聚苯胺电致变色薄膜在不同颜色区间的电化学循环稳定性研究

本文采用电位阶跃和循环伏安法结合紫外可见光光度法研究了聚苯胺薄膜的电致变色性质. 聚苯胺薄膜颜色多变,颜色在浅黄色到绿色再到蓝色之间变化,本文研究在不同的颜色变化区间内聚苯胺薄膜的电化学循环稳定性. 研究结果表明,薄膜在黄色到蓝色(0.4 V ~ 1.2 V)以及绿色到蓝色(0.8 V ~ 1.2 V)区间变化时,电致变色循环性能较差,而在黄色和绿色(0.4 V ~ 0.8 V)之间变化时循环稳定性能良好,着色时间为4.5 s,着色效率高达159.48 cm²·C^-1.     

全钒液流电池高浓度下V(IV)/V(V)的电极过程研究

采用循环伏安、低速线性扫描和阻抗技术, 以石墨为电极, 研究了V(IV)/V(V)在较高浓度下的电极过程. 结果表明, 采用2.0 mol•L-1 的V(IV)溶液时, H2SO4浓度低于2 mol•L-1, V(IV)/V(V)反应极化大, 可逆性差, 表现为电化学和扩散混合控制; H2SO4浓度增至2 mol•L-1以上, V(IV)/V(V)反应的可逆性提高, 转为扩散控制, 且增加H2SO4浓度有利于阻抗的降低; 但H2SO4浓度超过3 mol•L-1, 溶液的粘度和传质阻力大, 阻抗反而增大. 在3 mol•L-1的H2SO4中, 随着V(IV)浓度的增加, 体系的可逆性和动力学改善, 阻抗减小; 但V(IV)浓度超过2.0 mol•L-1, 较高的溶液粘度导致溶液的传质阻力迅速增加, V(IV)/ V(V)的电化学性能衰减, 阻抗增大. 因此, 综合考虑电极反应动力学和电池的能量密度两因素, V(IV)溶液的最佳浓度为1.5～2.0 mol•L-1, H2SO4浓度为3 mol•L-1.     

基于原位聚合离子液体凝胶的固态电致变色器件的制备及性能研究

本文通过在离子液体BmimPF6中原位热聚合甲基丙烯酸甲酯得到了透明的离子液体凝胶。通过交流阻抗测定,当BmimPF6与甲基丙烯酸甲酯的质量比为5∶1时,离子液体凝胶的导电率为1.33×10-3Scm-1。将通过电化学沉积制得的三氧化钨(WO3)和普鲁士蓝(PB)修饰FTO电极,与上述离子液体凝胶一起组装得到了全固态的电致变色器件。原位吸收光谱数据显示所制得的电致变色器件,在±2V的工作电压下,具有稳定的电致变色响应,其着色和褪色时间分别为4.5s和4.0s,着色效率达190cm2C-1(λ=660nm)。     

原液着色阻燃共聚酯及其纤维的制备与表征北大核心CSCD

采用原液着色技术制备了掺杂无机、有机染料的原液着色阻燃共聚酯切片,并对其可纺性及所得着色阻燃纤维性能进行了研究。通过差示扫描量热仪(DSC)、热失重分析仪(TGA)、极限氧指数仪(LOI)、声速仪及纱线强伸度仪等对所得样品进行了表征测试。结果表明,染料的加入对阻燃共聚酯的结晶性能及热稳定性能影响很小,且原液着色阻燃共聚酯的LOI在33%～35%之间,呈现良好的阻燃性能。原液着色阻燃共聚酯切片具有很好的可纺性,热收缩测试表明染料掺杂阻燃共聚酯纤维的热收缩性能有所降低,尺寸稳定性有所提高,着色阻燃纤维的断裂强度能达到2.0cN/dtex以上,可满足纺织品对纤维的强度要求。     

电化学变色显示及其原理

材料在电场作用下能显示出一定的颜色,这种着色是由于一部份金属离子化合价的改变,这种现象叫做电化学变色(ECC)。电化学变色现象在液体和固体电解质中均可以发生,我们把这种离子或电子的化学着色     

Synthesis of Monoclinic Li_(0.33)MnO_2 and Its Electrochemical Properties in Different Potential Windows

Li0.33MnO2 cathode material was synthesized by solid state reaction. The material showed a small coherent domain size about 10 nm determined by X-ray diffraction and transmission electron microscopy. The electrochemical properties of the material were studied in different potential windows of 3.5―2.0 V and 4.3―2.0 V. An irreversible transformation to spinel phase was observed in the initial several cycles, which was more prominent on cycling at 4.3―2.0 V. Electrochemical impedance spectroscopy showed that the Li+ diffusion coefficient of the material was about 2×10–9 cm2/s. Li0.33MnO2 showed a reversible discharge capacity of 140 and 200 mA·h/g in the potential windows of 3.5―2.0 V and 4.3―2.0 V, respectively. But the capacity retention at 4.3―2.0 V was poor due to the thicker spinel layer formed on the material surface.     

Trace Determination of Zirconium（Ⅳ） by Anodic Adsorptive Voltammetry at a Carbon Paste Electrode

A new sensitive adsorptive voltammetric method was described for the determination ofzirconium at a carbon paste electrode (CPE) in the presence of alizarin complexone (ALC).Optimal analytical conditions are: 1.0~ l0“6 or 5.0x l0“7 mol/L ALC, 0.20 mol/L HAC-NaAc (pH4.3), accumulation for 60 s at 0 V (vs. SCE), and linear scanning from 0 V to 1.0 V at 250 mV/s.The peak potential of the complex is at 0.81 V. By using a model JP-303 polarographic analyzer,2.0~ l0l~ mol/L (S/N=3) zirconium can be detected with a 90 s accumulation, when the 2nd-orderderivative linear sweep technique is used, and the linear range is 6.0~ 10l~-2.0~ l0s mol/L (5.0~ l07mol/L ALC) and 2.0~108-2.0~ l07 mol/L (1.0~ 10.6 mol/L ALC), respectively. The developedmethod was applied to the determination of trace zirconium in the ore samples with satisfactoryresults.     

一种新型DNB-L-脯氨酸手性键合相的合成及联萘酚衍生物的拆分

以3,5-二硝基苯甲酰-L-脯氨酸为手性选择子,通过11-氨基十一酸臂和3-氨丙基硅烷偶联剂,制备了一种新型的硅胶手性键合固定相。采用V(正己烷)∶V(乙醇)∶V(乙酸)=98.0∶2.0∶0.5作为流动相,在柱温30℃,流速1.0mL·min-1和紫外254nm检测条件下,拆分了4种联萘酚及其衍生物对映体。     

脉冲激光沉积CuF2薄膜的电化学性能

采用脉冲激光沉积法在不锈钢基片上制备了纳米结构的CuF2薄膜,其充放电性能显示该薄膜具有540mAh·g-1可逆容量,对应于每个CuF2可与2.0个Li发生反应.其循环伏安特性显示在2.2和2.8 V(νs Li/Li+)处出现了一对新的氧化还原峰.充放电后薄膜的组成与结构通过非原位高分辨电子显微和选区电子衍射来表征.结果揭示了纳米结构CuF2薄膜的电化学反应机理,LiF在过渡金属Cu的驱动下可以发生可逆的分解和形成.     

脉冲激光沉积CuF2薄膜的电化学性能

采用脉冲激光沉积法在不锈钢基片上制备了纳米结构的CuF2薄膜, 其充放电性能显示该薄膜具有540 mAh·g-1可逆容量, 对应于每个CuF2可与2.0个Li发生反应. 其循环伏安特性显示在2.2和2.8 V (vs Li/Li+)处出现了一对新的氧化还原峰. 充放电后薄膜的组成与结构通过非原位高分辨电子显微和选区电子衍射来表征. 结果揭示了纳米结构CuF2薄膜的电化学反应机理, LiF在过渡金属Cu的驱动下可以发生可逆的分解和形成.     

Liquid Crystalline Coronene Derivatives with Extraordinary Fluorescence Properties

Tempering of polystyrene films containing the novel liquid crystalline coronenebis(dicarboximide)s 2 , which are formed by an easy route from perylene-3,4;9,10-tetracarboxylic dianhydride ( 1 ), leads to a shift of the emission within a few seconds. This could be used for dot-by-dot coloring and thus optical displays. The photoluminescence properties of 2 in the solid matrix are dependent on the nature of the aggregates formed.     

TiO2-PTPAT纳米核/壳结构复合膜的制备及电致变色性能

通过水热法在氟掺杂氧化锡(FTO)导电玻璃基底上制备了垂直生长的二氧化钛(TiO₂)纳米棒阵列, 以TiO₂纳米棒阵列为模板采用电化学聚合法, 原位制备了TiO₂-聚三[2-(4-噻吩)苯]胺(PTPAT)纳米核/壳结构的复合薄膜, 相比于纯PTPAT薄膜, TiO₂-PTPAT复合薄膜显示出更好的电致变色(EC)性能. PTPAT薄膜在600 nm波长下的对比度为28%, 在1100 nm波长下的对比度为60%, 其褪色时间为3.86 s, 着色时间为5.52 s; TiO₂- PTPAT复合薄膜在600 nm波长下的对比度为43%, 在1100 nm波长下的对比度为79%, 其褪色时间为3.35 s, 着色时间为4.43 s, 表明核/壳复合结构薄膜的光学对比度和响应时间性能更加优异. 将PTPAT薄膜和TiO₂-PTPAT复合薄膜作为电致变色层组装成固态EC器件, 基于复合薄膜的器件具有更好的循环稳定性和更高的耐受电压. 复合薄膜在保持PTPAT薄膜原有的EC性能的基础上, 由于有序生长的纳米阵列结构的引入增加了薄膜的比表面积, 为电致变色过程中离子的掺杂和脱掺杂提供了更多有序通道, 从而加快了离子扩散速度. TiO₂阵列的引入也改善了聚合物薄膜与透明导电电极之间的界面结合情况, 从而提升了器件的稳定性.     

Ion Tunneling in Polymeric Solid Electrolytes for Batery and Electrochromic Display in the Dry State

Polymeric solid electrolytes which show bi-or single-ionic tunneling were prepared, and their unique ion conduction was applied for the design of some devices. Poly [(oligooxyethylene) methacrylatel] /MX hybrids and poly [(oligooxyethylene) methacrylate-co-methacrylic acid alkali metal salts] were prepared as typical models of those tunneling systems. These showed ionic conductivities above 10^?5 and 10^?7 S/cm at room temperature, respectively. An all-solid-state electrochromic display and a dry battery were prepared with these polymeric solid electrolytes. The all-solid-state electrochromic display showed excellent coloring and bleaching response by 1–3 V. The all-solid-state battery showed V _oc = 3.1 V stability for over 2 weeks. Their characteristics as well as their mechanism are also reported.     

Determination of thermodynamic formation values for some solid charge-transfer complexes of iodine

The standard Gibbs free energy, enthalpy, and entropy of complex formation of five solid molecular complexes of iodine have been determined by comparing the e.m.f.'s of galvanic cells having either solid iodine or the iodine complex as cathode. All of the complexes were found to have a negative enthalpy of formation, which was in the range ?5 to ?14 kJ mol^?1, except for one very weak complex. The relative stability of the complexes was largely determined by the standard entropy of formation which varied from +18 J K^?1 mol^?1, for the most stable of the complexes studied, to ?21 J K^?1 mol^?1.     

4-(5-氯-2-吡啶)-偶氮-1,3-二氨基苯显色光度法测定钯(Ⅱ)

研究了4-(5-氯-2-吡啶)-偶氮-1,3-二氨基苯(5-Cl-PADAB)与Pd的显色反应,在0.48 mol/L H3PO4介质和100℃水浴条件下,5-Cl-PADAB与Pd(Ⅱ)反应生成2:1稳定络合物,其最大吸收波长为570nm,表观摩尔吸光系数为6.39×104 L.mol-1.cm-1。结果表明:Pd含量在0～1.2 mg/L内符合比尔定律,方法已用于矿样中微量Pd的测定,结果与AAS法相符。样品分析结果的相对标准偏差小于4%,加标回收率为98.5%～103.0%。     

A new near‐infrared switchable electrochromic polymer and its device application

A new near‐infrared switchable electrochromic polymer containing carbazole pendant (poly‐SNSC), synthesized by electrochemical polymerization of 2,5‐bis‐dithienyl‐1H‐pyrrole (SNS) main chain, has been prepared. The electrochemical and optical properties of SNSC monomer and its polymer have been investigated. Because of having two different electro‐donor moieties; that is, carbazole and SNS, SNSC gave two separate electrochemical oxidation and also light brown color of the film in the neutral state turn into gray on oxidation. An electrochromic device, contructed in the sandwich configuration [indium tin oxide (ITO)‐coated glass/anodically coloring polymer (poly‐SNSC)//gel electrolyte//cathodically coloring polymer (PEDOT)/ITO‐coated glass] and exhibited a high coloration efficiency (1216 cm² C^–1), a very short response time (about 0.3 s), low driving voltage, and a high redox stability. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

铀-2-(3,5-二溴-2-吡啶偶氮)-5-二乙氨基苯酚-Triton X-100析相体系的研究及应用

本文研究了铀-2-(3,5-二溴-2-吡啶偶氨)-5-二乙氨基苯酚(3,5-diBr-PADAP)-Triton X-100析相光度体系,建立了矿石中微量铀的测定方法,在pH 7.5三乙醇胺-盐酸介质中,将胶束溶液在 95±1℃加热 1h.络合物即被Triton X-100相完全富集.络合物最大吸收峰位于565nm.摩尔吸光系数为1.02×10～5L·mol～(-1)·cm～(-1),铀含量在0～12μg/5mL服从比耳定律.采用TBP萃淋树脂分离干扰离子,测定矿石中微量铀,结果满意.     

Hydroxy double salt anion exchange kinetics: effects of precursor structure and anion size

(1)H NMR spectroscopy and powder X-ray diffraction have been used to explore the details of anion exchange reactions of two layered hydroxy double salts (HDSs), zinc copper hydroxy acetate (ZCA), nickel zinc hydroxy acetate (NZA), and a related layered material, zinc hydroxy acetate (ZHA), at room temperature (21-22 degrees C). Reactions that followed Avrami-Erofe'ev kinetics with respect to temporal profiles for acetate release, ZCA with butyrate (k = 1.7 x 10(-3) s(-1)), and octanoate (k = 0.79 x 10(-3) s(-1)) anions, as well as ZHA with octanoate (k = 2.6 x 10(-3) s(-1)), demonstrate that rate constants for acetate release are influenced by the exchange anion relative size as well as by the solid precursor structure/composition. The reaction of NZA with octanoate deviated from expected Avrami-Erofe'ev behavior, with evidence for an intermediate species in the solid phase that may influence the rate of acetate release into solution. The reaction of ZCA with formate anions exhibited a unique zeroth-order kinetics release of acetate, providing the possibility of developing tunable nanostructured anion release sources by use of variations in the size of the exchange species.     

Electrochromic Properties of ‘Trimeric' Thiophene‐pyrrole‐thiophene Derivative Grown from Electrodeposited 6‐(2,5‐di(thiophen‐2‐yl)‐1H‐pyrrol‐1‐yl)hexan‐1‐amine and its Copolymer

A centrosymmetric polymer precursor, namely 6‐(2,5‐di(thiophen‐2‐yl)‐1H‐pyrrol‐1‐yl)hexan‐1‐amine (TPHA), was synthesized via a Knorr–Paal reaction using 1,4‐di(2‐thienyl)‐1,4‐butanedione and hexane‐1,6‐diamine. The resultant monomer was characterized by Nuclear Magnetic Resonance (¹H‐NMR). Electroactivity of TPHA was investigated via cyclic voltammetry. The electronic structure and the nature of electrochromism in P(TPHA) and its copolymer with EDOT, (P(TPHA‐co‐EDOT)), were examined via spectroelectrochemistry studies. P(TPHA) switches between claret red neutral state and blue oxidized state. Optical response times for coloring and bleaching processes of the P(TPHA) and P(TPHA‐co‐EDOT) were found as 2.1 s and 1.6 s, respectively.

The copolymer of TPHA was used to construct dual type polymer electrochromic devices (ECDs) against poly(3,4‐ethylenedioxythiophene) (PEDOT). Spectroelectrochemistry and electrochromic switching out of the devices were investigated.