized by inductively coupled plasma(ICP)mass spectrometry,elemental analysis,scanning electron microscopy(SEM),Fourier transform infra-red(FTIR)spectroscopy,X-ray diffraction(XRD),^(13)C and^(31)P nuclear magnetic resonance(NMR)spectroscopy.The polydivinylbenzene-co-1-n-octyl-3-vinyl imidazole phosphotungstate(P(DVB-OVIm)PW)exhibited the highest DBT removal efficiency(99.9%)and remarkable recyclability,and could be reused eight times without reducing its activity.Finally,an extraction-free ODS mechanism is proposed.

Synthesis,characterization and antitumor activity of rare earth(Y,La) substituted phosphotungstates containing 5-fluorouracil

Two rare earth substituted Keggin-type phosphomngstates containing 5-fluorouracil, K10C4H4FN2O2Y（PW11O39）2· 10H2O （FYPW） and Kg（C4H4FN2O2）2La（PWl1O39）2· 18H2O （FLaPW） were synthesized in aqueous solution, and the structures were characterized by Fourier transform infrared spectroscopy （FT-IR）, element analysis, inductively coupled plasma spectrometry （ICP）, X-ray powder diffraction （XRD） and 1H nuclear magnetic resonance （NMR）. Thermal analysis showed that the decomposition processes of the two compounds could be di- vided into three steps, the loss of crystal water, the decomposition of 5-fluorouracil unit and the decomposition of Keggin-type polyanions. The in vitro cytotoxicities against HEK 293, HeLa and HepG-2 cells were studied by methyl thiazolyl tetrazolium （MTT） assay. The results showed that FYPW and FLaPW had higher antitumor activities than 5-fluorouracil, C4H4FN2O2H2PW12O40.8H2O and rare earth substituted polyoxometalates KllLn（PW11O39）2@nH2O （Ln-Y, La）. It was concluded that introducing 5-fluorouracil and rare earth （Y or La） into its structure was a considerable way to enhance antitumor activities ofpolyoxometalates.

Synthesis and antitumor activities of rare earth substituted phosphotungstates containing 5-fluorouracil

Two novel rare earth substituted phosphotungstates containing 5-fluorouracil,K 9（C 4 H 4 FN 2 O 2） 2 Nd（PW 11 O 39） 2 ·25H 2 O（FNdPW） and K 9（C 4 H 4 FN 2 O 2） 2 Ce（PW 11 O 39） 2 ·23H 2 O（FCePW）,were synthesized and characterized by elementary analysis,FT-IR spectra,X-ray powder diffraction and 1 H NMR.The thermal analysis showed that FNdPW decomposed at 210 and 493 oC,and FCePW decomposed at 223 and 471 oC,both of which had good thermal stabilities.MTT tests were performed to study the antitumor activities against HeLa cells and HepG-2 cells of FNdPW,FCePW,5-fluorouracil,C 4 H 4 FN 2 O 2 H 2 PW 12 O 40 ·8H 2 O and K 11 Ln（PW 11 O 39） 2 ·xH 2 O（Ln=Nd,Ce）,and their cytotoxicities against HEK 293 cells.The results showed that FNdPW and FCePW possessed higher antitumor activities and lower cytotoxicities than those of 5-fluorouracil and C 4 H 4 FN 2 O 2 H 2 PW 12 O 40 ·8H 2 O,of which FNdPW exhibited the highest antitumor activates against HeLa cells（EC 50 =3.41×10-6 mol/L） and HepG-2 cells（EC 50 =6.24×10-6 mol/L）.Thus the introduction of rare earth elements and 5-fluorouracil could significantly enhance antitumor effect of polyoxometalates.

Phosphotungstic acid immobilized on amino-functionalized TS-1 zeolite as a solid acid catalyst for the synthesis of tributyl citrate

The amino-functionalization of TS-1 zeolite followed by immobilization of phosphotungstic acid(HPW)was presented to prepare a strong solid acid catalyst for the synthesis of bio-based tributyl citrate from the esterification of citric acid and n-butanol.γ-Aminopropyltriethoxysilane(APTES)was first grafted on the TS-1 zeolite via the condensation reactions with surface hydroxyl groups,and subsequently the HPW was immobilized via the reaction between the amino groups and the protons from HPW-forming strong ionic bonding.The Keggin structure of HPW and MFI topology of TS-1 zeolite were well maintained after the modifications.The amino-functionalization generated abundant uniformly distributed active sites on TS-1 for HPW immobilization,which promoted the dispersity,abundance,as well as the stability of the acid sites.The tetrahedrally coordinated framework titanium and non-framework titania behaved as weak Lewis acid sites,and the protons from the immobilized HPW acted as the moderate or strong Brønsted acid sites.An optimized TBC yield of 96.2%(mol)with a conversion of-COOH of 98.1%(mol)was achieved at 150℃for 6 h over the HPW immobilized on amino-functionalized TS-1.The catalyst exhibited good stability after four consecutive reaction runs,where the activity leveled off at still a relatively high level after somewhat deactivation possibly caused by the leaching of a small portion of weakly anchored APTES or HPW.

THE SYNTHESIS AND STRUCTURE OF BI-VACANT D AWSON PHOSPHOTUNGSTATE K_(10)Na_2H_2P_2W_(16)O_(60)·18H_2O

The conclusion has been made that mono- and tri-vacant Dawson phosphotungstates (shown as P2W17 and P2W15)exist. The bi-vacant Dawson phosphotungstate (P2W16) which was synthesized by hydrolyzing P2W18 with Na2CO3 soluti on, has been reported by Contant et al., however this was soon rejected by themselves. It has also

Study on the Synthesis of Octyl Acetate by Phosphotungstate Heteropolyacid with Keggin Structure

1 Results Octyl Acetate is an important chemical material.It is widely used as solvent in many industries,such as plasterer,artificial leather,and lacquer varnish,spice and medicine industries.At the present time,it is prepared with acetic acid and 1-octanol in industry,by using sulfuric acid as the catalyst.This technique has many shortcomings,which include erosion of facility,many side reactions and difficulties of post-treatment.The most severe problem is its pollution to the environment[1-2],so this...

Facile synthesis of efficient pentaethylenehexamine-phosphotungstic acid heterogeneous catalysts for oxidative desulfurization

The ultra-deep desulfurization of oil needs to be solved urgently due to various problems,including environmental pollution and environmental protection requirements.Oxidative desulfurization(ODS)was considered to be the most promising technology.The facile synthesis of highly efficient and stable HPW-based heterogeneous catalysts for oxidative desulfurization is still a challenging task.In this paper,pentamethylene hexamine(PEHA)and phosphotungstic acid(HPW)were combined by a simple one-step method to prepare a heterogeneous catalyst of PEHA-HPW for the production of ultra-deep desulfurization fuel oil.The composite material exhibited excellent catalytic activity and high recyclability,which could reach a 100% dibenzothiophene(DBT)removal rate in 30 min and be recycled at least 5 times.Experiments and DFT simulations were used to better examine the ODS mechanism of PEHA-HPW.It was proved that the rich amino groups on the surface of PEHA-HPW play a crucial role.This work provides a simple and feasible way for the manufacture of efficient HPW-based catalysts.

Encapsulation of ionic liquid, phosphotungstic acid inside the nanocages of MIL-101(Cr): Effective and reusable catalyst for efficient solvent-free oxidative desulfurization from fuel oil

Oxidative desulfurization from fuel oil is one of the important methods for deep desulfurization.The development of efficient oxidative desulfurization catalysts is crucial for improving the desulfurization performance.Successful encapsulation of phosphotungstic acid(HPW)and ionic liquid(BMImBr)inside the mesoporous cages of MIL-101(Cr)was accomplished through a combination of“bottle around ship”and“ship in bottle”methods.The obtained BMImPW@MIL-101(Cr)composite was characterized by XRD,FTIR,BET,SEM,XPS and ICP methods.Results indicated that the BMImPW@MIL-101(Cr)composites with PW^(3−) loading of 23.1–50.7 wt%were obtained,demonstrating that the“bottle around ship”method is beneficial to make full use of nanocages of MIL-101(Cr)to obtain expected high loading of active PW^(3−) .The BMImPW@MIL-101(Cr)exhibits excellent reusability with no evidence of leaching of active PW^(3−) and BMIm^(+),and well-preserved structure after successive cycles of regeneration and reuse.The significantly improved stability of BMImPW@MIL-101(Cr)as compared to HPW@MIL-101(Cr)is possibly because the leaching of the active PW^(3−) −sites can be greatly suppressed by forming large size of BMImPW owing to introduction of BMIm^(+)cation.The BMImPW@MIL-101(Cr)exhibited excellent catalytic activity for solvent free oxidative desulfurization of refractory sulfides.The enhanced oxidative desulfurization activity as compared to HPW@MIL-101(Cr)can be explained by the intimate contact of sulfides with active PW^(3−) sites owing the strong attraction of BMIm^(+)cation with the sulfides.

Study on the epoxidation of olefins with H_(2)O_(2)catalyzed by biquaternary ammonium phosphotungstic acid

Selective epoxidation of olefins is an important field in chemical industry.In this work,we developed a new phosphotungstic acid catalyst{[(C_8H_(17))(CH_(3))_(2)N]_(2)(CH_(2))_(3)}_(1.5){PO_(4)[WO(O_(2))_(2)]_(4)}with long carbon chain and biquaternary ammonium cation.Cyclohexene could be epoxidized to cyclohexene oxide in 96.3%conversion and 98.2%selectivity.The catalyst type,solvent type,catalyst loading,initial molar ratio,temperature,cycle performance and substrate extensibility were studied and optimized,the kinetic parameters about overall reaction and unit reaction were also calculated.Dynamic light scattering analysis was carried out to explain the different catalytic performance between catalysts with different carbon chain length.This novel catalyst and the corresponding dynamics and mechanism study could probably help the industrial application on the epoxidation of cyclohexene with H_(2)O_(2).

Styrene epoxidation catalyzed by polyoxometalate/quaternary ammonium phase transfer catalysts: The effect of cation size and catalyst deactivation mechanism

Catalytic epoxidation of alkenes is an important type of organic reaction in chemical industry,and the deep insight into catalyst deactivation will help to develop new epoxidation process.In this work,series of quaternary ammoniums bearing different cationic sizes,i.e.MTOA+(methyltrioctylammonium,[(C_(8)H_(17))_(3)CH_(3)N]+),HTMA+(hexadecyltrimethylammonium,[(C_(16)H_(33))(CH_(3))_(3)N]+) and DMDOA+(dimethyldioctadecylammonium,[(C_(18)H_(37))_(2)(CH_(3))_(2)N]+) were incorporated with polyoxometalate (POM) anions to prepare phase transfer catalysts (PTCs),which were used in the styrene epoxidations.Among them,(MTOA)_(3)PW_(4)O_(24)exhibits the best catalytic performance judged from the highest styrene conversion rate(52%) and styrene oxide selectivity (93%),during which the styrene epoxidation conditions were optimized.Meanwhile,the deactivation mechanism of this kind of PTCs was proposed firstly,i.e.in the case of low H_(2)O_(2) content,the oxidant can only be used in the styrene epoxidation,in which the catalyst can transform into stable Keggin-type POM.But when the content of H_(2)O_(2) is higher,the excess H_(2)O_(2) can reactivate the Keggin-type POM into active (PW_(4)O_(24))_(3)-anions,which can trigger the ring-opening polymerization of styrene oxide.Consequently,the catalyst is deactivated by adhered poly(styrene oxide)irreversibly,which was determined by NMR spectra.In this situation,the active moiety{PO_(4)[WO(O_(2))_(2)]_(4)}_(3)-in phase-transfer catalytic system can break into some unidentified species with low W/P ratio with the presence of epoxides.This work will be beneficial for the design of new PTCs in alkene epoxidation in fine chemical industry.

Preparation,Characterization of Dawson-type Heteropoly Acid Cerium（Ⅲ） Salt and Its Catalytic Performance on the Synthesis of n-Butyl Acetate

A novel cerium(Ⅲ) salt of Dawson type tungstophosphoric acid(Ce2P2W18O62·16H2O) was prepared by doping cerous nitrate in H6P2W18O62·13H2O powder and characterized by thermogravimetry and differential thermal analyses(TG/DTA),Fourier transform infrared spectroscopy(FT-IR),X-ray powder diffraction(XRD),pyridine infrared spectroscopy(Py-IR) and scanning electron microscopy(SEM).Its catalytic activity was evaluated by the probe reaction of synthesis of n-butyl acetate with acetic acid and n-butanol.The effects of various parameters such as molar ratio of n-butanol to acetic acid,reaction temperature,reaction time,and catalyst amount have been studied by single factor experiment.The results show that Ce2P2W18O62·16H2O behaved as an excellent heterogeneous catalyst in the synthesis of n-butyl acetate.The optimum synthetic conditions were determined as follows︰molar ratio of n-butanol to acetic acid at 2.0︰1.0,mass of the catalyst being 1.44% of the total reaction mixture,reaction temperature of 120 ℃ and reaction time of 150 min.Under above conditions,the conversion of acetic acid was above 97.8%.The selectivity of n-butyl acetate based on acetic acid was,in all cases,nearly 100%.The catalysts could be recycled and still exhibited high catalytic activity with 90.4% conversion after five cycles of reaction.It was found by means of TG-DTA and Py-IR that the catalyst deactivation was due to the adsorption of a complex of by-product on the active sites on catalysts surface or the catalyst loss in its separation from the products.Compared with using sulfuric acid as catalyst,the present procedure with Ce2P2W18O62·16H2O is a green productive technology due to simple process,higher yield,catalyst recycling and no corrosion for the production facilities.

One-pot synthesis of a hierarchical microporous-mesoporous phosphotungstic acid-HKUST-1 catalyst and its application in the selective oxidation of cyclopentene to glutaraldehyde

A hierarchical microporous-mesoporous metal-organic framework of HKUST-l（Cu）-encapsulated phosphotungstic acid （HPW） material, referred to as HPWs@Meso-HKUST-1, is prepared by a one-pot synthesis method using cetyltrimethylammonium bromide as the supramolecular template. The addition of HPWs to the synthesis mixture of hierarchical porous HKUST-1 results in the direct encapsulation of HPWs inside the mesopores of the HKUST-1 structure, with a homogeneous distribution over the HKUST-1 crystals, which is confirmed by XRD, FT-IR, N2 adsorption, UV-Vis DRS, and TEM. FT-IR-CO adsorption experiments indicated that additional Lewis acid sites were present in the HPWs@Meso-HKUST-1 sample. The novel heterogeneous catalyst demonstrates excellent catalytic performance for the selective oxidation of cyclopentene （CPE） to glutaraldehyde CGA） using tert-butyl hydroperoxide and acetonitrile （MeCN） as the oxidant and solvent, respectively. The high activity of the catalyst is attributed to the mesostructure of the catalyst and the nature and appropriate abundance of the HPWs--being highly dispersed with the addition of Lewis sites. After a reaction for 36 h, the 30% wt% HPWs@Meso-HKUST-1 catalyst exhibits a CPE conversion of 92.5% and a high GA yield of 73%. Furthermore, the HPWs@Meso-HKUST-1 material is sufficiently stable to prevent the leaching of HPWs, and behaves as a true heterogeneous catalyst that can be repeatedly recycled without sustaining a loss of activity and selectivity in the selective oxidation of CPE.

Nano-porous Composites Based on Liquid： Synthesis, Characterization, Esterification Heteropolyacid Functionalized Ionic and Catalytic Performance in

Fhnctionalized ionic liquid samples （bmim-PW12） were synthesized by 1-butyl-3-methyl- imidazolium bromide （bmimBr） and 12-phosphotungstic heteropolyacid （PW12）. The samples were annealed at 100-450 ℃ and were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscope, thermal gravity-DTG, brunauer emmett teller, and NHa-temperature programmed desorption. The results showed that the bmim-PW12 samples were crystal and maintained intact Keggin structure. The organic parts of those samples were partly decomposed at a temperature more than 350 ℃. The sample annealed at 400 ℃ exhibited nano-porous structure, strong acidity, and excellent catalytic activity on the esterification of n-butanol with acetic acid. The higher ester yield was obtained when the mass ratio of catalyst over the reactants amount was 5% for bmim-PW12 catalyst annealed at 400 ℃.

An Organic-inorganic Hybrid Two-dimensional Bilayer Assembled from 1:2-Type[Er(α-PW11O39)2]^11–Moieties and[Cu(dap)2]^2+Linkers

A new organic-inorganic hybrid phosphotungstate-based Cu^Ⅱ-Er^Ⅲ heterometallic derivative[Cu（dap）2（H2O）][Cu（dap）2]4.5[Er（α-PW11O39）2]·4H2O（1,dap = 1,2-diaminopropane） has been hydrothermally prepared and characterized by elemental analysis,IR spectra and X-ray single-crystal diffraction.1 belongs to the triclinic space group P1 with a = 13.453（3）,b =20.137（4）,c = 24.565（4） A,α = 103.468（4）,β = 103.829（4）,γ = 98.296（4）°,V= 6148.0（19） A°3,Z =2,μ = 22.212 mm^-1,GOOF = 1.030,R = 0.0744 and wR = 0.1700.Structural analysis indicates that1 exhibits a special two-dimensional double-layer structure constructed from l：2-type[Er（α-PW11O39）2]^11- moieties and[Cu（dap）2]^2＋ linkers.From the topological viewpoint,1 displays a scare two-dimensional five-connected topology in which the[Er（α-PW11O39）2]^11- moieties function as the five-connected nodes.Furthermore,its thermogravimetric behavior has been studied.

Catalytic synthesis of acetals and ketals with H3PW12O40/PAn

A new environmental friendly catalyst H3PW12O40/PAn was prepared and identified by means of FT-IR,XRD,and TG/DTA.The optimum conditions have been found;that is,the mass ratio of PAn to H3PW12O40 is 1：1.5,the volume of methanol is 20 mL,and the reflux reaction time is 3 h.The structural identity of Keggin units is preserved after the incorporation into polyaniline matrix.Catalytic activities of H3PW12O40/PAn in synthesizing 2-methyl-2-ethoxycarbonylmethyl-1,3-dioxolane,2,4-dimethyl-2-ethoxycarbonylmethyl-1,3-dioxolane,cyclohexanone ethylene ketal,cyclohexanone 1,2-propanediol ketal,butanone ethylene ketal,butanone 1,2-propanediol ketal,2-phenyl-1,3-dioxolane,4-methyl-2-phenyl-1,3-dioxolane,2-propyl-1,3-dioxolane,and 4-methyl-2-propyl-1,3-dioxolane were reported.It has been demon-strated that H3PW12O40/PAn is an excellent catalyst.Various factors concerned in these reactions were investigated.The optimum conditions are as follows：the molar ratio of aldehyde/ketone to glycol（r） is 1：1.5,the mass ratio of the catalyst used to the reactants is 0.6%,and the reaction time is 1.0 h.Under these conditions,the yield is as follows：2-methyl-2-ethoxycarbonylmethyl-1,3-dioxolane,69.0%;2,4-dimethyl-2-ethoxycarbonylmethyl-1,3-dioxolane,79.5%;cyclohexanone ethylene ketal,78.9%;cyclohexanone 1,2-propanediol ketal,85.3%;butanone ethylene ketal,56.9%;butanone 1,2-propanediol ketal,78.1%;2-phenyl-1,3-dioxolane,76.3%;4-methyl-2-phenyl-1,3-dioxolane,94.2%;2-propyl-1,3-dioxolane,70.7%;and 4-methyl-2-propyl-1,3-dioxolane,79.2%.

A Hybrid Membrane of Poly(vinyl alcohol) and Phosphotungstic Acid for Fuel Cells

Proton conducting membranes composed of phosphotungstic acid (PWA) and poly(vinyl alcohol) (PVA)were prepared. Conductivity and Fourier transform infrared spectrometer(FTIR) measurements show that most ofthe acid embedded are stable in the PVA matrix when the membrane is immerged in water or methanol solution atroom temperature. Conductivity of the composite membranes scatters around 10-3 S.cm-1 at room temperature.The methanol crossover through the membranes is about an order of magnitude lower than that through Nafion117 membrane.

Insight into the oxidative desulfurization of high-sulfur petroleum coke under mild conditions:a journey of vanadium-substituted Dawson-type phosphotungstic acid

High-sulfur petroleum coke(HSPC),that is a by-product from slag oil in the coking process of refning,shows versatility values in practical applications and,however,concentrates the majority of organic sulfur.Herein,we design and construct a highly efective CTAB@HPA composites to be explored for the catalytic oxidative desulfurization of HSPC under mild conditions using hydrogen peroxide as the oxidant and 1-butyl-3-methylimidazole tetrafuoroborate ionic liquid as the extractant.The results demonstrate that the sulfur content of HSPC could be strikingly reduced from 4.46 wt%to 2.48 wt%under 60℃ and atmospheric pressure,and that the organic sulfur in HSPC is mainly oxidized to sulfoxide,sulfone and sulfate,which latter can be directly separated from petroleum coke.Moreover,the efect of reaction conditions on the desulfurization performance of HSPC as well as the catalytic oxidation reaction kinetic of HSPC desulfurization was systematically investigated.Furthermore,a mechanism for the oxidative desulfurization of HSPC over CTAB@HPA catalysts was proposed.Therefore,this work provides new insight into how to construct active catalysts for the desulfurization of HSPC under mild conditions.

Synthesis of Bimodal Mesoporous TiO_(2)-PTA/BMMS and Its Enhanced Performance in the Photocatalytic Oxidative Desulfurization

With the bimodal mesoporous silica(BMMS)acting as the support and the composite of TiO2 with phosphotungstic acid(PTA)functioning as the active constituent,TiO_(2)-PTA/BMMS was synthesized by the two-step impregnation route.This catalyst was applied in the photocatalytic oxidative desulfurization(PODS)process,with dibenzothiophene serving as the model sulfur compound.PODS proceeds in one pot,in which H_(2)O_(2) acts as the oxidant and methanol plays the role of the solvent.TiO_(2)-PTA/BMMS was characterized by XRD,N_(2) adsorption and desorption,XRF,FTIR,UV-vis,SEM,EDS and TEM techniques.It showed that the introduction of PTA contributes higher order,higher surface area and pore volume to the bimodal mesoporous support.With TiO_(2)-PTA/BMMS used as the catalyst under the UV irradiation,the desulfurization rate can reach 99.6%.This result is obviously higher than that achieved by TiO_(2)/BMMS.The catalyst also has no significant drop in catalytic activity after eight runs of reusing.In such catalytic system,the synergistic effects of this photocatalytic oxidation and the extraction with the methanol serving as the solvent played an indispensable role.

Synergistic Effect between Zr-MOF and Phosphotungstic Acid for Oxidative Desulfurization

PTA/UiO-66 composites were successfully synthesized by the hydrothermal method.The results showed that the synergistic effect between phosphotungstic acid(PTA)and UiO-66 could enhance the oxidative desulfurization(ODS)activity.The XRD results proved that UiO-66 retained its structure in the PTA/UiO-66 composites.The SEM results showed that the PTA/UiO-66 catalysts exhibited regular octahedral shape.The Raman spectra revealed that PTA in the composites retained the Keggin structure.The XPS results showed that the electron transfer occurred from Zr-MOF to PTA.The ODS reaction mechanism was discussed.Electrons transfer from Zr-MOF to PTA can promote the generation of active species(·OH)and thus enhance the ODS activity.This explanation can be confirmed by the formation of oxygen vacancy and W0 as revealed by the XPS analysis.

A phosphotungstic acid coupled silica-Nafion composite membrane with significantly enhanced ion selectivity for vanadium redox flow battery

An ultra-high ion-selective Nafion composite membrane modified by phosphotungstic acid(PWA)coupled silica for vanadium redox flow battery(VRB)was constructed and prepared through solution casting.The composite membrane exhibits excellent proton conductivity and vanadium ions blocking property by incorporating the nanohybrid composed of silica and PWA into the Nafion ionomer.Simple tuning for the filling amount of the nanohybrid endows the obtained membranes preeminent vanadium barrier property including a minimum vanadium permeability of 3.13×10-7cm2min-1and a maximum proton conductivity of 0.081 S cm-1at 25°C.These indicate an ion selectivity of 2.59×105S min cm-3,which is 6.8times higher than that of recast Nafion(0.33×105S min cm-3).As a result,the VRB with the composite membrane shows superior battery performance containing a lower self-discharge rate,higher capacity retention and more robust cyclic stability compared with recast Nafion over a range of current densities from 40 to 100 m A cm-2.