乙酸-三氟化硼乙醚混合质子电解质

乙酸和三氟化硼乙醚(BFEE)本身离子电导率很低, 向乙酸中加入少量BFEE可以形成良好的混合质子电解质溶液. 随着乙酸中BFEE浓度的变化, 混合电解质溶液的离子电导率迅速上升, 当BFEE摩尔分数为65%时具有最大值, 达5800 μS/cm. 红外光谱和¹H NMR研究表明混合电解质中的主要导电离子为CH₃COOH₂^＋和CH₃COOBF₃^－.     

离子液体在多孔碳电极上的电化学性能

制备了数种离子液体及离子液体有机溶液电解质,用线性电位扫描法测试了它们的电化学窗口;并通过循环伏安、交流阻抗、电势阶跃等电化学方法,对它们在多孔碳电极中的电化学性能进行了研究.实验结果表明:溶剂对1-乙基-3-甲基咪唑类离子液体有机溶液电解质的电化学窗口有较大的影响.离子液体及离子液体有机溶液电解质在多孔碳电极上的电化学性能与其电导率密切相关,电导率越大,充电时间常数越小,比容量越大;但比容量降低的倍率远小于电导率降低的倍率.     

聚乙烯醇/聚乙烯吡咯烷酮碱性复合膜的制备及其性能

通过在不同浓度KOH溶液中进行掺杂,制备出了聚乙烯醇/聚乙烯吡咯烷酮(PVA/PVP)碱性聚合物电解质膜.详尽考察了膜的组成、微观结构、热稳定性、离子电导率和甲醇吸收率.结果表明,PVA与PVP两者具有较好的相容性,当m(PVA)∶m(PVP)=1∶0.5时,膜断面致密、均匀,未发生大尺度相分离.PVP的混入可以极大提高复合膜的电导率和热稳定性.当m(PVA)∶m(PVP)=1∶1时,复合膜的电导率可达2.01×10-3 S.cm-1.PVA/PVP/KOH膜的甲醇吸收率随温度的升高没有明显变化,100℃时其甲醇吸收率仅为同条件下Nafion 115膜的1/4.这表明该复合膜有望作为一种新型的碱性直接甲醇燃料电池用固体电解质膜且可提高膜的使用温度.     

9,10-二氢化菲在三氟化硼乙醚-浓硫酸混酸中的电化学聚合

在三氟化硼乙醚(BFEE)-浓硫酸混合电解质体系中直接氧化9,10-二氢化菲获得了高质量聚(9,10-二氢化菲)膜, 其电导率为3.8×10－1 S/cm. 9,10-二氢化菲在BFEE＋10%浓硫酸体系中的起始氧化电位为0.93 V vs. SCE, 远低于其在乙腈＋0.1 mol/L Bu4NBF4溶液中的起始氧化电位(1.75 V vs. SCE). 在BFEE＋10%浓硫酸体系中获得的聚(9,10-二氢化菲)膜具有良好的电化学性质. 聚合物部分溶于二甲基亚砜、四氢呋喃、氯仿等极性溶剂. FT-IR和量化计算表明聚合反应主要发生在2, 7位或者3, 6位. 荧光光谱和热重分析表明聚合物是一种良好的蓝色荧光材料且具有良好的热稳定性.     

9,9-二乙基芴在三氟化硼乙醚中的电化学聚合

在三氟化硼乙醚(BFEE)中,9,9-二乙基芴(DEF)直接阳极氧化聚合可以获得高质量聚(9,9-二乙基芴)膜(PDEF,电导率2×10-2S.cm-1).DEF在BFEE中的起始氧化电位为1.20 VvsSCE,远低于单体在0.1 mol.L-1Bu4NBF4的CH3CN溶液中的起始氧化电位(1.70 V).在BFEE中获得的PDEF膜具有良好的电化学性质.红外光谱和1H NMR结果表明聚合反应主要发生在2,7位.     

电导率和摩尔电导率与浓度关系的教学讨论

根据电导率和摩尔电导率的物理意义,通过简单计算,确定了参与导电的离子数目与电解质溶液浓度或电离度之间的关系,由此分析说明了电导率和摩尔电导率与电解质浓度的关系。方法简单清晰,便于学生领会理解。     

离子的本性对溶液导电能力的影响

借助电导率传感器探究向硫酸氢钠溶液中滴入氢氧化钡溶液时溶液导电能力的变化,并对实验结果进行理论分析与解释：电解质溶液的导电能力由离子本性决定,受离子浓度等影响。     

分子凝胶电解质的电导率研究

凝胶因子4,4'-二(硬脂酰胺基)二苯醚(BSDE)在水和非水介质(如二甲基甲酰胺、二甲基亚砜、碳酸丙烯酯等)中利用非共价键相互作用自组装成有序的三维纤维网络结构,使介质凝胶化.该凝胶被称之为分子凝胶.同样,BSDE也能使锂盐溶液凝胶化,制备一种新型分子凝胶电解质.水分子凝胶锂离子电解质的室温离子电导率达到10^-1～10^-2S·cm^-1,碳酸丙烯酯分子凝胶锂离子电解质的室温离子电导率也能达到10^-2～10^-3S·cm^-1.分子凝胶的离子电导率研究表明,锂盐在凝胶中的行为和其在溶液中的行为相似.在-35℃的低温下,分子凝胶的电导率与其溶液相比约低1～2个数量级.     

PEO-LiClO4-ZSM-5复合聚合物电解质——ZSM-5对锂离子选择通过的影响

通过溶液浇铸法制得了一系列以不同分子筛和蒙脱土为填料的PEO基复合聚合物电解质,利用交流阻抗-稳态电流方法研究了填料对复合聚合物电解质锂离子迁移数(TLi+)的影响.实验结果表明,所有填料都有利于同时提高复合聚合物电解质的TLi+和离子电导率,但以Li-ZSM-5为填料时TLi+最高,这是因为ZSM-5的特殊二维孔道结构有利于阳离子Li+的进入,而排斥阴离子ClO4-的通过.较高的TLi+和室温离子电导率说明PEO-LiClO4-ZSM-5有可能作为全固态锂离子聚合物电池的电解质材料.     

PEO-LiClO_4-ZSM5复合聚合物电解质II.ZSM-5对离子电导率的影响

通过XRD ,DSC ,FT IR和SEM等方法对PEO LiClO4 ZSM5复合电解质进行了研究 ,结果表明ZSM 5可以有效地降低PEO LiClO4 ZSM5复合电解质中PEO的结晶度和玻璃化温度 ,从而提高其低温区域的离子电导率 .温度高于PEO的结晶熔融温度后 ,复合电解质离子电导率的提高则是由于在ZSM 5表面形成了有利于Li离子迁移的导电通道所引起的 .较高的离子电导率和较宽的电化学稳定窗口表明PEO LiClO4 ZSM5复合电解质在全固态锂离子二次电池领域具有良好的应用前景 .     

1H NMR spectral studies on the polymerization mechanism of indole and its derivatives

The existence of NH bond according to the hydrogen nuclear magnetic resonance ((1)H NMR) spectra of polyindole and its derivatives, such as poly(5-bromoindole), poly(5-cyanoindole), poly(5-nitroindole), poly(5-methylindole), proved polymerization of high-quality polyindoles, which were electrosynthesized from middle strong Lewis acid boron trifluoride diethyl etherate (BFEE) and its mixed electrolytes with additional diethyl ether, occurred at 2,3-position. The elongation of the conjugation length made the chemical shift of all the protons of polyindoles to lower field in comparison with those of monomers.     

ELECTROCHEMICAL POLYMERIZATION OF 5-CYANOINDOLE IN MIXED ELECTROLYTES OF BORON TRIFLUORIDE DIETHYL ETHERATE AND DIETHYL ETHER

High quality poly（5-cyanoindole） （P5CI） films were electrosynthesized by direct anodic oxidation of 5-cyanoindole on stainless steel sheet in the mixed electrolytes of boron trifluoride diethyl etherate （BFEE） and diethyl ether （EE） （by volume 1：1） ＋ 0,05 mol L^-1 Bu4NBF4. The film formed can be peeled off the electrode into freestanding films, The addition of EE into BFEE can improve the solubility of monomer. P5CI films obtained from this medium showed excellent electrochemical behavior with conductivity of 10^-2 S cm^-1, Structural studies showed that the polymerization of 5-cyanoindole occurred at the 2,3 position. As-formed P5CI films were thoroughly soluble in strong polar organic solvent dimethyl sulfoxide （DMSO） while partly soluble in tetrahydrofuran （THF） or acetone. Fluorescence spectral studies indicated that P5CI was a good blue-ight emitter.     

ELECTROCHEMICAL COPOLYMERIZATION OF 3-（4-FLUOROPHENYL）THIOPHENE AND 3-METHYLTHIOPHENE IN BORON TRIFLUORIDE DIETHYL ETHERATE

The copolymer poly（3-（4-fluorophenyl）thiophene-co-3-methylthiophene） was successfully prepared from mixtures of 3-（4-fluorophenyl）thiophene （FPT） and 3-methylthiophene （MET） via electrochemical oxidation in boron trifluoride diethyl etherate （BFEE） and its mixed electrolytes with acetonitrile （ACN）. The influence of monomer concentration ratios on the copolymerization was investigated by using linear sweep voltammetry and cyclic voltammetry. The structure and morphology of these copolymer films were elucidated by UV-Vis, infrared spectroscopy, elemental analysis, thermal analysis and scanning electron microscopy （SEM）, respectively. The results showed that the molar ratio of FPT and MeT units, when copolymer was electrodeposited from feed ratio of FPT：MeT = 1：2, was about 1.08：1. In addition, the introduction of ACN into BFEE has little effect on the properties of as-formed copolymers.     

邻二取代苯电化学氧化聚合的实验及理论计算研究

用电化学阳极氧化方法尝试了一系列邻二取代苯衍生物的聚合反应,结果表明在三氟化硼乙醚(BFEE)溶液中邻苯二酚(oHDB)、邻二甲氧基苯(oDMOB)、1-羟基-2-甲氧基苯(HMOB)能够电化学聚合并获得聚合物,而其它邻二取代苯单体无法用此方法获得聚合物.NMR分析和理论研究证明oHDB、oDMOB、HMOB的聚合位点发生在(C4,C5)位.用密度泛函理论对单体进行分子轨道和负电荷密度分析,表明邻二取代苯单体进行电化学氧化聚合并获得聚合物满足至少两个条件,即聚合位点HOMO-LUMO满足轨道对称性匹配且能隙最小;负电荷密度绝对值高于某一临界值(估计为|0.09|).     

三氟化硼乙醚溶液中聚(二苯并呋喃)的电化学合成

在三氟化硼乙醚-硫酸混合电解质溶液中,二苯并呋喃直接阳极氧化聚合可以获得高质量聚(二苯并呋喃)膜.二苯并呋喃在纯三氟化硼乙醚中的起始氧化电位为1.30 VvsSCE,远低于单体在0.1 mol.L-1Bu4NBF4乙腈溶液中的起始氧化电位(2.14 V).硫酸的加入进一步降低了二苯并呋喃的氧化电位.在三氟化硼乙醚-硫酸混合电解质溶液中,二苯并呋喃的起始氧化电位可降低至1.0 V;同时在该体系中获得的聚(二苯并呋喃)膜具有良好的电化学性质和荧光性质.     

N,N-dihalophosphoramides-XVI: Ionic addition of diethyl n,n-dibromophosphoroamidate (DBPA) to alkenes and cycloalkenes

The addition of DBPA to a variety of phenylethylenes, straight-chain terminal and nonterminal alkenes as well as cycloalkenes in the presence of boron trifluoride etherate has been investigated. It was found that the reaction proceeds smoothly at -20° by adding an olefin to the solution of equimolar amounts of DBPA and boron trifluoride etherate in tetrachloromethane. N-Bromoadducts (mixtures or single isomers depending upon the structure of the olefin) initially formed could be reduced in situ with sodium bisulphite solution to give the corresponding diethyl N-(β-bromoalkyl)phosphoroamidates which in turn afforded β-bromoamine hydrochlorides upon treatment with hydrogen chloride in benzene at room temperature. The regiospecificity typical for Markovnikov addition, as proven by NMR and MS evidence, was observed for unsymmetrical phenylethylenes. The addition of DBPA to (E)-1-phenylpropene, (E)-2-butene, and (Z)-2-butene was also found to proceed stereospecifically affording the corresponding anti-adducts. These results are fully compatible with an ionic addition pathway and can be rationalized by assuming the intermediate formation of an electrophilic complex between DBPA and boron trifluoride. The reaction offers a new approach to aminobromination of alkenes and cycloalkenes and makes possible an easy access to β-bromoamines, the convenient precursors of aziridines.     

BF3·Et2O catalyzed intramolecular cyclization of diethyl 2-(dialkoxyphosphorylethynyl)-2-arylaminomalonates to 3-phosphonylated indoles

The boron trifluoride diethyl etherate catalyzed intramolecular cyclization of diethyl 2-(dialkoxyphosphorylethynyl)-2-arylaminomalonates afforded a series of novel 3-phosphonylated indoles, diethyl 2-[3-(dialkoxyphosphoryl)-1H-indol-2-yl]propanedioates. Decarboxylation of the latter compounds resulted in the formation of ethyl 2-[3-(dialkoxyphosphoryl)-1H-indol-2-yl]acetates.     

Direct conversion of tert-butyl 2-hydroxyalkyl sulfides to 1,3-oxathiolanes

tert-Butyl 2-hydroxyalkyl sulfides, prepared by reaction of epoxides with 2-methylpropane-2-thiol, are converted directly to 1,3-oxathiolanes upon treatment with pivalaldehyde and boron trifluoride diethyl etherate in the presence of thioanisole.     

Synthesis of glycosyl dipyrromethanes

Treatment of peracetylated sugar trichloroacetimidates with dipyrromethane in the presence of boron trifluoride diethyl etherate gave peracetylated glycosyl dipyrromethanes in good yields. Regio- and stereo-selectivity of the glycosylation reactions were established.