含有不同卤素阴离子的离子液体作为倒置聚合物太阳电池阴极界面层的研究

采用离子液体作为阴极界面层来制备高效的倒置聚合物太阳电池,并考察了含有不同卤素阴离子的离子液体对器件光电转换效率的影响规律.由1-苄基-3-甲基咪唑阳离子和卤素阴离子组成的离子液体作为阴极界面层、PBDTTT-C:PC71BM作为活性层制备的倒置器件,光电转换效率达到6.55%,高于不采用离子液体作为阴极界面层的器件效率;当采用PTB7-Th:PC71BM作为活性层时,可获得8.24%的光电转换效率.离子液体通过界面偶极作用可以有效降低电极和活性层之间的接触势垒,减小串联电阻,从而提高器件效率.同时,发现碘离子作为阴离子的1-苄基-3-甲基咪唑离子液体比含氯离子、溴离子的1-苄基-3-甲基咪唑离子液体作为阴极界面层更有利于提高倒置器件的光伏性能.     

硬脂酸二茂铁酯L-B膜修饰SnO2电极的阻抗研究

测定了二茂铁衍生物——硬脂酸二茂铁酯L-B膜修饰SnO₂电极在Fe(CN)₆^3-/4-溶液中的阻抗性能,用单纯形法求出了等效电路中的元件参数值,计算了电极反应速度常数K_s。从分析SnO₂电极修饰不同层的硬脂酸二茂铁酯L-B膜的界面阻抗和电极反应的动力学性能,表明与在固相中研究的硬脂酸二茂铁酯L-B膜的阻抗性能明显不同,在Fe(CN)₆^3-/4-溶液中表现了电活性分子修饰电极的界面阻抗行为,进一步证实了修饰在SnO₂电极上的硬脂酸二茂铁酯L-B膜在Fe(CN)₆^3-/4-的氧化还原电极反应过程中,起电荷传递的中介作用。     

二茂铁衍生物L—B膜修饰SnO2电极的性能

用外层单电子快速转移的氧化还原剂二茂铁及其衍生物修饰电极,在电极/溶液界面作为电子传递的中介物,可使电极上进行的慢反应得到加速、起中介催化作用。目前研究较多的是共价键合和高分子膜的修饰,其他方式的修饰报道不多。用能实现分子有序化排列的L-B膜技术进行氧化还原电活性分子的修饰电极还未见报道。我们用L-B膜技术在SnO_2电极上修饰了二茂铁的衍生物-硬脂酸二茂铁酯(FcOCOC_(17)H_(35))双亲化合物,曾研究了修饰膜的电化学可逆行为和稳定性。本文研究硬脂酸二茂铁酯L-B膜修饰的SnO_2电极     

离子液体中PMBA脱羧反应及界面水影响的电化学SERS研究

基于气-液界面自组装法和转移技术制备了负载Au纳米粒子单层膜的玻碳电极（Au MLF@GC）,并将其用于离子液体-电化学体系界面过程现场的研究.以对巯基苯甲酸（PMBA）的表面等离激元共振（SPR）催化脱羧生成苯硫酚（TP）反应为探针,采用电化学-表面增强拉曼光谱（SERS）技术,通过电位阶跃法研究了其在离子液体体系中的反应动力学行为.结果表明,亲水性离子液体[BMIm]BF4/Au MLF@GC的零电荷电位（pzc）为-0.95 V, PMBA脱羧反应仅在pzc以正区间发生;通过SERS谱峰强度变化以二级反应拟合获得该反应的速率常数,发现其反应速率常数的对数与阶跃后电位呈线性关系;随着体系外加水的含量（摩尔分数）由0增至0.001和0.003,阶跃后发生脱羧反应的起始电位负移,且同一阶跃电位下反应速率常数随着外加水量的增加而增大.     

新型二茂铁甲基季铵盐离子液体的合成与表征

以二茂铁与二甲胺为原料合成了碘化二茂铁甲基季铵盐,再经复分解反应得到乙酸二茂铁甲基季铵盐离子液体;表征了离子液体的结构,测定了其熔点和溶解性.结果表明,合成的乙酸二茂铁甲基季铵盐离子化合物熔点低于100℃,是一种新型的二茂铁甲基季铵盐离子液体.     

添加剂对染料敏化太阳电池电解质性能的影响

以N-甲基咪唑、苯并咪唑、叔丁基吡啶和离子液体1-甲基-3-乙基咪唑三氟乙酸盐(EMITA)作为染料敏化太阳电池(DSCs)电解质溶液中的添加剂, 使用超微电极通过循环伏安法研究其对液体电解质中I-3和I-氧化还原行为的影响, 通过电化学阻抗谱研究了上述四种添加剂对Pt电极电解质界面的影响. 结果表明, 添加剂EMITA的加入使I-3在电解质中的扩散系数减小, Pt电极电解质界面上的界面传输电阻Rct增大, 电解质的电阻降低; 光伏性能测试表明, EMITA的添加提高了DSCs的开路电压和填充因子, 其DSCs的光电转换效率达到了5.72%.     

二茂铁基-1,1’-二烷基二茂铁甲醇的合成与性质

10种二茂铁甲酰基 -1 ,1 -二烷基二茂铁经 Li Al H4还原得到 1 0种相应的二茂铁基 -1 ,1 -二烷基二茂铁甲醇 .这类羟基化合物对酸的敏感性很高 .由 2种二茂铁基 -1 ,1 -二乙基二茂铁甲醇与 BF3在二氯甲烷中反应形成了稳定的二茂铁基 -1 ,1 -二乙基二茂铁甲基碳正离子 .无需从反应混合物中分离 ,该离子与乙胺作用得到了 2种 N-取代产物 .由元素分析、红外光谱和核磁共振氢谱证实了化合物的结构     

用三电极系统研究水/硝基苯界面上的电荷转移反应

将含有氧化还原电对的水溶液滴涂在铂电极上, 然后将该电极插入到硝基苯溶液中, 与参比电极和对电极构成常规的三电极系统. 利用该系统研究了水相与硝基苯相之间界面上的离子转移和电子转移反应. 以铁氰化钾/亚铁氰化钾为电对观察到钾离子在水/硝基苯界面上的转移反应以及铁氰化钾与二茂铁之间的电子转移反应；以硫酸铁/硫酸亚铁为电对观察到锂离子、钠离子、氢离子、铵离子和钾离子在水/硝基苯界面的转移. 利用该方法得到的离子的转移式电位和Gibbs转移能与用四电极系统和其他方法所测定的结果相接近.     

室温离子液体电解液中尖晶石LiMn_2O_4的电化学性质

应用循环伏安、恒电流充放电和电化学阻抗技术研究了尖晶石L iMn2O4于室温离子液体电解液中的电化学性质.实验表明,以室温离子液体作电解液,L iMn2O4的首次放电容量可达108.2 mAh/g、循环效率高于90%,温度和电流密度显著影响电极的电化学性能.交流阻抗测定了L i+在电极/电解液相界面迁移的活化能,为55 kJ/mol.根据界面反应的高活化能解释了L iMn2O4在该离子液体电解液中低温性能和倍率充放电性能不佳的原因.     

双通道微米管支撑的微-液/液界面上电荷转移反应的研究

将有机相和水相分别灌入双通道玻璃微米管θ管中的一个管中,利用θ管表面的亲水特征,在灌有有机相的微米管口附近形成微-液/液界面.利用循环伏安法研究了电荷在这种微-液/液界面上的转移反应,包括简单离子(四甲基铵离子TMA⁺)转移、加速离子转移(DB18C6加速K⁺离子)和电子转移(二茂铁/铁氰化钾+亚铁氰化钾体系)反应过程.结果表明,这种双通道微米管所得到的微-液/液界面具有不对称扩散场的特性.此装置是目前最简单的可用于研究液/液界面上的电荷转移反应的装置之一,即所谓的可进行"无溶液"液/液界面电化学及电分析化学研究的装置.     

基于室温离子液体的电导型气体传感器

本文利用室温离子液体对水或有机蒸气吸收后其离子导电性的改变,研制了以离子液体BmimPF6为敏感材料的电导型气体传感器.考查了BmimPF6用量对传感器响应的影响,测定了传感器对不同浓度的水蒸汽及乙醇、二氯甲烷等饱和有机蒸气的响应.实验结果显示,该传感器具有制作方便、结构简单、稳定性高及线性范围宽等优点,可被用于不同浓度的水或有机蒸气/氮气混合气氛中,水蒸汽或有机蒸气浓度的测定.此外,还针对该传感器对乙醇等不同饱和有机蒸气响应信号与这些有机溶剂的理化性质参数间的定量关系,采用化学计量学方法进行了建模分析.     

乙酰胺-氯化锌新型离子液体的合成及物化性质

合成了CH3CONH2-ZnCl2体系离子液体;利用红外光谱仪分析了CH3CONH2-ZnCl2离子液体的化学特征,采用步冷曲线法绘制了CH3CONH2-ZnCl2二元体系熔点图,测定了其物化性质.结果表明,CH3CONH2-ZnCl2二元体系的最低熔点为8℃;当CH3CONH2与ZnCl2的摩尔比为3:1时,Zn2+...     

An abnormal resonance light scattering arising from ionic-liquid/DNA/ethidium interactions

In the aqueous phase, ethidium bromide (EB) intercalates into the double helix structure of dsDNA (ds=double-stranded) with a notable enhancement in fluorescence and resonance light scattering (RLS). However, when dsDNA was extracted into an ionic liquid (IL), 1-butyl-3-methylimidazolium hexafluorophosphate (BmimPF(6)), an abnormal RLS arising from the interactions of IL-DNA-EB was observed, with a substantial decrease of the recorded RLS. The cationic Bmim(+) groups of BmimPF(6) intercalate into the DNA helix structure, in which they interact with the P-O bonds of phosphate groups in DNA strands and result in a reduction of the base-pair interstice along with transformation of DNA conformations that consequently prohibits the intercalation of EB with DNA. Thus, in the IL phase, the interactions between ethidium and DNA were dominated by electrostatic interactions and hydrogen bonding, leading to a congregation of EB entities around the DNA strands that results in an increase of absorption by ethidium, and consequently the inner filter effect leads to a reduction of the RLS. The present observation has been applied to the direct quantification of DNA in an ionic-liquid phase after DNA from human whole blood was extracted into BmimPF(6).     

水合肼在BmimPF_6银电极上的电化学行为研究

应用电化学循环伏安法,以银作工作电极研究了水合肼在离子液体BmimPF6中的氧化过程.结果显示,银离子对水合肼的氧化过程具有催化作用,其氧化峰电位0.16V(vs.SCE)电催化反应速率决定步骤为1电子的氧化还原过程.在0～3.4mmol/L肼浓度范围内,催化反应峰电流与肼浓度间具有良好的线性关系.     

N-centered hexazirconium chloride clusters: excision and redox chemistry

The tightly cross-linked solid Zr(6)Cl(15)N yields [(Zr(6)NCl(12))Cl(6)](3-) upon heating with bis(triphenylphosphine)iminium chloride (PPNCl), in MeCN at 90 degrees C. Purple solutions containing [(Zr(6)NCl(12))Cl(6)](3-) were obtained and characterized with (15)N NMR. Cyclic voltammetric (CV) measurements on the series of [(Zr(6)ZCl(12))Cl(6)](n-) cluster ions (Z = Be, B, C, and N) in acetonitrile reveal that these cluster ions exhibit multiple reversible redox waves at potentials that can be systematically understood, including a reversible redox wave corresponding to the [(Zr(6)NCl(12))Cl(6)](3-/4-) couple. Preparation of the reduced cluster ion, [(Zr(6)NCl(12))Cl(6)](4-), (with 15 cluster-bonding electrons) was achieved by reduction of [(Zr(6)NCl(12))Cl(6)](3-) with (C(5)(CH(3))(5))(2)Co. Several new N-centered cluster complexes: (PPN)(3)[(Zr(6)NCl(12))Cl(6)].CH(2)Cl(2), [(C(5)(CH(3))(5))(2)Co(+)](3)[(Zr(6)NCl(12))Cl(6)], and (Et(4)N)(4)[(Zr(6)NCl(12))Cl(6)].2CH(3)CN have been isolated and structurally characterized.     

Synthesis and characterization of ionic liquids incorporating the nitrile functionality

A series of imidazolium salts with the nitrile functional group attached to the alkyl side chain, viz. [CnCNmim][X] (where CnCNmim is the 1-alkylnitrile-3-methylimidazolium cation and Cn= (CH2)(n), n = 1-4; X = Cl, PF(6), and BF(4)) and [C3CNdmim][X] (where CnCNdmim is the 1-alkylnitrile-2,3-dimethylimidazolium cation and C(n) = (CH2)(n), n = 3; X = Cl, PF(6), and BF(4)), have been prepared and characterized using spectroscopic methods. The majority of the nitrile-functionalized imidazolium salts can be classed as ionic liquids since they melt below 100 degrees C. Four of the imidazolium salts have been characterized in the solid state using single-crystal X-ray diffraction analysis to reveal an extensive series of hydrogen bonds between H atoms on the cation and the anion. The relationship between the solid-state structure and the melting point is discussed. Key physical properties (density, viscosity, and solubility in common solvents) of the low melting ionic liquid have been determined and are compared with those of the related 1-alkyl-3-methylimidazolium and 1-alkyl-2,3-dimethylimidazolium ionic liquids. It was envisaged that these ionic liquids could act as both solvent and ligand for catalyzed reactions, and this application is demonstrated in hydrogenation reactions, which show that retention of the catalyst in the ionic liquid during product extraction is extremely high.     

聚苯乙烯-co-聚(2,3,4,5,6-五氟苯乙烯)共聚物: 合成及其多孔薄膜的制备

利用原子转移自由基聚合(ATRP)方法, 分别在三氟甲苯、含氟离子液体以及三氟甲苯/含氟离子液体混合溶剂体系中合成了聚苯乙烯-co-聚(2,3,4,5,6-五氟苯乙烯)(PS-co-PPFS)共聚物, 通过¹H NMR、¹⁹F NMR、元素分析以及凝胶渗透色谱法(GPC)对所得聚合物的分子链结构和组成进行了分析和表征. 随后, 利用静态呼吸图法分别在CS₂, CHCl₃ 和CH₂Cl₂ 中制备了有序多孔薄膜, 用扫描电子显微镜(SEM)观察其表面形貌, 并与利用分子量大小相当的聚苯乙烯均聚物(PS)制备的多孔薄膜进行了对比. 研究结果表明: 在三氟甲苯和含氟离子液体溶剂体系中, 均可利用ATRP 聚合方法获得窄分子量分布的PS-co-PPFS 共聚物(M_n＝5200～7900 g·mol^-1, i>M_w/M_n＝1.12～1.22). 对聚合物薄膜的扫描电子显微镜(SEM)观察和分析显示: 分别以CS₂, CHCl₃ 和CH₂Cl₂ 作为溶剂, 利用静态呼吸图法均可制备出PS-co-PPFS 共聚物多孔薄膜. 然而, 与在CHCl₃ 和CH₂Cl₂ 中制备的PS 均聚物多孔薄膜的表面形貌不同的是, PS-co-PPFS 共聚物多孔薄膜呈现出无序排列、平均孔径大小不同的两种孔结构; 在CHCl₃ 中制备所得薄膜的孔结构有序性相对较好, 两种孔的平均孔径分别为0.75 和0.37 μm.     

Michael addition of thiols to alpha-enones in ionic liquids with and without organocatalysts

Seventeen organocatalyts were tested for their ability to catalyst the addition of thiophenols to chalcones in [bmim]PF6. The products were isolated in high yield after a short reaction time, but no stereoselectivity was observed. The reactions also proceeded (without any stereoselectivity) in four other ionic liquids. In contrast, 16% and 26% ee were observed when L-proline and cinchonine, respectively, were used as the catalysts in CH2Cl2. Addition of thiophenols is also catalysed by HCl, as well as D-mandelic and L-tartaric acids. Addition of thiophenols to chalcones also occurred in neat ionic liquids, without any additional catalyst, but the rate of the reaction depended considerably on the structure of ionic liquid. The scope of the non-catalysed reaction in ionic liquids was tested by the reactions of 5 different thiols and 3 different alpha-enones.     

Water-soluble ruthenium(II) catalysts [RuCl2(eta6-arene)[P(CH2OH)3]] for isomerization of allylic alcohols and alkyne hydration

The novel water-soluble ruthenium(II) complexes [RuCl(2)(eta(6)-arene)[P(CH(2)OH)(3)]]2a-c and [RuCl(eta(6)-arene)[P(CH(2)OH)(3)](2)][Cl]3a-c have been prepared in high yields by reaction of dimers [[Ru(eta(6)-arene)(micro-Cl)Cl](2)](arene = C(6)H(6)1a, p-cymene 1b, C(6)Me(6)1c) with two or four equivalents of P(CH(2)OH)(3), respectively. Complexes 2/3a-c are active catalysts in the redox isomerization of several allylic alcohols into the corresponding saturated carbonyl compounds under water/n-heptane biphasic conditions. Among them, the neutral derivatives [RuCl(2)(eta(6)-C(6)H(6))[P(CH(2)OH)(3)]]2a and [RuCl(2)(eta(6)-p-cymene)[P(CH(2)OH)(3)]]2b show the highest activities (TOF values up to 600 h(-1); TON values up to 782). Complexes 2/3a-c also catalyze the hydration of terminal alkynes.     

二氯甲烷同步辐射光电离的动力学研究

采用VUV同步辐射光源，在超声射流冷却条件下研究了二氯甲烷（CH2Cl2）光电离及其解离电离的动力学过程，测得CH2Cl2的电离能（IP）为11．32士0．01eV．通过对CH2Cl2光解离电离过程产生的碎片离子的出现势（AP）的测定，并结合有关中性分子的热力学数据，估算出该体系中有关离子的标准生成焓、中性分子和离子型分子中的键能及母体离子的解离能（DE）等一系列热力学数据．对CH2Cl2分子VUV光解离电离通道进行了细致的分析．