钒钨酸盐/刚果红电致变色复合膜及器件研究

应用Layer-by-Layer自组装技术, 采用聚乙烯亚胺(PEI)阳离子将无机电致变色材料[P₂W₁₅V₃O₆₂]^8?(P₂W₁₅V₃)阴离子与刚果红(CR)阴离子通过静电引力复合, 构筑了复合膜[PEI/P₂W₁₅V₃/PEI/CR]₂₀及对比膜 [PEI/P₂W₁₅V₃]₂₀. 利用扫描电子显微镜、 紫外-可见吸收光谱和电化学工作站研究了复合膜的形貌与电致变色性能. 对比研究表明, 复合膜可实现浅红色-蓝紫色-浅红色的可逆颜色调变, 且保持了[P₂W₁₅V₃O₆₂]^8?阴离子的电致变色性能, 光反差22.55%, 着色效率122.67 cm²/C.复合膜循环测试400圈后透过率(500 nm)处损耗仅为6.94%, 稳定性良好; 由复合膜组装的电致变色器件也实现了由浅红色到蓝紫色的颜色变化. 本研究可为解决多酸电致变色材料颜色变化单一的问题提供参考.     

可吸附紫精化合物电致变色器件

研究报道了一种基于可吸附的固态紫精化合物电致变色器件. 我们设计并合成了一种新型可吸附的不对称紫精化合物,其一端引入三苯胺基团用以修饰紫精化合物的电致变色性质,另一端引入膦酸基团使其固定于电极上,以提高变色速度,增加器件稳定性. 将所合成的材料应用于器件中,得到了高透过差值和高稳定的电致变色器件. 我们利用紫外-可见-红外分光光度计、电化学工作站以及CIE 1931 %Y_Lxy色度系统对其电致变色性能以及颜色进行了表征.     

旋转涂布法制备MoO3变色薄膜的研究

近二十年来,过渡金属氧化物半导体薄膜因其具有光致变色/电致变色特性,可作为无机变色材料广泛应用于信息存储、显示以及灵敏器件等方面,而成为材料科学领域的研究热点之一^[1～4].     

含噁二唑大环冠醚的合成、 结构及金属离子识别性能

合成了含有1,3,4-噁二唑基团的大环冠醚: 2,3,11,12-二苯并-4,7,10,16-四氧-14,15-二氮杂双环[11.2.1]-十六烷-13,15-二烯(2)、 2,3,14,15-二苯并-4,7,10,13,19-五氧-17,18-二氮杂双环[14.2.1]-十九烷-16,18-二烯(3)和2,3,17,18-二苯并-4,7,10,13,16,22-六氧-20,21-二氮杂双环[17.2.1]-二十二烷-19,21-二烯(4), 并培养得到其单晶; 通过核磁共振波谱、 高分辨质谱及X射线单晶衍射对其结构进行了表征. 结果表明, 冠醚2属正交晶系, Pna2₁空间群; 冠醚3属于单斜晶系, C2/c空间群; 冠醚4属正交晶系, Pbca空间群. 在3个主体化合物中均存在分子间氢键和π-π相互作用将分子连接成三维空间结构. 采用荧光光谱测定了开链冠醚2,5-二[2-(2-甲氧乙氧基)苯基]-1,3,4-噁二唑(1)和不同环空腔大小的噁二唑冠醚(2~4)对金属离子Li ⁺, Na ⁺, K ⁺, Rb ⁺, Mg ²⁺和Ca ²⁺的键合行为. 研究结果表明, 开链冠醚1和冠醚4对碱土金属Mg ²⁺和Ca ²⁺表现出荧光猝灭行为, 且对Ca ²⁺表现出良好的键合能力和选择性; 而冠醚2对Na ⁺和K ⁺表现出良好的键合能力, 但其Na ⁺/K ⁺的选择性较差.     

席夫碱型环磷腈类化合物的合成及光谱性质

通过亲核取代反应, 在2,2'-联苯二酚氧基环氯磷腈母体N₃P₃(O₂C₁₂H₈)₂Cl₂ (1)和N₃P₃(O₂C₁₂H₈)Cl₄ (2)上引入2-醛基吡啶与对胺基苯酚形成的席夫碱侧基, 合成了两种新型环磷腈化合物N₃P₃(O₂C₁₂H₈)₂(p-O-Ph-N＝C-Py)₂ (3)和N₃P₃(O₂C₁₂H₈)(p-O-Ph-N＝C-Py)₄ (4), 这些化合物是一类能形成配合物的多齿配体. 通过元素分析, IR, ¹H NMR, ³¹P NMR和TOFMS确定其结构, 研究了它们的吸收光谱和荧光光谱. H^＋和Cu^＋离子对其光谱性质的影响研究表明两种化合物的吸收和荧光光谱对H^＋和Cu^＋离子异常敏感, 因而在作为这些阳离子的荧光探针方面具有应用前景.     

两种砷钼杂化多酸盐的合成、 结构及变色性质

分别以2种V形羧酸[1,3-苯二甲酸(H₂BDC)和5-羟基-1,3-苯二甲酸(H₂OIP)]与钼酸铵进行反应, 得到了 2种有机酸根与无机酸根缩合构成的杂化砷钼酸盐： (NH₄)₁₇H₄[(AsMo₆O₂₁)₂(AsMo₆O₂₃)(BDC)₄]·28H₂O(1)和 (NH₄)₅Cs₈H₆[(AsMo₆O₂₁)₃(OIP)₅]·40H₂O(2). 利用单晶X射线衍射对2种化合物进行了结构分析, 发现二者均为三聚结构. 对2种化合物的光致变色及热致变色性质进行了研究, 发现在氙灯照射下2种化合物均可在5 min内变色. 当将2种化合物的样品加热到373 K时, 均出现颜色变化, 并随着温度升高颜色逐渐加深. 光致变色与热致变色过程前后的EPR检测结果均提示化合物的颜色变化与Mo^VI转化为Mo^V有关.     

原位烷基化调控无机-有机杂化类钙钛矿材料的结构及其性能※

无机-有机杂化类钙钛矿材料由于结构可调和独特的光电特性而引起了人们的广泛关注. 通过选用不同的烷基化溶剂, 一步水热法原位合成了两种新型的无机-有机杂化材料——二维(2D)结构的[(Me₃)ODA(Me₃)]₃Pb₅I₁₆ (1)和一维(1D)结构的[H(Et₂)ODA(Et₂)H]Pb₂I₆•H₂O (2) (ODA=4,4-二氨基二苯醚). 化合物1由2D的无机类钙钛矿层[Pb₅I₁₆]^6–和有机阳离子[(Me₃)ODA(Me₃)]²⁺组成, 化合物2由1D无机类钙钛矿链[Pb₂I₆]^2–、有机阳离子[(Et₂)ODA(Et₂)]²⁺和水分子组成. 实验表明, 两种不同维度的化合物虽然都具有典型的半导体性能, 但却表现出不同的化学稳定性以及光、电等物理特性. 其中, 化合物1对波长为400~700 nm的光呈现出明显的光电响应, 而化合物2在对水和有机溶剂表现出良好稳定性的同时, 还表现出优异的湿敏响应性能.     

芳香寡聚磺酸酯桥联大环化合物的合成及其对Sn2+和Bi3+的识别作用

以4,6-二烷氧基-1,3-苯二磺酰氯和芳香二酚为原料,三乙胺作缚酸剂,二氯甲烷作溶剂,采取一步成环法合成了3种磺酸酯桥联大环化合物。合成产物的结构用IR、¹H NMR、¹³C NMR和MALDI-TOF等技术手段进行了确认。利用紫外光谱分析的方法研究了4,6,16,18-四正戊氧基-11,23-二甲基-1,3,13,15-四磺酸酯间苯芳香大环(5)对Ca²⁺、Pb²⁺及部分过渡金属等20种金属离子的识别。结果发现,其对Sn²⁺显示出一定的选择性,由于Sn²⁺和Bi³⁺协同作用的影响,在化合物5-Sn²⁺的体系中加入Bi³⁺,紫外吸收光谱在325 nm左右的吸收增强了许多,这说明化合物5对Bi³⁺显示出优于Sn²⁺的较好选择性。     

固态聚苯胺电致变色器件的制备和性能

采用CeO2-TiO2复合物薄膜作为聚苯胺电致变色器件的对电极, 选用聚合物固态电解质(PE: PMMA-PC-EC-LiClO4), 构筑了新型双层结构(Dual-type)聚苯胺(PANI)固态电致变色(EC)器件. 用电化学现场紫外-可见光谱法表征了该EC器件(ITO|PANI||PE||CeO2-TiO2|ITO)的电致变色性能, 并与单层结构(Single-type)EC器件(ITO|PANI||PE|| ITO)进行了比较. 研究结果表明, 双层结构EC器件比单层结构EC器件的电致变色性能好, 如响应速度快, 循环寿命长. 同时, 考察了电解质组分对聚苯胺电致变色稳定性的影响. EC器件(ITO|PANI||PE||CeO2-TiO2|ITO)的颜色呈现由透明的黄色(-1.5 V, PANI vs. CeO2-TiO2)到蓝色(1.0 V)的可逆变化, 在700 nm处的透射率由42.19%变到13.35%, 经过150个循环, 其透射率差仍保持不变, 着色效率为152.1 cm2/C.     

基于吡咯并吡咯二酮和苯并噻二唑聚合物的合成及其近红外电致变色性能

给-受体型窄带隙聚合物是一类新型可见-近红外电致变色材料,虽然可调性强、颜色丰富,但是其电致变色性能如对比度、稳定性等需要进一步提高。 通过调节聚合物中构筑单元吡咯并吡咯二酮(DPP)、苯并噻二唑(BTZ)和噻吩(T)的比例(n(DPP):n(BTZ):n(T)分别为1:0:1、1.5:0.5:1、2:1:1和3:2:1),合成了4种新型窄带隙电致变色聚合物,研究聚合物结构和电致变色性能的关系。 研究发现,这类聚合物在近红外光谱区具有较高的对比度(ΔT:50%60%)和变色效率(CE:300600 cm²/C),尤其是在1550 nm处,聚合物P3的ΔT高达63%、P4的CE高达471 cm²/C。 相比之下,含有BTZ基团的聚合物的吸收更长、对比度更高且更稳定。 这为设计给-受体型高性能电致变色聚合物提供了新的思路。     

Synthesis and electropolymerization of 5,12-dihydrothieno[3′,4′:2,3][1,4]dioxocino[6,7-b]quinoxaline and its electrochromic properties

Synthesis of a new thiophene-based monomer; 5,12-dihydrothieno[3′,4′:2,3][1,4]dioxocino[6,7-b]quinoxaline (DDQ), was realized. The chemical structure of the monomer was characterized by ¹H NMR, FTIR and mass spectroscopy techniques. Electrochemical polymerization of DDQ and characterization of the resulting polymer [P(DDQ)] was performed. Moreover, the spectroelectrochemical and electrochromic properties of the polymer film were investigated. P(DDQ) has a low oxidation potential (0.9 V) and low band gap (1.73 eV) compared to polythiophene. In addition, dual-type polymer electrochromic device (ECD) based on P(DDQ) with poly(3,4-ethylenedioxythiophene) (PEDOT) was constructed. Spectroelectrochemistry, electrochromic switching, stability and open-circuit stability of the device were studied. It was observed that polymer have good switching time, reasonable contrast and optical memory.     

离子液体中聚3-己基噻吩的制备及电致变色性质和器件的研究

以室温离子液体1-丁基-3-甲基咪唑六氟磷酸盐[BMIM]PF₆为溶剂及支持电解质,通过电化学方法制备聚(3-己基噻吩)(PHexT)膜。采用循环伏安法和扫描电子显微镜,对膜的电化学性质及形貌结构进行表征。同时通过紫外可见光谱、计时电流、计时库仑以及计时吸收曲线等方法研究聚合物膜的光谱电化学和电致变色特性,并在此基础上制备PHexT膜的电致变色器件。实验结果表明,在离子液体中制备的PHexT膜光滑致密,掺杂态时为蓝色,脱掺杂时为桔红色,并且具有高的颜色对比度 (40%),较短的响应时间 (2.5 s) 和高的电致变色着色效率 (230cm²/C),该膜制成的固态电致变色器件具有很好的电致变色性能和长的循环寿命。     

Ag/WO3纳米复合膜的制备及其电致变色性质和器件的研究

通过真空镀膜方法制备的纳米Ag薄膜均匀致密, 表面光滑. 然后通过电化学方法在Ag纳米薄膜上沉积一层三氧化钨(WO3), 制备纳米Ag/WO3复合膜. 并在此基础上构筑五层式玻璃/ITO/纳米Ag-WO3复合膜/固态电解质/聚(3-甲基噻吩)/ITO/玻璃电致变色器件. 实验结果表明, 与传统的WO3膜相比, 纳米Ag/WO3复合膜具有更好的电化学活性、更高的对比度、更短的响应时间, 以及更好的稳定性. 由该复合膜组装的电致变色器件工艺简单, 电致变色性能良好.     

Electrochemical synthesis and investigation of poly(1,4-bis(2-(3,4-ethylenedioxy)thienyl)benzene) and its application in an electrochromic device

1,4-Bis(2-(3,4-ethylenedioxy)thienyl)benzene, prepared by Stille cross-coupling reaction was successfully electrochemically polymerized to give polymer 1,4-bis(2-(3,4-ethylenedioxy)thienyl)benzene (PEBE). Characterizations of the resulting polymer PEBE were performed by cyclic voltammetry (CV), UV–vis, Fourier transform infrared spectroscopy and scanning electron microscopy. Moreover, the spectroelectrochemical and electrochromic properties of the polymer film were investigated. The resulting polymer film has distinct electrochromic properties and shows three different colors (deep red, gray, and light blue) under various potentials. At the dedoped state of the polymer, the π–π* transition absorption peak is located at 510?nm and the optical band gap (E _g) was calculated as 1.92?eV. The PEBE film shows a maximum optical contrast (ΔT%) of 31.0?% at 500?nm with a response time of 0.85?s. The coloration efficiency of PEBE film was calculated to be 182.2?cm²C^?1. An electrochromic device (ECD) based on PEBE and poly(3,4-ethylenedioxythiophene) was also constructed and characterized. The response time was measured as 0.4?s, and the coloration efficiency of the device was calculated to be 225.4?cm²C^?1. Furthermore, this ECD exhibited satisfactory optical memories and redox stability.     

Synthesis and electrochromic properties of polybismaleimides containing triphenylamine units

The bismaleimide (BMI) monomer containing triphenylamine was prepared firstly. Then BMI was reacted with different diamines by Michael addition to obtain prepolymers, respectively. Finally, polyimides (PIs) were obtained through melting procedure. The effects of the structure of BMI moiety and thermal curing condition on thermal stability of PIs were studied by thermogravimetric analysis. PIs have excellent processing properties for film casting. Cyclic voltammetry of PI films was carried out on an indium-doped tin oxide-coated glass substrate. Results which exhibit two reversible oxidations at 0.71–0.78 and 1.06–1.16 V vs Ag/AgCl. The electrochromic performance was investigated by spectroelectrochemical methods. These anodically coloring polymer films not only showed good electrochromic properties but also exhibited high optical contrast ratio of transmittance with a color changing from yellow to green. After 100 cyclic switches, the polymer films still retained excellent redox and electrochromic activity.     

A new donor‐acceptor type polymeric material from a thiophene derivative and its electrochromic properties

A new electrochromic polymer, poly(2,3,5,8‐tetra(thiophen‐2‐yl)quinoxaline) (PTTQ), was synthesized electrochemically and its electrochromic properties were investigated. The polymer was characterized by Cyclic Voltammetry, Fourier Transform infrared spectroscopy, UV‐Vis‐NIR Spectroscopy, and colorimetry. Spectroelectrochemistry analysis demonstrated that the polymer can undergo both p‐ and true n‐type doping processes. The polymer, (PTTQ), has three accessible color states: an oxidized transmissive, a neutral light bluish‐green, and a reduced transmissive light gray. Switching ability of the polymer was evaluated by kinetic studies. The polymer revealed an excellent optical contrast of 98% in the NIR region. Outstanding optical contrast in the NIR region, high stability and fast switching times make this polymer an excellent candidate for NIR device applications. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3723–3731, 2008     

Fluorene-based donor-acceptor-type multifunctional polymer with bicarbazole pendant moiety for optoelectronic applications

Since limited examples are in the literature in which both organic light-emitting diodes (OLEDs) and electrochromic (EC) applications were performed using the same conjugated polymer, we presented comprehensive EC and electroluminescence (EL) studies of fluorene-based electroactive polymer (e.g., CFP6) consisting of a bicarbazole pendant moiety with quinoxaline as an acceptor bridge. CFP6 was synthesized by a Suzuki cross-coupling polymerization reaction and utilized as an active and emissive layers of the electrochromic device (ECD) and OLED, respectively, due to its high photoluminescence quantum yield intensity and fine thin film forming capability. The optical, electrochemical, cyclic voltammetry measurements, and density functional theory calculations were realized. Electrochemical cross-linking process was applied over the electroactive carbazole subunit of the CFP6 polymer. After the crosslinking process, EC performance was greatly improved. On the other hand, light emission and EL characteristics of OLEDs based on CFP6 emissive layer were realized in detail with six different device architectures to understand light output profile behavior. As a result, CFP6 emitted bright greenish yellow emission with a maximum brightness of 1777 cd/m² at 215 mA/cm² in the indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS)/CFP6:%10 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP)/Alq3/LiF/Al device architecture.     

Preparation of a Star Network PEG-based Gel Polymer Electrolyte and Its Application to Electrochromic Devices

A star network polymer with a pentaerythritol core linking four PEG-block polymeric arms was synthesized, and its corresponding gel polymer electrolyte based on lithium perchlorate and plasticizers EC/PC with the character being colorless and highly transparent has been also prepared. The polymer host was characterized and confirmed to be of a star network and an amorphous structure by FTIR, ^1H NMR and XRD studies. The polymer host hold good mechanical properties for pentaerythritol cross-linking. Maximum ionic conductivity of the prepared polymer electrolyte has reached 8.83 × 10 ^-4 S·cm^-1 at room temperature. Thermogravimetry （TG） of the polymer electrolyte showed that the thermal stability was up to at least 150 ℃. The gel polymer electrolyte was further evaluated in electrochromic devices fabricated by transparent PET-ITO and electrochromically active viologen derivative films, and its excellent performance promised the usage of the gel polymer electrolyte as ionic conductor material in electrochrornic devices.     

Synthesis and Electrochemical Properties of a Novel Poly(ether sulfone) with Oligoaniline Pendants

A novel poly(ether sulfone) with oligoaniline pendants(PESOP) was prepared by K₂CO₃-mediated nucleophilic polycondensation and characterized with Fourier-transform infrared spectrometry(FTIR), ¹H nuclear magnetic resonance(¹H NMR) and gel permeation chromatography(GPC). The cyclic voltammetry(CV) curve of PESOP reveals the reversible electroactivity. In the electrochromism study, PESOP film exhibited good electrochromic properties with a high contrast value, moderate switching time and acceptable coloration efficiency. After running 1000 cycles, the PESOP/indium-tin oxide(ITO) electrochromic device remained unchanged except for the drifting of base line, which certified its good electro-photo stability of the fabricated electrochromic device. Moreover, the polarization technique and electrochemical impedance spectroscopy(EIS) were used to study the anticorrosion performance of PESOP coatings on the cold rolled steel(CRS) in a 5%(mass fraction) NaCl solution. All the results indicate that the obtained PESOP is a competitive candidate as anticorrosion material.     

SYNTHESIS AND CHARACTERIZATIONS OF NEAR INFRARED ABSORBING POLYMERS

A series of near infrared (NIR) absorbing dinuclear ruthenium dicarbonylhydrazine complexes (DCH-Ru),[{Ru(bpy)_2)_2μ-DCH]~(n ) (where bpy = 2,2'-bipyridinc and n = 2, 3 or 4), were prepared. The DCH-Ru complexes areelectrochromic in the NIR region with a high absorption coefficient at 1550-1600 nm typically over 10000 M~(-1)cm~(-1). DCH-Ru complex polymers with good NIR electrochromic properties were also obtained and processed to make a device foroptical attenuation at a wavelength of 1550 nm. The potential of these DCH-Ru polymers for use in a variable opticalattenuator has been demonstrated with an attenuating power at the 1550-nm telecommunication wavelength over 7.0 dB permicron of polymer film thickness. Other classes of NIR active materials are the pentacenediquinones and the correspondingpoly(ether pentacenediquinone)s. These polymers can be electrochemically reduced to the corresponding semiquinone(radical anion) having NIR absorption within a telecom window (e. g., 1310 nm).