纳米TiO_2增强阴离子导电膜中碱性离子液体稳定性
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摘要
以N-甲基吡咯为原料,通过两步法合成碱性甲基吡咯烷离子液体([DMPy]OH)。通过物理掺杂方式在聚乙烯醇(PVA)膜基质中引入碱性离子液体[DMPy]OH和纳米二氧化钛(Nano-TiO_2),然后引入戊二醛(GA)交联PVA,制得PVA-[DMPy][OH]-TiO_2复合膜。借助X射线衍射(XRD)和Mapping(元素分析)测试证实了Nano-TiO_2和[DMPy]OH间自组装作用的存在。对复合膜的机械性能、热稳定性能、电导率、耐碱性等指标进行了测试。结果表明,该系列复合膜形貌平整、均一;当离子液体质量分数为25%、Nano-TiO_2质量分数为1%、80℃时,PVA-[DMPy][OH]-TiO_2复合膜的电导率(σ)为2.78×10-3 S/cm,室温下水中浸渍12 h后,离子液体流失率为23.2%;与未添加Nano-TiO_2的PVA-[DMPy][OH]膜相比,80℃时电导率提高了19.3%,室温下离子液体流失率降幅约34.3%;室温下,3 mol/L KOH水溶液中耐碱性测试120 h后,电导率和初始值相比并无明显变化,具有优异的耐碱稳定性。热稳定性测试结果表明,该膜分解温度高于200℃,具有良好的热稳定性。
A new pyrrolidonium ionic liquid([DMPy]OH) was synthesized with 1-methylpyrrolidine as a raw material via two-step method.Subsequently,[DMPy]OH and nano titanium dioxide(Nano-TiO_2) were introduced into polyvinyl alcohol(PVA) as matrix by physical doping,and then glutaraldehyde(GA) was used to cross-link PVA to obtain PVA-[DMPy] [OH]-TiO_2 composite membrane.The existence of selfassembly between Nano-TiO_2 and [DMPy]OH was confirmed by X-ray diffraction(XRD) and Mapping.The mechanical properties,thermal stability,conductivity,alkali resistance,and other properties of the composite membrane were also tested.The result indicated that the morphology of PVA-[DMPy]OH]-TiO_2 composite membrane was uniform.When the mass fraction of [DMPy]OH and Nano-TiO_2 was 25% and 1%,respectively,the prepared PVA-[DMPy][OH]-TiO_2 composite membrane had a conductivity of 2.78× 10-3 S/cm at 80 ℃.After the PVA-[DMPy][OH]-TiO_2 composite membrane was immersed in water for 12 h at room temperature,its ionic liquid loss rate was 23.2%.Compared with the PVA-[DMPy][OH] composite membrane without Nano-TiO_2 addition,the conductivity of PVA-[DMPy][OH]-TiO_2 composite membrane increased by 19.3% at 80 ℃,and the loss rate of ionic liquid decreased by 34.3% at room temperature.No obvious variety in conductivity was observed for the composite membrane after immersing in 3 mol/L KOH aqueous solution at room temperature,showing that the composite membrane had excellent alkali stability.TGA analysis revealed that this composite membrane exhibited good thermal stability,its initial decomposition temperature was higher than 200 ℃.
A new pyrrolidonium ionic liquid([DMPy]OH) was synthesized with 1-methylpyrrolidine as a raw material via two-step method.Subsequently,[DMPy]OH and nano titanium dioxide(Nano-TiO_2) were introduced into polyvinyl alcohol(PVA) as matrix by physical doping,and then glutaraldehyde(GA) was used to cross-link PVA to obtain PVA-[DMPy] [OH]-TiO_2 composite membrane.The existence of selfassembly between Nano-TiO_2 and [DMPy]OH was confirmed by X-ray diffraction(XRD) and Mapping.The mechanical properties,thermal stability,conductivity,alkali resistance,and other properties of the composite membrane were also tested.The result indicated that the morphology of PVA-[DMPy]OH]-TiO_2 composite membrane was uniform.When the mass fraction of [DMPy]OH and Nano-TiO_2 was 25% and 1%,respectively,the prepared PVA-[DMPy][OH]-TiO_2 composite membrane had a conductivity of 2.78× 10-3 S/cm at 80 ℃.After the PVA-[DMPy][OH]-TiO_2 composite membrane was immersed in water for 12 h at room temperature,its ionic liquid loss rate was 23.2%.Compared with the PVA-[DMPy][OH] composite membrane without Nano-TiO_2 addition,the conductivity of PVA-[DMPy][OH]-TiO_2 composite membrane increased by 19.3% at 80 ℃,and the loss rate of ionic liquid decreased by 34.3% at room temperature.No obvious variety in conductivity was observed for the composite membrane after immersing in 3 mol/L KOH aqueous solution at room temperature,showing that the composite membrane had excellent alkali stability.TGA analysis revealed that this composite membrane exhibited good thermal stability,its initial decomposition temperature was higher than 200 ℃.
引文
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[2]Zhu X,Wang B,Wang H.Effects of[Bmim]OH on structure and conductive properties of alkaline PVA/[Bmim]OH membranes[J].Polymer Bulletin,2010,65(7):719-730.
[3]Yi S,Zhang F,Wei L,et al.Anhydrous elevated-temperature polymer electrolyte membranes based on ionic liquids[J].Journal of Membrane Science,2011,366(1):349-355.
[4]Che Q,Zhou L,Wang J.Fabrication and characterization of phosphoric acid doped imidazolium ionic liquid polymer composite membranes[J].Journal of Molecular Liquids,2015,206:10-18.
[5]Chu F,Lin B,Yan F,et al.Macromolecular protic ionic liquid-based proton-conducting membranes for anhydrous proton exchange membrane application[J].Journal of Power Sources,2011,196(19):7979-7984.
[6]Wang S,Cao Z,Li S,et al.A molecular dynamics simulation of the structure of ionic liquid([BMIM][PF6])/rutile(110)interface[J].Scientia Sinica:Chimica(中国科学:化学),2009,52(9):1434-1437.
[7]Meng H,Chen X W,Wang J H.One-pot synthesis of N,N-bis[2-methylbutyl]imidazolium hexafluorophosphate-TiO2 nanocomposites and application for protein isolation[J].Journal of Materials Chemistry,2011,21(38):14857-14863
[8]Chang H C,Chang S C,Hung T C,et al.A high-pressure study of the effects of TiO2 nanoparticles on the structural organization of ionic liquids[J].Chromosome Research An International Journal on the Molecular Supramolecular and Evolutionary Aspects of Chromosome Biology,2011,10(7):571-577.
[9]Zhang Min(张敏),Yang Yu(杨鱼),Li Chengtao(李成涛),et al.Preparation and properties of fast water absorption PVA/HEC porous composites[J].Fine Chemicals(精细化工),2017,34(5):505-512.
[10]Macfarlane D R,Forsyth S A,Golding J,et al.Ionic liquids based on imidazolium,ammonium and pyrrolidinium salts of the dicyanamide anion[J].Green Chemistry,2002,4(5):444-448.
[11]Chu Y,Chen Y,Chen N,et al.A new method for improving the ion conductivity of anion exchange membranes by using TiO2nanoparticles coated with Ionic liquid[J].Rsc Advances,2016,6(99):96768-96777.
[12]Liu He(柳鹤),Wang Suli(王素力),Jiang Luhua(姜鲁华),et al.The stability of poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether)based anion exchange membranes used for alkaline fuel cell[J].Scientia Sinica:Chimica(中国科学:化学),2011,41(12):1857-1863.
[13]Fu J,Lin R,Lv H,et al.Preparation and properties of poly(vinyl alcohol)/poly(vinyl pyrrolidone)composites for solid alkaline electrolyte membranes[J].Acta Physico-Chimica Sinica,2010,26(10):2653-2658.
[14]Qiao J,Takeo Hamaya A,Okada T.Chemically modified poly(vinyl alcohol)-poly(2-acrylamido-2-methyl-1-propanesulfonic acid)as a novel proton-conducting fuel cell membrane[J].Chemistry of Materials,2005,17(9):2413-2421.
[15]Tang D P,Pan J,Lu S F,et al.Alkaline polymer electrolyte fuel cells:Principle,challenges,and recent progress[J].Scientia Sinica:Chimica(中国科学:化学),2010,53(2):357-364.
[16]Wang Y,Wan H,Wang J,et al.Hydroxide ion highway constructed by orderly aligned quaternary ammonium groups in anion exchange membranes[J].Journal of the Electrochemical Society,2017,164(12):F1051-F1062.
[17]Kan C W,Au C H.Effect of biopolishing and UV absorber treatment on the UV protection properties of cotton knitted fabrics[J].Carbohydrate Polymers,2014,101(1):451-456.
[18]Li Tuanle(李团乐),Pei Hongchang(裴洪昌),Yuan Weijin(袁威津),et al.Preparation and characterization of polyvinyl alcohol copolymer grafted with 4'-formoxylbenzo-15-crown-5-ether for Lithium isotopes separation[J].Acta Polymerica Sinica(高分子学报),2015,(7):792-799.
[19]Zhu Zipei(朱子沛),Tang Xu(汤旭),He Qi(何其).Preparation and performance of modified Al2O3/PVDF hybrid membrane[J].Fine Chemicals(精细化工),2016,33(11):1201-1206,1211.
[20]Sun Fengyu(孙奉玉),Wu Ming(吴鸣).Relationship between optical surface properties and photo catalytic activity of titanium dioxide[J].Chinese Journal of Catalysis(催化学报),1998,19(2):121-124.