钛酸四丁酯/季铵化壳聚糖无机/有机杂化膜的制备及耐碱性
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摘要
将钛酸四丁酯(TBT)均匀地掺入到季铵化壳聚糖(QCS)中制备无机/有机杂化膜。借助红外光谱、扫描电镜等分析膜样品的结构和形貌;通过力学性能、含水率、离子交换量、电导率等性能指标进行膜性能测试。试验过程中,将膜浸渍在3 mol/L和6 mol/L的Na OH溶液中,考察不同浓度、不同时间对膜耐碱性能的影响,以此探讨其作为燃料电池电解质膜使用的可行性。结果表明,随着TBT含量的增加,膜的力学性能增加,而膜的含水率、离子交换量和电导率均呈现降低趋势。碱处理之后除了膜的含水率增加,其余各项性能指标均比相应未碱处理的膜样品有所降低,降低幅度小于5%;电导保留率随着温度升高、碱液浓度增加也在一定程度上有所降低,但均保持在90%以上,而且膜外观形貌无明显变化,说明该膜具有较好的耐碱稳定性能。
The inorganic material tetrabutyl titanate( TBT) was uniformly incorporated into quaternized chitosan( QCS),to prepare inorganic-organic hybrid membranes. The structure and morphology of sample membranes were analyzed by FT-IR and SEM,then the performance including mechanical properties,water uptake,ion exchange capacity and conductivity were tested. The membranes were impregnated in 3 mol/L and 6 mol/L NaOH solution to inspect the influence of alkali stability at different concentration and different time,and to discuss the feasibility of electrolyte membranes in fuel cell. The results show that the mechanical properties increase with increase of the TBT content,but the water uptake,ion exchange capacity( IEC) and conductivity of the hybrid membranes decrease. The other properties of membranes after alkali treatment are lower than those of the corresponding untreated membranes,except the water uptake is increased,the changed rate is not more than 5%. The conductivity retention decreases with rising of the temperature and NaOH content in some extent,but all remain above 90%,and no apparent change in appearance,indicating that the membranes have good alkali resistance.
The inorganic material tetrabutyl titanate( TBT) was uniformly incorporated into quaternized chitosan( QCS),to prepare inorganic-organic hybrid membranes. The structure and morphology of sample membranes were analyzed by FT-IR and SEM,then the performance including mechanical properties,water uptake,ion exchange capacity and conductivity were tested. The membranes were impregnated in 3 mol/L and 6 mol/L NaOH solution to inspect the influence of alkali stability at different concentration and different time,and to discuss the feasibility of electrolyte membranes in fuel cell. The results show that the mechanical properties increase with increase of the TBT content,but the water uptake,ion exchange capacity( IEC) and conductivity of the hybrid membranes decrease. The other properties of membranes after alkali treatment are lower than those of the corresponding untreated membranes,except the water uptake is increased,the changed rate is not more than 5%. The conductivity retention decreases with rising of the temperature and NaOH content in some extent,but all remain above 90%,and no apparent change in appearance,indicating that the membranes have good alkali resistance.
引文
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[16] Kan C W,Au C H. Effect of biopolishing and UV absorber treatment on the UV protection properties of cotton knitted fabrics[J]. Carbohydr. Polym.,2014,101:451-456.
[2] Brouzgou A,Podias A,Ts P,et al. PEMFCs and AEMFCs directly fed with ethanol:a current status comparative review[J]. J. Appl.Electrochem.,2013,43:119-136.
[3] Zheng H,Shi B,Ding R,et al. Composite anion exchange membrane from quaternized polymer spheres with tunable and enhanced hydroxide conduction property[J]. Ind. Eng. Chem. Res.,2016,55:9064-9076.
[4] Muzzarelli R A A,Tanfanif F. The N-permethylation of chitosan and the preparation of N-trimethyl chitosan iodide[J]. Carbohydr.Polym.,1985,5:297-307.
[5] Arthanareeswaran G,Thanikaivelan P,Srinivasn K,et al.Synthesis,characterization and thermal studies on cellulose acetate membranes with additive[J]. Eur. Polym. J.,2004,40:2153-2159.
[6] Ji L W,Quan T C,Rong H H,et al. Positively charged polystyrene blended quaternized chitosan for anion exchange membranes[J]. J.Electrochem. Soc.,2013,60:F168-F174.
[7]韩克飞,杨起涛,于书平,等.用于碱性膜燃料电池的新型聚苯醚阴离子交换膜的制备与性能[J].高等学校化学学报,2013,34(10):2437-2444.Han K F,Yang Q T,Yu S P,et al. Preparation and characterization of novel poly(2,6-dimethyl-1,4-phenylene oxide)anion-exchange membranes for alkaline fuel cells[J]. Chemical Journal of Chinese Universities,2013,34(10):2437-2444.
[8] Qiao J,Hamaya T,Okada T. New highly proton conductive polymer membrane spoly(vinylalcohol)-acrylamido-2-methyl-1-propanesulfonic acid(PVA-PAMPS)[J]. J. Mater. Chem.,2005,15:4414-4423.
[9] Feng T,Lin B,Zhang S. Imidazolium-based organic-inorganic hybrid anion exchange membranes for fuel cell applications[J]. J.Membr. Sci.,2016,508:7-14.
[10]朱子沛,汤旭,何其,等.双改性Al2O3/PVDF杂化膜的制备和性能[J].精细化工,2016,33(11):1201-1206.Zhu Z P,Tang X,He Q. Preparation and performance of modified Al2O3/PVDF hybrid membrane[J]. Fine Chemicals,2016,33(11):1201-1206.
[11]李团乐,裴洪昌,袁威津,等.苯并15-冠-5接枝聚乙烯醇制备优化及其锂同位素分离效应研究[J].高分子学报,2015(7):792-799.Li T L,Pei H C,Yuan W J. Preparation and characterization of polyvinyl alcohol copolymer grafted with 4'-formoxylbenzo-15-crown-5-ether for lithium isotopes separation[J]. Acta Polymerica Sinica,2015(7):792-799.
[12] Zhang Y,Wang J,Wang L,et al. Study on adsorption properties of QCS/PS-G 8-2-8,anion exchange membrane for Rhodamine B[J].J. Mol. Struct.,2015,1089:116-123.
[13]韩克飞,杨起涛,于书平,等.用于碱性膜燃料电池的新型聚苯醚阴离子交换膜的制备与性能[J].高等学校化学学报,2013,34(10):2437-2444.Hang K F,Yang Q T,Yu S P. Preparation and characterization of novel poly(2,6-dimethyl-1,4-phenylene oxide)anion-exchange membranes for alkaline fuel cells[J]. Chemical Journal of Chinese Universities,2013,34(10):2437-2444.
[14]王一夫,董金鑫,王璐璐,等.介孔SiO2孔道内Gemini分子有序自组装构筑正相胶束辅助传递OH-离子[J].高等学校化学学报,2017,38(1):141-149.Wang Y F,Dong J X,Wang L L,et al. Ordered self-assembly of Gemini molecules in mesoporous silica channels constructing normal micelles to assist the migration of OH-[J]. Chemical Journal of Chinese Universities,2017,38(1):141-149.
[15] Zhao Y,Pan J,Yu H,et al. Quaternary ammonia polysulfone-PTFE composite alkaline anion exchange membrane for fuel cells application[J]. Int. J. Hydrogen Energy,2013,38:1983-1987.
[16] Kan C W,Au C H. Effect of biopolishing and UV absorber treatment on the UV protection properties of cotton knitted fabrics[J]. Carbohydr. Polym.,2014,101:451-456.
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