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 chlorometh...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.展开更多
A novel series of poly(aryl ether sulfone ketone)s (PPESKs) containing phthalazinone and biphenyl moieties were prepared by two-step nucleophilic polycondensation reaction. The ^-Mw values of these copolymers were...A novel series of poly(aryl ether sulfone ketone)s (PPESKs) containing phthalazinone and biphenyl moieties were prepared by two-step nucleophilic polycondensation reaction. The ^-Mw values of these copolymers were between 38,330 and 67,900. The glass transition temperatures (Tg) and 5% decomposition temperatures were ranged in 253-269 ℃ and 488-500 ℃, respectively, The structures of these copolymers were confirmed by FT-IR and ^1H NMR. Moreover, all the resultant copolymers were amorphous determined by wide angle X-ray diffraction (WAXD).展开更多
A novel type of crosslinkable poly(aryl ether sulfone)(PAES) bearing an allyl pendant(PES-OAllyl) was synthesized by a grafting reaction of hydrophenyl-containing PAES(PES-OH) and allyl bromide. PES-OH was pre...A novel type of crosslinkable poly(aryl ether sulfone)(PAES) bearing an allyl pendant(PES-OAllyl) was synthesized by a grafting reaction of hydrophenyl-containing PAES(PES-OH) and allyl bromide. PES-OH was prepared by a demethylation reaction of a methoxyphenylated PAES(PES-OCH3) in the presence of pyridine/hydrochlo- ride. The PES-OCH3 was synthesized by an aromatic nucleophilic substitution of bis(4-chlorophenyl)sulfone and (p-methoxy)phenylhydroquinone. Both DSC and solubility investigation were used to study the crosslinking behavior of PES-OAllyl. After heat treatment, the glass transition temperature(Tg) value of PES-OAllyl sharply increased from 165 ℃ to 227 ℃. Meanwhile, PES-OAllyl changed from a soluble polymer to an insoluble thermoset. In addition, TGA(thermogravimetric analysis) result suggests that the thermal stability of the crosslinked product was improved. All the data prove that the crosslinked PES-OAllyl could be a potential solvent-resistance high-performance material.展开更多
A series of Poly(arly ether sulfone ether ketone)s containing pendant methyl groups were synthesized by the reaction of 4,4'-[sulfonylbis (1,4-phenylene)dioxy] dibenzoyl chloride (SODBC) with 4,4'- diphenoxy d...A series of Poly(arly ether sulfone ether ketone)s containing pendant methyl groups were synthesized by the reaction of 4,4'-[sulfonylbis (1,4-phenylene)dioxy] dibenzoyl chloride (SODBC) with 4,4'- diphenoxy diphenylsulfone (DPODPS), 4,4'- di(2-methylphenoxy) diphenylsulfone (o-Me-DPODPS), 4,4'- di(3-methylphenoxy) diphenylsulfone (m-Me-DPODPS), 4,4'- di (2,6-bimethylphenoxy) biphenylsulfone(o-Me2-DPODPS) respectively, in a mixture of 1,2-dichloroethane (DCE) and N-methylpyrrolidone (NMP). These reactions were catalyzed by anhydrous aluminum chloride (AlCl). The characteristic of copolymers were studied by means of advanced analytical techniques such as FT-IR,1H-NMR, DSC, TGA and WAXD. The results show glass transition temperature (Tg) in the range of 193-206℃, thermally stable in excess of 434℃ and excellent solubility in polar solvents. Methyl-substituted Poly(aryl ether sulfone ketone)s had higher glass transition temperatures, lower initial decomposition temperatures than the unsubstituted ones.展开更多
A kind of novel heat-resistant, high performance engineering thermoplastic phthalazinone poly(aryl ether sulfone ketone) (PPESK) containing a carboxyl group in its side chain was prepared by the nucleophilic displacem...A kind of novel heat-resistant, high performance engineering thermoplastic phthalazinone poly(aryl ether sulfone ketone) (PPESK) containing a carboxyl group in its side chain was prepared by the nucleophilic displacement reaction of 4-(4-hydroxylphenyl)- 1 (2H)-phthalazinone with di(4-chlorophenyl) sulfone, 4,4'-difluoro-benzophenone and phenolphthalin in sulfolane in the presence of K2CO3 to produce high molecular weight polymers which can be dissolved in some polar solvents such as chloroform and nitrobenzene at room temperature and can be easily cast into flexible, yellowish and transparent films. PPESK is an amorphous polymer having a decomposition temperature above 400degreesC, which indicates that it has high thermal stability. At the same time, the thermal properties of PPESKs with dicyandiamide (DICY) as curing agent indicated that the heat-resistance properties of the PPESKs are improved after curing. The apparent activation energy (A-E) of the cross-linking reaction and the reaction order (n) of PPESK/DICY were found to be 52.2 kJ/mol and ca. 1.0, respectively. Therefore, the cross-linking reaction is approximately a first order reaction.展开更多
A novel poly (ether sulfone ketone) containing the phthalazinone moiety was prepared by the reaction of 4-)4-hydroxyphenyl) (2H) phthalazin-1-one with activated dichloro-monomers. The polymer was characterized by FT-I...A novel poly (ether sulfone ketone) containing the phthalazinone moiety was prepared by the reaction of 4-)4-hydroxyphenyl) (2H) phthalazin-1-one with activated dichloro-monomers. The polymer was characterized by FT-IR, H-1-NMR, DSC, TGA and X-ray diffraction.展开更多
Novel poly(aryl ether sulfone ketone)s (PAESK) were synthesized from bisphenol A (BPA), 9,9'-bis(4-hydroxyphenyl) fluorene (BHPF), 4,4'-dichlorodiphenylsulfone (DCS) and 4,4'-difluorobenzophenone (DFB...Novel poly(aryl ether sulfone ketone)s (PAESK) were synthesized from bisphenol A (BPA), 9,9'-bis(4-hydroxyphenyl) fluorene (BHPF), 4,4'-dichlorodiphenylsulfone (DCS) and 4,4'-difluorobenzophenone (DFB) via nucleophilic substitution polymerization, which were subsequently used to fabricate ultrafiltration membrane by phase-inversion method for high temperature condensed water treatment. The obtained high molecular weight co-polymers with fluorene group with good solubility and good thermal stability, can be easily cast into flexible, white and non-transparent fiat films. The influence of molar ratio of BPA and BHPF on the properties of the prepared co-polymers and membranes was investigated in detail. SEM study of the morphology of the membranes indicated that the prepared membranes possessed homogeneous pores on the top surface and were sponge-like or finger-like in cross-section. Pure water flux of the membranes increased from 71.87 L·m-2.h-1 to 247.65 L·m-2.h-1, while the retention of BSA decreased slightly, and the water contact angle decreased from 82.1 ° to 55.6° with the PVP concentration from 0 wt% to 10 wt%. With increasing concentration of PVP, the mechanical properties of membranes decreased, while the thermal stability increased. The permeate flux measurement showed that the PAESK membrane had the potential for high temperature condensed water treatment.展开更多
A series of cardo poly(aryl ether sulfone) copolymers bearing pendent sulfonic acid groups (SPES-X) have been prepared by a facile chemical graft method. The structure was confirmed by 1H-NMR spectra. The side-cha...A series of cardo poly(aryl ether sulfone) copolymers bearing pendent sulfonic acid groups (SPES-X) have been prepared by a facile chemical graft method. The structure was confirmed by 1H-NMR spectra. The side-chain-type SPES-X membranes show significantly reduced swelling behavior and excellent mechanical properties as well as appropriate proton conductivity compared to the main-chain-type sulfonated polymers with similar ion exchange capacity (IEC) value. Moreover, they show methanol permeability in the range of 0.6 × 10^-7-5.7 × 10^-7 cmE/s which is lower than that of Nafion 117. All the results indicate that the SPES-Xmembranes are promising candidates for the direct methanol fuel cells.展开更多
A series of novel TiO2/poly(aryl ether sulfone) ultrafiltration membranes with anti-fouling and self-cleaning properties was designed and prepared. First, anti-photocatalytic degraded fluorine contained polv(aryl ethe...A series of novel TiO2/poly(aryl ether sulfone) ultrafiltration membranes with anti-fouling and self-cleaning properties was designed and prepared. First, anti-photocatalytic degraded fluorine contained polv(aryl ether sulfone) matrix(PAES-F) was synthesized. Then the composite membranes were prepared via TiO2 nanopartides and PAES-F polymer matrix by solution blending and non-solvent induced phase inversion methods. Further, separation efficiency, fouling behavior and self-cleaning property of the composite ultrafiltration(UF) membranes were investigated by dead-end filtration experiments using a polyacn lamide solution. The composite UF membranes exhibited outstanding self-cleaning efficiency and anti-photocatalytic degraded property after exposure to simulated sunliglit irradiation.The water flux recovery ratios(FRR)of the optimal composite UF membranes could reach 74.24%, which was attributable to photocatalytic degradation of the organic contaminant by TiO2. And the retention rates of the composite UF membranes could maintain over 97%, which indicated the excellent photocatalytic degradation resistance of the fluorine contained PAES-F matrix. The novel high perfomiance composite UF membranes have a broad application prospect in water treatment.展开更多
In the field of proton exchange membranes(PEMs),it is still a great challenge to explore new Nafion alternatives,maintaining the high proton conductivity and lowering the cost of practical application.In this work,a s...In the field of proton exchange membranes(PEMs),it is still a great challenge to explore new Nafion alternatives,maintaining the high proton conductivity and lowering the cost of practical application.In this work,a series of low sulfonated poly(aryl ether ketone sulfone)(SPAEKS)membranes hybridized by[Bi_(6)O_(5)(OH)_(3)]_(2)(NO_(3))10⋅6H_(2)O(H_(6)Bi_(12)O_(16))have been successfully fabricated.When the doping amount of H6Bi12O16 reaches 5 wt%,the DS15-Bi12-5 showing the best proton conductive ability and mechanical properties.The proton conductivity can achieve 72.8 mS⋅cm−1 at 80℃ and the tensile strength can reach 43.57 MPa.Confirmed by experimental data and activation energy(Ea)calculations,the existence of Bi cluster makes more hydrogen bonds,providing additional proton hopping sites and offers more proton transport vehicles,leading to a high proton conduction performance.This work proved that polyoxometalates(POMs)can replace the role of sulfonate groups in SPAEKS to a certain extent and work out the defects of high sulfonation,making a remarkable contribution to the practical application of low sulfonated SPAEKS.展开更多
The occurrence of ultrafiltration(UF)membrane fouling frequently hampers the sustainable advancement of UF technology.Reactive self-cleaning UF membranes can effectively alleviate the problem of membrane fouling.Never...The occurrence of ultrafiltration(UF)membrane fouling frequently hampers the sustainable advancement of UF technology.Reactive self-cleaning UF membranes can effectively alleviate the problem of membrane fouling.Nevertheless,the self-cleaning process may accelerate membrane aging.Addressing these concerns,we present an innovative design concept for composite self-healing materials based on self-cleaning UF membranes.To begin,TiO_(2)nanoparticles were incorporated into the polymer molecular structure via molecular design,resulting in the synthesis of TiO_(2)/carboxyl-polyether sulfone(PES)hybrid materials.Subsequently,the nonsolvent-induced phase inversion technique was employed to prepare a novel of UF membrane.Lastly,a polyvinyl alcohol(PVA)hydrogel coating was applied to the hybrid UF membrane surface to create PVA@TiO_(2)/carboxyl-PES self-healing reactive UF membranes.By establishing a covalent bond,the TiO_(2)nanoparticles were effectively and uniformly dispersed within the UF membrane,leading to exceptional self-cleaning properties.Furthermore,the water-absorbing and swelling properties of PVA hydrogel,along with its capacity to form hydrogen bonds with water molecules,resulted in UF membranes with improved hydrophilicity and active self-healing abilities.The results demonstrated that the water contact angle of PVA@5%TiO_(2)/carboxyl-PES UF membrane was 43.1°.Following a 1-h exposure to simulated solar exposure,the water flux recovery ratio increased from 48.16%to 81.03%.Moreover,even after undergoing five cycles of 12-h simulated sunlight exposure,the UF membranes exhibited a consistent retention rate of over 97%,thus fully demonstrating their exceptional self-cleaning,antifouling,and selfhealing capabilities.We anticipate that the self-healing reactive UF membrane system will serve as a pioneering and comprehensive solution for the self-cleaning antifouling challenges encountered in UF membranes while also effectively mitigating the aging effects of reactive UF membranes.展开更多
A series of novel organic-inorganic hybrid proton-conducting electrolyte membranes with silane-crosslinked sulfonated poly(aryl ether ketone)(SC-SPAEK) networks was prepared via a simple procedure that includes soluti...A series of novel organic-inorganic hybrid proton-conducting electrolyte membranes with silane-crosslinked sulfonated poly(aryl ether ketone)(SC-SPAEK) networks was prepared via a simple procedure that includes solution casting and acid treatment. The organosilicon pendants of the silane-grafted SPAEK, which were expected to serve as coupling and crosslinking agents, were found to play a key role in the homogenous dispersion of inorganic particles and improved the performance of hybrid membranes. The hybrid membranes exhibited enhanced proton conductivity, and SC-SPAEK/TiO2-4 showed an extremely high proton conductivity of 0.1472 S/cm at 100℃. The crosslinked hybrid membranes also demonstrated good chemical resistance, oxidative stability, and mechanical properties. The crosslinked hybrid membranes with excellent comprehensive performance may be a promising material for proton exchange membrane fuel cells.展开更多
Sulfonated poly(ether ketone)s containing 3,5-dimethyl phthalazinone moieties (SPPEK-DMs) with different degrees of sulfonation (DS) were synthesized via direct polycondensation from 4-(3,5-dimethyl-4-hydroxyph...Sulfonated poly(ether ketone)s containing 3,5-dimethyl phthalazinone moieties (SPPEK-DMs) with different degrees of sulfonation (DS) were synthesized via direct polycondensation from 4-(3,5-dimethyl-4-hydroxyphenyl)-2,3- phthalazinone, 4,4'-difluorobenzophenone and 3,3'-disulfonate-4,4'-difluorobenzophenone. The chemical structure of SPPEK-DMs was characterized by FTIR and 1H-NMR. Thermal stability of SPPEK-DMs was characterized by the thermogravimetric analysis. The membranes prepared from SPPEK-DMs exhibited ion exchange capacities (IEC) ranging from 0.93 mmol.g-1 to 1.86 mmol.g-1. Water uptake, swelling, oxidative stability and methanol permeability of SPPEK- DMs membranes were investigated. SPPEK-DMs membranes exhibited high oxidative stability. The methanol permeability values of SPPEK-DMs membranes were in the range 5.15× 10^-8-6.61×10^-7 cm^2.s-1, which was much lower than those of Nafion117. The proton conductivity of SPPEK-DM40 membranes was 1.1 ×10^-2 S.cm^-1 at 70℃.展开更多
基金partly financed by the Major State Basic Research Development Program of China(No.2003 CB615700)the National Natural Science Foundation of China(No.20604005).
文摘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.
文摘A novel series of poly(aryl ether sulfone ketone)s (PPESKs) containing phthalazinone and biphenyl moieties were prepared by two-step nucleophilic polycondensation reaction. The ^-Mw values of these copolymers were between 38,330 and 67,900. The glass transition temperatures (Tg) and 5% decomposition temperatures were ranged in 253-269 ℃ and 488-500 ℃, respectively, The structures of these copolymers were confirmed by FT-IR and ^1H NMR. Moreover, all the resultant copolymers were amorphous determined by wide angle X-ray diffraction (WAXD).
基金Supported by the National Natural Science Foundation of China(No.50973040)the Science and Technology Development Plan of Jilin Province, China(No.20090322)
文摘A novel type of crosslinkable poly(aryl ether sulfone)(PAES) bearing an allyl pendant(PES-OAllyl) was synthesized by a grafting reaction of hydrophenyl-containing PAES(PES-OH) and allyl bromide. PES-OH was prepared by a demethylation reaction of a methoxyphenylated PAES(PES-OCH3) in the presence of pyridine/hydrochlo- ride. The PES-OCH3 was synthesized by an aromatic nucleophilic substitution of bis(4-chlorophenyl)sulfone and (p-methoxy)phenylhydroquinone. Both DSC and solubility investigation were used to study the crosslinking behavior of PES-OAllyl. After heat treatment, the glass transition temperature(Tg) value of PES-OAllyl sharply increased from 165 ℃ to 227 ℃. Meanwhile, PES-OAllyl changed from a soluble polymer to an insoluble thermoset. In addition, TGA(thermogravimetric analysis) result suggests that the thermal stability of the crosslinked product was improved. All the data prove that the crosslinked PES-OAllyl could be a potential solvent-resistance high-performance material.
基金This work was supported by National Science Foundation of China (No. 20264001 ), National Science Foundation of Jiangxi Province, Innovation Fund for Technology Based Firms of China (No. 06C26213601342).
文摘A series of Poly(arly ether sulfone ether ketone)s containing pendant methyl groups were synthesized by the reaction of 4,4'-[sulfonylbis (1,4-phenylene)dioxy] dibenzoyl chloride (SODBC) with 4,4'- diphenoxy diphenylsulfone (DPODPS), 4,4'- di(2-methylphenoxy) diphenylsulfone (o-Me-DPODPS), 4,4'- di(3-methylphenoxy) diphenylsulfone (m-Me-DPODPS), 4,4'- di (2,6-bimethylphenoxy) biphenylsulfone(o-Me2-DPODPS) respectively, in a mixture of 1,2-dichloroethane (DCE) and N-methylpyrrolidone (NMP). These reactions were catalyzed by anhydrous aluminum chloride (AlCl). The characteristic of copolymers were studied by means of advanced analytical techniques such as FT-IR,1H-NMR, DSC, TGA and WAXD. The results show glass transition temperature (Tg) in the range of 193-206℃, thermally stable in excess of 434℃ and excellent solubility in polar solvents. Methyl-substituted Poly(aryl ether sulfone ketone)s had higher glass transition temperatures, lower initial decomposition temperatures than the unsubstituted ones.
基金This project was supported by the National Ninth Five-Year-Plan Key Project "The pilot-scale production and the applied development of polyaryl ether concerning phthalazinone moiety" (No. 97-564-01-07).
文摘A kind of novel heat-resistant, high performance engineering thermoplastic phthalazinone poly(aryl ether sulfone ketone) (PPESK) containing a carboxyl group in its side chain was prepared by the nucleophilic displacement reaction of 4-(4-hydroxylphenyl)- 1 (2H)-phthalazinone with di(4-chlorophenyl) sulfone, 4,4'-difluoro-benzophenone and phenolphthalin in sulfolane in the presence of K2CO3 to produce high molecular weight polymers which can be dissolved in some polar solvents such as chloroform and nitrobenzene at room temperature and can be easily cast into flexible, yellowish and transparent films. PPESK is an amorphous polymer having a decomposition temperature above 400degreesC, which indicates that it has high thermal stability. At the same time, the thermal properties of PPESKs with dicyandiamide (DICY) as curing agent indicated that the heat-resistance properties of the PPESKs are improved after curing. The apparent activation energy (A-E) of the cross-linking reaction and the reaction order (n) of PPESK/DICY were found to be 52.2 kJ/mol and ca. 1.0, respectively. Therefore, the cross-linking reaction is approximately a first order reaction.
文摘A novel poly (ether sulfone ketone) containing the phthalazinone moiety was prepared by the reaction of 4-)4-hydroxyphenyl) (2H) phthalazin-1-one with activated dichloro-monomers. The polymer was characterized by FT-IR, H-1-NMR, DSC, TGA and X-ray diffraction.
基金financial support under Heilongjiang Postdoctoral Fund (No.LBH-Z09175)
文摘Novel poly(aryl ether sulfone ketone)s (PAESK) were synthesized from bisphenol A (BPA), 9,9'-bis(4-hydroxyphenyl) fluorene (BHPF), 4,4'-dichlorodiphenylsulfone (DCS) and 4,4'-difluorobenzophenone (DFB) via nucleophilic substitution polymerization, which were subsequently used to fabricate ultrafiltration membrane by phase-inversion method for high temperature condensed water treatment. The obtained high molecular weight co-polymers with fluorene group with good solubility and good thermal stability, can be easily cast into flexible, white and non-transparent fiat films. The influence of molar ratio of BPA and BHPF on the properties of the prepared co-polymers and membranes was investigated in detail. SEM study of the morphology of the membranes indicated that the prepared membranes possessed homogeneous pores on the top surface and were sponge-like or finger-like in cross-section. Pure water flux of the membranes increased from 71.87 L·m-2.h-1 to 247.65 L·m-2.h-1, while the retention of BSA decreased slightly, and the water contact angle decreased from 82.1 ° to 55.6° with the PVP concentration from 0 wt% to 10 wt%. With increasing concentration of PVP, the mechanical properties of membranes decreased, while the thermal stability increased. The permeate flux measurement showed that the PAESK membrane had the potential for high temperature condensed water treatment.
基金financially supported by the National Natural Science Foundation of China(No.51203151)the Program of Jilin Education Department(No.93201201)
文摘A series of cardo poly(aryl ether sulfone) copolymers bearing pendent sulfonic acid groups (SPES-X) have been prepared by a facile chemical graft method. The structure was confirmed by 1H-NMR spectra. The side-chain-type SPES-X membranes show significantly reduced swelling behavior and excellent mechanical properties as well as appropriate proton conductivity compared to the main-chain-type sulfonated polymers with similar ion exchange capacity (IEC) value. Moreover, they show methanol permeability in the range of 0.6 × 10^-7-5.7 × 10^-7 cmE/s which is lower than that of Nafion 117. All the results indicate that the SPES-Xmembranes are promising candidates for the direct methanol fuel cells.
基金Supported by the National Natural Science Foundation of China(Nos.51508078, 51478095)the Jilin Provincial Science and Technology Development Project of China(No.20160520023JH)+1 种基金the Science and Technology Research Project of the Jilin Provincial Education Department, China(No.JJKH20180021KJ)the Fundamental Research Funds for the Central Universities ofCliina(No.2412018ZD016).
文摘A series of novel TiO2/poly(aryl ether sulfone) ultrafiltration membranes with anti-fouling and self-cleaning properties was designed and prepared. First, anti-photocatalytic degraded fluorine contained polv(aryl ether sulfone) matrix(PAES-F) was synthesized. Then the composite membranes were prepared via TiO2 nanopartides and PAES-F polymer matrix by solution blending and non-solvent induced phase inversion methods. Further, separation efficiency, fouling behavior and self-cleaning property of the composite ultrafiltration(UF) membranes were investigated by dead-end filtration experiments using a polyacn lamide solution. The composite UF membranes exhibited outstanding self-cleaning efficiency and anti-photocatalytic degraded property after exposure to simulated sunliglit irradiation.The water flux recovery ratios(FRR)of the optimal composite UF membranes could reach 74.24%, which was attributable to photocatalytic degradation of the organic contaminant by TiO2. And the retention rates of the composite UF membranes could maintain over 97%, which indicated the excellent photocatalytic degradation resistance of the fluorine contained PAES-F matrix. The novel high perfomiance composite UF membranes have a broad application prospect in water treatment.
基金NationalNatural Science Foundation of China,Grant/Award Numbers:21701016,51803011Science and Technology Development Planning of Jilin Province,Grant/Award Number:20190103129JH+2 种基金Education Department of Jilin Province,Grant/Award Number:JJKH20200666KJChina Scholarship Council,Grant/Award Number:201802335014Welch Foundation,Grant/Award Number:B-0027。
文摘In the field of proton exchange membranes(PEMs),it is still a great challenge to explore new Nafion alternatives,maintaining the high proton conductivity and lowering the cost of practical application.In this work,a series of low sulfonated poly(aryl ether ketone sulfone)(SPAEKS)membranes hybridized by[Bi_(6)O_(5)(OH)_(3)]_(2)(NO_(3))10⋅6H_(2)O(H_(6)Bi_(12)O_(16))have been successfully fabricated.When the doping amount of H6Bi12O16 reaches 5 wt%,the DS15-Bi12-5 showing the best proton conductive ability and mechanical properties.The proton conductivity can achieve 72.8 mS⋅cm−1 at 80℃ and the tensile strength can reach 43.57 MPa.Confirmed by experimental data and activation energy(Ea)calculations,the existence of Bi cluster makes more hydrogen bonds,providing additional proton hopping sites and offers more proton transport vehicles,leading to a high proton conduction performance.This work proved that polyoxometalates(POMs)can replace the role of sulfonate groups in SPAEKS to a certain extent and work out the defects of high sulfonation,making a remarkable contribution to the practical application of low sulfonated SPAEKS.
基金supported by the National Natural Science Foundation of China(51978133,52100026,U20A20322,52170151,51978132)the Fundamental Research Funds for the Central Universities of China(2412021QD022)+1 种基金the Key Research and Development Project of Hainan Province(ZDYF2022SHFZ298)the Industrialization Cultivation Project of Jilin Provincial Department of Education(JJKH20221174CY)。
文摘The occurrence of ultrafiltration(UF)membrane fouling frequently hampers the sustainable advancement of UF technology.Reactive self-cleaning UF membranes can effectively alleviate the problem of membrane fouling.Nevertheless,the self-cleaning process may accelerate membrane aging.Addressing these concerns,we present an innovative design concept for composite self-healing materials based on self-cleaning UF membranes.To begin,TiO_(2)nanoparticles were incorporated into the polymer molecular structure via molecular design,resulting in the synthesis of TiO_(2)/carboxyl-polyether sulfone(PES)hybrid materials.Subsequently,the nonsolvent-induced phase inversion technique was employed to prepare a novel of UF membrane.Lastly,a polyvinyl alcohol(PVA)hydrogel coating was applied to the hybrid UF membrane surface to create PVA@TiO_(2)/carboxyl-PES self-healing reactive UF membranes.By establishing a covalent bond,the TiO_(2)nanoparticles were effectively and uniformly dispersed within the UF membrane,leading to exceptional self-cleaning properties.Furthermore,the water-absorbing and swelling properties of PVA hydrogel,along with its capacity to form hydrogen bonds with water molecules,resulted in UF membranes with improved hydrophilicity and active self-healing abilities.The results demonstrated that the water contact angle of PVA@5%TiO_(2)/carboxyl-PES UF membrane was 43.1°.Following a 1-h exposure to simulated solar exposure,the water flux recovery ratio increased from 48.16%to 81.03%.Moreover,even after undergoing five cycles of 12-h simulated sunlight exposure,the UF membranes exhibited a consistent retention rate of over 97%,thus fully demonstrating their exceptional self-cleaning,antifouling,and selfhealing capabilities.We anticipate that the self-healing reactive UF membrane system will serve as a pioneering and comprehensive solution for the self-cleaning antifouling challenges encountered in UF membranes while also effectively mitigating the aging effects of reactive UF membranes.
基金Supported by the National Natural Science Foundation of China(Nos.51873076,21404013)tlie Science and Technology Development Project of Jilin Province,China(Nos.20170101110JC,20180201076GX,20180201075GX)the Open Research Fund of State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,China(No.201826).
文摘A series of novel organic-inorganic hybrid proton-conducting electrolyte membranes with silane-crosslinked sulfonated poly(aryl ether ketone)(SC-SPAEK) networks was prepared via a simple procedure that includes solution casting and acid treatment. The organosilicon pendants of the silane-grafted SPAEK, which were expected to serve as coupling and crosslinking agents, were found to play a key role in the homogenous dispersion of inorganic particles and improved the performance of hybrid membranes. The hybrid membranes exhibited enhanced proton conductivity, and SC-SPAEK/TiO2-4 showed an extremely high proton conductivity of 0.1472 S/cm at 100℃. The crosslinked hybrid membranes also demonstrated good chemical resistance, oxidative stability, and mechanical properties. The crosslinked hybrid membranes with excellent comprehensive performance may be a promising material for proton exchange membrane fuel cells.
基金supported by the Natural Science Foundation of Liaoning Province of China(No.20041076)
文摘Sulfonated poly(ether ketone)s containing 3,5-dimethyl phthalazinone moieties (SPPEK-DMs) with different degrees of sulfonation (DS) were synthesized via direct polycondensation from 4-(3,5-dimethyl-4-hydroxyphenyl)-2,3- phthalazinone, 4,4'-difluorobenzophenone and 3,3'-disulfonate-4,4'-difluorobenzophenone. The chemical structure of SPPEK-DMs was characterized by FTIR and 1H-NMR. Thermal stability of SPPEK-DMs was characterized by the thermogravimetric analysis. The membranes prepared from SPPEK-DMs exhibited ion exchange capacities (IEC) ranging from 0.93 mmol.g-1 to 1.86 mmol.g-1. Water uptake, swelling, oxidative stability and methanol permeability of SPPEK- DMs membranes were investigated. SPPEK-DMs membranes exhibited high oxidative stability. The methanol permeability values of SPPEK-DMs membranes were in the range 5.15× 10^-8-6.61×10^-7 cm^2.s-1, which was much lower than those of Nafion117. The proton conductivity of SPPEK-DM40 membranes was 1.1 ×10^-2 S.cm^-1 at 70℃.