WO2017016177A1 - 异吡咯并吡咯二酮染料及其应用 - Google Patents

异吡咯并吡咯二酮染料及其应用 Download PDF

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WO2017016177A1
WO2017016177A1 PCT/CN2015/100048 CN2015100048W WO2017016177A1 WO 2017016177 A1 WO2017016177 A1 WO 2017016177A1 CN 2015100048 W CN2015100048 W CN 2015100048W WO 2017016177 A1 WO2017016177 A1 WO 2017016177A1
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dye
photoanode
prepared
tio
deionized water
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曹德榕
臧旭峰
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South China University of Technology SCUT
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South China University of Technology SCUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/004—Diketopyrrolopyrrole dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/008—Triarylamine dyes containing no other chromophores
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2022—Light-sensitive devices characterized by he counter electrode
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/311—Purifying organic semiconductor materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • H01G9/2013—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte the electrolyte comprising ionic liquids, e.g. alkyl imidazolium iodide
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention relates to the technical field of organic dyes and dye-sensitized solar cells, in particular to isopyrrolopyrroledione dyes and applications.
  • DSSCs dye-sensitized solar cells
  • Sensitizing dyes are an important part of the battery, which directly affects the performance and practical application of the battery, and can be divided into two categories: pure organic dyes and metal complex dyes.
  • metal complex dyes have the advantage of high photoelectric conversion efficiency
  • pure organic dyes also have the advantages of large structural adjustability, easy synthesis and separation, and relatively low cost.
  • DPP pyrrolopyrroledione
  • isoDPP isopyrrolopyrroledione
  • the invention designs and synthesizes a pure organic dye which uses 4,4'-dihexyloxytriphenylamine as an electron donor, isopyrrolopyrroledione as a ⁇ bridge, and cyanoacetic acid as an electron acceptor and anchoring group.
  • the dye has the advantages of simple structure, easy synthesis, good photoelectric conversion performance and the like.
  • the invention discloses a dye based on isopyrrolopyrroledione as a ⁇ bridge and its application in dye-sensitized solar cells.
  • the invention synthesizes a novel class of metal-free pure organic photosensitive dyes, such dyes are 4,4'-dihexyloxytriphenylamine as electron donor, isopyrrolopyrroledione is ⁇ bridge, and cyanoacetic acid is A pure organic dye of an electron acceptor and an anchor group, and an alkyl chain is introduced on the isopyrrolopyrroledione group.
  • These dyes have good application properties on dye-sensitized solar cells. Its structural formula is as follows:
  • R 1 and R 2 are a C 1 -C 20 linear alkyl group, a C 1 -C 20 branched alkyl group or a C 1 -C 20 alkoxy group, and R 1 and R 2 may be the same or different;
  • a 1 and A 2 are thiophene, benzene ring, furan, 3,4-dioxyethylenethiophene or pyrrole, and A 1 and A 2 may be the same or different.
  • the method for synthesizing a dye based on isopyrrolopyrroledione as a ⁇ bridge is simple, and the raw material is cheap and easy to obtain, for example
  • the synthesis steps are as follows:
  • the use of the isopyrrolopyrroledione dye synthesized by the invention in dye-sensitized solar cells including dye-sensitized sun Battery composition and construction, preparation steps and battery performance test:
  • Composition and structure of dye-sensitized solar cells divided into conductive glass substrates (usually fluorine-doped SnO 2 transparent conductive glass, ie FTO), photoanodes, sensitizers, electrolytes and counter electrodes (generally platinized) Conductive glass) five components; wherein the photo-anode substrate working area is provided with a nanoporous TiO 2 film in the middle of the conductive glass, which can be used to adsorb the dye; the counter electrode is also called the photocathode, and a catalyst is arranged in the middle of the conductive glass on the working area of the substrate.
  • conductive glass substrates usually fluorine-doped SnO 2 transparent conductive glass, ie FTO
  • photoanodes sensitizers
  • electrolytes electrolytes
  • counter electrodes generally platinized Conductive glass
  • the catalyst is mostly Pt; the photoanode and the photocathode are relatively spaced apart, and the periphery of the nanoporous TiO 2 film is sealed with a sealing material to form a closed cavity filled with an electrolyte and a sensitizer (ie, isopyrrolopyrrole II) Ketone dye).
  • a sensitizer ie, isopyrrolopyrrole II
  • FTO conductive glass
  • the nanocrystalline TiO 2 prepared particles were added to ethanol, acetic acid, terpineol, ethyl cellulose, the The mixture is sufficiently ground to obtain a slurry-like substance, and the desired white viscous TiO 2 nanocrystalline slurry is obtained by ultrasonication;
  • the conductive surface of the treated conductive glass is faced upward, the screen plate is placed above the glass, the mesh distance of 0.5 to 3 cm is controlled, and the prepared TiO 2 nanocrystalline slurry is placed on the screen for printing.
  • the thickness of the TiO 2 film is controlled as needed, and is about 8 to 20 ⁇ m (area of 2 to 4 ⁇ 2 to 4 mm).
  • the prepared photoanode is placed in an oven and dried at 100 to 150 ° C, and then placed in a muffle. The furnace is sequentially treated at different temperatures (baked at 300-350 ° C for 3-10 min, baked at 300-400 ° C for 3-10 min, baked at 400-500 ° C for 10-20 min, baked at 450-550 ° C for 10-20 min) to fully remove.
  • the organic substance on the membrane is then immersed in the prepared 0.1-0.3M TiCl 4 aqueous solution for 30 min to 1.5 h, and the treatment is finished with deionized water and ethanol, and placed in a muffle furnace to raise the temperature to 450-550 ° C again. Bake for 25 to 40 minutes, cool to 60 to 80 ° C and set aside;
  • preparation steps of the dye-sensitized solar cell include the following specific steps:
  • FTO conductive glass
  • the treated conductive glass was placed with the conductive surface facing up, the screen plate was placed above the glass, the mesh distance of 1 cm was controlled, and the prepared TiO 2 nanocrystal slurry was placed on the screen for printing.
  • the thickness of the TiO 2 film is controlled as needed, and is about 17 ⁇ m (area of 4 ⁇ 4 mm) used in this chapter.
  • the prepared photoanodes were placed in an oven and dried at 125 °C. It was placed in a muffle furnace and then treated at different temperatures (bake at 325 ° C for 5 min, 375 ° C for 5 min, 450 ° C for 15 min, and 500 ° C for 15 min) to remove the organic matter on the membrane.
  • Battery performance test The lead wire is taken out from the photoanode and the photocathode of the battery respectively, and connected to the battery performance test device.
  • the working area of the battery is 0.16 cm 2 , and the sunlight is simulated by a solar simulator to adjust the light intensity to 100 mW.
  • the /cm 2 test is based on the JV curve of the dye-sensitized battery.
  • the present invention has the following advantages and technical effects:
  • isopyrrolopyrroledione groups in the ⁇ bridge can expand the spectral response, effectively inhibit dye aggregation and electron recombination, prolong the electron lifetime, and improve the photoelectric conversion efficiency of the sensitized solar cell.
  • Example 1 The dye obtained in Example 1 was subjected to ultraviolet-visible absorption spectroscopy, and its ultraviolet-visible absorption spectrum is shown in Fig. 1.
  • the dye-sensitized solar cell of the present invention is produced as follows:
  • the treated conductive glass was placed with the conductive surface facing up, the screen plate was placed above the glass, the mesh distance of 1 cm was controlled, and the prepared TiO 2 nanocrystal slurry was placed on the screen for printing.
  • the thickness of the TiO 2 film is controlled as needed, and is about 17 ⁇ m (area of 4 ⁇ 4 mm) used in this chapter.
  • the prepared photoanodes were placed in an oven and dried at 125 °C. It was placed in a muffle furnace and then treated at different temperatures (bake at 325 ° C for 5 min, 375 ° C for 5 min, 450 ° C for 15 min, and 500 ° C for 15 min) to remove the organic matter on the membrane.
  • the tape is made into a suitable inner hole plastic by a puncher, and the insulating film is placed on the sensitized photoanode so that the photoanode is just in the inner hole of the insulating film.
  • 1 to 2 drops of the electrolyte prepared in (4) were added dropwise, and the platinum counter electrode prepared by capping on the photoanode was fixed with clips on both sides to form an open sensitizing dye solar cell to be tested.
  • Battery performance test The lead wire is taken out from the photoanode and the photocathode of the battery, and connected to the battery performance test device.
  • the working area of the battery is 0.16 cm 2 , and the sunlight is simulated by a solar simulator to adjust the light intensity to 100 mW.
  • the /cm 2 test is based on the JV curve of the dye-sensitized battery.
  • the dyes synthesized in the first embodiment were assembled into batteries, and the wires were taken out from the photoanode and the photocathode respectively, and connected to the battery performance test device.
  • the solar simulator simulates sunlight, and the light intensity is adjusted to 100 mW/cm 2 to test the JV curve of the battery based on the dye sensitization, respectively.
  • the dye isoDPP exhibits high photoelectric conversion efficiency with good short-circuit current and open circuit voltage. This is mainly due to the dye's ability to capture light and to inhibit aggregation.

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Abstract

本发明公开了异吡咯并吡咯二酮染料及其应用。本发明以4,4'-二己氧基三苯胺为电子给体，异吡咯并吡咯二酮为π桥，氰基乙酸为电子受体和锚固基团，并在异吡咯并吡咯二酮基团上引入烷基链合成了一系列的基于异吡咯并吡咯二酮的纯有机染料。该类型的染料具有较好的捕光性能，具有较大空间位阻，吸附在半导体膜上不容易聚集，以异吡咯并吡咯二酮为电子π桥的纯有机染料在染料敏化太阳电池中应用，具有良好的抑制电子复合的能力，染料敏化太阳电池的光电转换效率高。

Description

异吡咯并吡咯二酮染料及其应用 技术领域
本发明涉及有机染料及染料敏化太阳电池技术领域，具体涉及异吡咯并吡咯二酮染料及应用。
技术背景
化石能源长期大范围的使用，不仅造成了化石能源的日益紧缺导致将来面临枯竭，还带来了难以治理的环境问题。因此，开发利用太阳能等可持续的洁净能源引起了世界各地科研工作者的广泛关注。其中，染料敏化太阳电池(DSSCs)是光伏产业的代表之一，在近二十年来得到了快速的发展。敏化染料是该电池的重要组成部分，直接影响着电池的性能和实际应用，并且可以分为纯有机染料和金属配合物染料两大类。虽然金属配合物染料具有光电转换效率较高的优势，但纯有机染料也拥有结构可调性大，易于合成和分离，成本相对较低等特点而使其也具有竞争力。
其中基于吡咯并吡咯二酮(DPP)的纯有机染料具有优越的捕光性能，有较宽的光覆盖范围，而且有良好的光化学性质和良好的光稳定性、化学稳定性，有较好的发展潜力。DPP有结构十分相似的同分异构体，即异吡咯并吡咯二酮(isoDPP)。两者的差别只在于内酰亚胺键中的羰基和氮原子位置不同。到目前为止还没有基于isoDPP的纯有机染料的报道。本发明设计并合成一类以4,4′-二己氧基三苯胺为电子给体，异吡咯并吡咯二酮为π桥，氰基乙酸为电子受体和锚固基团的纯有机染料。该染料具有结构简单，合成容易，光电转化性能良好等优点。
发明内容
本发明公开了基于异吡咯并吡咯二酮为π桥的染料及其在染料敏化太阳电池中的应用。本发明合成一类新型的不含金属的纯有机光敏染料，这类染料以4,4′-二己氧基三苯胺为电子给体，异吡咯并吡咯二酮为π桥，氰基乙酸为电子受体和锚固基团的纯有机染料，并在异吡咯并吡咯二酮基团上引入烷基链。这类染料在染料敏化太阳电池上具有良好的应用性能。其结构通式如下：
Figure PCTCN2015100048-appb-000001
其中：R1、R2为C1～C20的直链烷基、C1～C20的支链烷基或C1～C20的烷氧基，R1和R2可以相同或不同；A1、A2为噻吩、苯环、呋喃、3,4-二氧乙撑噻吩或吡咯，A1和A2可以相同或不同。
本发明的基于异吡咯并吡咯二酮为π桥的染料的合成方法简单，原料价廉易得，举例说 明，其合成步骤如下：
当R1为正己氧基，R2为异辛基，A1和A2为苯基时的合成路线为：
Figure PCTCN2015100048-appb-000002
化合物2的合成方法：
以DMF为溶剂，将化合物1、3份的CsCO3，在Ar保护下油浴升温到60℃搅拌1小时。将6份的溴代异辛烷的DMF溶液缓慢注入上述反应液。注入完毕后将油浴升温到120℃继续反应24小时。冷却，往反应瓶中加入水，用二氯甲烷萃取，有机层水洗，干燥，浓缩粗产物柱层析得化合物2。
化合物3的合成方法：
以甲苯为溶剂，加入上述化合物2和2份的4,4′-二己氧基三苯胺硼酸酯，8％份的Pd(PPh3)4，2份的2M的K2CO3水溶液。在Ar保护下油浴升温至80℃反应19h。冷却，往反应瓶中加入水，用二氯甲烷萃取，有机层水洗，干燥，浓缩粗产物柱层析得化合物3。
化合物4的合成方法：
以THF为溶剂，加入化合物3，降温至0℃,然后在避光下加入1.5份的NBS，让其自然反应至常温12h。倒入水中，加入二氯甲烷萃取，有机层水洗，干燥，浓缩粗产物柱层析。再将柱层析产物转移，以甲苯为溶剂，加入2份的4-甲酰基苯硼酸，8％份的Pd(PPh3)4，2份的2M的K2CO3水溶液。在Ar保护下油浴升温至80℃反应24h。冷却，往反应瓶中加入水，用二氯甲烷萃取，有机层水洗，干燥，浓缩粗产物柱层析得化合物4。
化合物5的合成方法：
以甲苯为溶剂，加入化合物4和2份氰基乙酸叔丁酯，2份醋酸铵，2mL醋酸。在Ar保护下油浴升温反应液回流反应5h。倒入冷水中，加入二氯甲烷萃取，有机层水洗，干燥，浓缩，粗产物通过柱层析分离提纯得化合物5。
染料isoDPP的合成方法：
以三氟乙酸为溶剂，加入化合物4于室温下搅拌反应4h。倒入去离子水中，待固体析出，过滤收集固体，并用去离子水反复洗涤直至洗涤产生的液体的pH值显示为中性，干燥。
本发明合成的异吡咯并吡咯二酮染料在染料敏化太阳电池中的应用，包括染料敏化太阳 电池的组成和构造、制备步骤和电池性能测试：
(1)染料敏化太阳电池的组成和构造：分导电玻璃基质(通常为掺氟的SnO2透明导电玻璃，即FTO)、光阳极、敏化剂、电解质和对电极(一般为镀铂的导电玻璃)五大组成部分；其中光阳极基板工作区域一侧导电玻璃中间设有纳米多孔TiO2薄膜，可用以吸附染料；对电极也称光阴极，其基板工作区域一侧导电玻璃中间设有催化剂层，其中催化剂多为Pt；光阳极和光阴极相对间隔设置，所述纳米多孔TiO2薄膜周边用密封材料密封形成密闭的腔体，腔体内填充有电解质和敏化剂(即异吡咯并吡咯二酮染料)。
(2)染料敏化太阳电池的制备步骤：
(1)导电玻璃(FTO)的预处理：将裁好的FTO超声清洗，并用去离子水冲洗3～6次，再置于KOH的饱和乙醇溶液中浸泡16～36h，再依次用去离子水、丙酮、去离子水和乙醇超声清洗，干燥后保存待用；
(2)光阳极的制备：室温下，将10～25mLTi(OBu)2和15～30mLEtOH的混合液剧烈搅拌下加入35～80mL乙酸和去离子水并继续搅拌30min～2h，将此混合液移入内衬特氟隆(聚四氟乙烯)的高压釜中，于200～280℃处理8～20h后自然冷却至室温，将所得的悬浊液过滤，依次用去离子水和乙醇洗涤3～6次，于烘箱中40～60℃下烘4～8h至干后得到TiO2纳晶颗粒，向制备好的TiO2纳晶颗粒中分别加入乙醇、乙酸、松油醇、乙基纤维素后，将该混合物充分研磨得到泥浆状物质，经超声得到所需的白色粘性TiO2纳晶浆料；
将处理好的导电玻璃导电面朝上，将丝网板置于玻璃上方，控制0.5～3cm的网距，将制备好的TiO2纳晶浆料置于丝网上进行印刷。根据需要控制TiO2膜厚度，所采用的约为8～20μm(面积为2至4×2至4mm)，将制备好的光阳极放入烘箱中于100～150℃干燥，再放于马弗炉中依次在不同的温度下处理(300～350℃烘焙3～10min，300～400℃烘焙3～10min，400～500℃烘焙10～20min，450～550℃烘焙10～20min)，以充分除去膜上的有机物质，然后浸于制备的0.1～0.3M的TiCl4水溶液中处理30min～1.5h，处理结束用去离子水和乙醇冲洗干净，置于马弗炉中升温到450～550℃再次烘焙25～40min，冷却至60～80℃后备用；
(3)染料溶液的配制：将权利要求1所述的异吡咯并吡咯二酮染料溶于氯仿/甲醇(v/v＝4/1～1/4)的混合溶剂中，配制成1×10-4至3×10-4mol·L-1染料溶液；
(4)电解质溶液的配制：0.5M～0.71-甲基-3-丙基碘化咪唑鎓(PMII)，0.03～0.07M硫氰酸胍，0.03～0.07M LiI，0.01～0.04M I2和0.15～0.40M叔丁基吡啶(TBP)溶于乙腈，并混合均匀得到澄清的溶液；
(5)光阳极的敏化：将步骤(2)制备的光阳极浸泡于步骤(3)配制的染料溶液中，在阴暗避光环境中染浴10～20小时后，取出并用氯仿/甲醇(v/v＝4/1～1/4)的混合溶剂冲洗除去表面的残留或膜表面的染料，吹干后保存干燥避光环境以待封装，备用；
(6)用打孔器将胶带制成合适的内孔塑料，将此绝缘薄膜置于已敏化的光阳极，使光阳极恰好处于绝缘薄膜内孔里，向TiO2膜表面滴加1～2滴步骤(5)制备的电解液，并在光阳极上盖制备的铂对电极，两边用夹子固定即形成待测的开放性敏化染料太阳电池。
进一步优化地，染料敏化太阳电池的制备步骤包括如下具体步骤：
a、导电玻璃(FTO)的预处理：将裁好的FTO(2～4cm×5～10cm)超声清洗，并用去 离子水冲洗数次。再置于KOH的饱和乙醇溶液中浸泡24h。再依次用去离子水、丙酮、去离子水和乙醇超声清洗，干燥后保存待用；
b、光阳极的制备：室温下，将15mLTi(OBu)2和20mLEtOH的混合液剧烈搅拌下加入50mL乙酸和去离子水并继续搅拌1h。将此混合液移入内衬特氟隆(聚四氟乙烯)的高压釜于230℃处理12h后自然冷却至室温。将所得的悬浊液过滤，依次用去离子水和乙醇洗涤多次，50℃下于烘箱中烘6h至干后得到TiO2纳晶颗粒。向制备的TiO2纳晶颗粒分别加入乙醇、乙酸、松油醇、乙基纤维素后，将该混合物充分研磨得到泥浆状物质。经超声得到所需的白色粘性TiO2纳晶浆料。
将处理好的导电玻璃导电面朝上，将丝网板置于玻璃上方，控制1cm的网距，将制备好的TiO2纳晶浆料置于丝网上进行印刷。根据需要控制TiO2膜厚度，本章所采用的约为17μm(面积为4×4mm)。将制备的光阳极需放入烘箱于125℃干燥。再放于马弗炉中依次在不同的温度下处理(325℃烘焙5min，375℃烘焙5min，450℃烘焙15min，500℃烘焙15min)，以充分除去膜上的有机物质。然后浸于制备的0.2M的TiCl4水溶液中处理半小时。处理结束用去离子水和乙醇冲洗干净，置于马弗炉中升温500℃再次烘焙30min。冷至70℃后备用；
c、染料溶液的配制：将权利要求1所述的异吡咯并吡咯二酮染料溶于氯仿/甲醇(v/v＝1/1)的混合溶剂中，配制成2×10-4mol·L-1染料溶液；
d、电解质溶液的配制：0.6M1-甲基-3-丙基碘化咪唑鎓(PMII)，0.05M硫氰酸胍，0.05M LiI，0.03M I2和0.25M叔丁基吡啶(TBP)的乙腈溶液；
e、光阳极的敏化：将步骤b制备的光阳极浸泡于步骤c配制的染料溶液中在阴暗避光环境中染浴15小时后，取出并用氯仿/甲醇(v/v＝1/1)的混合溶剂冲洗除去表面的残留或膜表面的染料，吹干后保存干燥避光环境以待封装，备用；
f、用打孔器将胶带制成合适的内孔塑料，将此绝缘薄膜置于完成敏化的光阳极，使光阳极恰好处于绝缘薄膜内孔里。向TiO2膜表面滴加1～2滴电解液(d制备的)，并在光阳极上盖制备的铂对电极，两边用夹子固定即形成待测的开放性敏化染料太阳电池。
(3)电池性能测试：从电池的光阳极和光阴极分别引出导线，接到电池性能测试装置上，电池的工作面积为0.16cm2，用太阳光模拟器模拟太阳光，将光强度调节至100mW/cm2测试基于该染料敏化的电池的J-V曲线。
与现有技术相比，本发明具有如下优点和技术效果：
在π桥中引入异吡咯并吡咯二酮基团可以起到扩大光谱响应，有效地抑制染料的聚集和电子的复合，延长了电子寿命，提高了敏化太阳电池的光电转换效率。
附图说明
图1为实施例1中所合成的染料在4-叔丁醇/乙腈混合溶液(v/v＝1/1)中紫外/可见吸收谱图。
图2为实施例3的染料敏化太阳电池的J-V曲线图。
具体实施方式
下面结合实施例对本发明做进一步地详细说明，但是本发明要求保护的范围并不局限于实施例表示的范围。
实施例1
π桥中含异吡咯并吡咯二酮的染料isoDPP的合成
(1)化合物2的合成
Figure PCTCN2015100048-appb-000003
在100mL两口反应瓶中分别加入化合物1(2.33g,6.25mmol)，CsCO3(6.11g,18.74mmol)和30mL干燥的DMF，用真空泵抽出装置中的空气，并充入Ar。将油浴升温到60℃搅拌1小时。将溴代异辛烷(7.24g,37.50mmol)的DMF(7mL)溶液用一次性注射器缓慢注入上述反应液。注入完毕后将油浴升温到120℃继续反应24小时。反应结束后降至室温，反应液搅拌下加入稀盐酸溶液调节溶液pH值显示为中性。用3×50mL二氯甲烷萃取，合并有机相并用饱和食盐水洗涤后用无水硫酸钠干燥，旋蒸除去二氯甲烷，残余物为中间体2的粗产物，柱层析分离后直接用于下一步反应。
(2)化合物3的合成
Figure PCTCN2015100048-appb-000004
在50mL两口反应瓶中分别加入上述化合物2，4,4′-二己氧基三苯胺硼酸酯(1.49g,2.60mmol)，Pd(PPh3)4(125.00mg,0.11mmol)，2M的K2CO3水溶液(2.20mL)和30mL重蒸的甲苯，用真空泵抽出装置中的空气，并充入Ar。将油浴升温到80℃反应19小时。反应结束后降至室温，反应液倒入水中，用3×50mL二氯甲烷萃取，合并有机相并用饱和食盐水洗涤后用无水硫酸钠干燥，旋蒸除去二氯甲烷，残余物以石油醚(bp 60–90℃)和乙酸乙酯(v/v＝20:1)为洗脱剂经硅胶柱层析色谱分离纯化，真空干燥后得橙红色固体3(0.11g,0.01mmol)，制备化合物2和化合物3两步的综合产率为0.16％，熔点是149-151℃。
1H NMR(CDCl3,400MHz,ppm):δ8.22(s,1H),7.79–7.76(m,1H),7.63(d,J＝8.0Hz,2H),7.51–7.49(m,1H),7.47–7.39(m,4H),7.08(d,J＝8.0Hz,4H),6.99(d,J＝8.0Hz,2H),6.84(d,J＝8.0Hz,4H),3.94(t,J＝6.0Hz,4H),3.85–3.55(m,4H),1.80–1.77(m,4H),1.58(s,9H),1.49–1.40(m,4H),1.37–1.32(m,12H),1.20–1.15(m,8H),0.94–0.88(m,6H),0.82–0.74(m,9H),0.65–0.60(m,3H).
(3)化合物4的合成
Figure PCTCN2015100048-appb-000005
在50mL的单口瓶中加入中间体3(0.65g,0.68mmol)和25mL的四氢呋喃。于冰浴下搅拌15分钟后，避光加入NBS(0.18g,1.01mmol)，并继续保持冰浴反应1小时，再转移至室温反应10小时。反应结束后，将反应液倒入水中，用3×50mL二氯甲烷萃取，合并有机相并用饱和食盐水洗涤后用无水硫酸钠干燥，旋蒸除去二氯甲烷。将该残余物转移至50mL的两口瓶中，并加入4-甲酰基苯硼酸(0.11g,72.00mmol)，Pd(PPh3)4(58.00mg,0.05mmol)，2M的K2CO3水溶液(0.50mL)和20mL重蒸的甲苯，用真空泵抽出装置中的空气，并充入Ar。将油浴升温到80℃反应24小时。反应结束后，将反应液倒入水中，用3×50mL二氯甲烷萃取，合并有机相并用饱和食盐水洗涤后用无水硫酸钠干燥，旋蒸除去二氯甲烷，残余物以石油醚(bp 60–90℃)和乙酸乙酯(v/v＝50:1)为洗脱剂经硅胶柱层析色谱分离纯化，真空干燥后得红色固体4(0.34g,0.32mmol)，产率为47.1％，熔点为114–116℃。
1H NMR(CDCl3,400MHz,ppm):δ9.97(s,1H),7.87(d,J＝7.2Hz,2H),7.76(d,J＝7.2Hz,2H),7.63–7.59(m,2H),7.49–7.40(m,5H),7.39–7.34(m,1H),7.08(d,J＝8.0Hz,4H),7.00–6.96(m,2H),6.84(d,J＝7.9Hz,4H),3.95–3.89(m,4H),3.82–3.75(m,2H),3.65–3.60(m,2H),1.83–1.75(m,4H),1.50–1.43(m,4H),1.38–1.32(m,8H),1.26–0.97(m,18H),0.94–0.89(m,6H),0.82–0.72(m,9H),0.65–0.60(m,3H).
(4)化合物5的合成
Figure PCTCN2015100048-appb-000006
在50mL两口反应瓶中分别加入中间体4(0.25g,0.235mmol)，氰基乙酸叔丁酯(66.00mg,0.47mmol)，醋酸铵(36.00mg,0.47mmol)，醋酸(2mL)和25mL的甲苯，用真空泵抽出装置中的空气，并充入Ar。将油浴升温反应液回流反应5小时。反应结束后降至室温，将反应液倒入水中，用3×50mL二氯甲烷萃取，合并有机相并用饱和食盐水洗涤后用无水硫酸钠干燥，旋蒸除去二氯甲烷，残余物以石油醚(bp 60–90℃)和乙酸乙酯(v/v＝20:1)为洗脱剂经硅胶柱层析色谱分离纯化，真空干燥后得红色固体5(0.25g,0.213mmol)，产率为90.7％，熔 点为123–125℃。
1H NMR(CDCl3,400MHz,ppm):δ8.01(s,1H),7.87(d,J＝7.6Hz,2H),7.59(d,J＝7.6Hz,2H),7.49(d,J＝7.6Hz,2H),7.37–7.24(m,6H),6.95(d,J＝8.0Hz,4H),6.86(d,J＝7.6Hz,2H),6.71(d,J＝8.0Hz,4H),3.83–3.77(m,4H),3.74–3.64(m,2H),3.57–3.40(m,2H),1.70–1.60(m,4H),1.47(s,9H),1.39–1.35(m,4H),1.28–1.20(m,8H),1.14–0.90(m,18H),0.81–0.75(m,6H),0.70–0.60(m,9H),0.55–0.45(m,3H).
(5)化合物6的合成
Figure PCTCN2015100048-appb-000007
于25mL的单口瓶中加入中间体5(0.13g,0.109mmol)和三氟乙酸(8mL)于常温下搅拌4h。反应结束后，将反应液倒入100mL的去离子水中。待固体析出，过滤收集固体，并用去离子水反复洗涤直至洗涤产生的液体的pH为中性。将固体干燥得黑色固体染料isoDPP(103.00mg,0.091mmol)，产率为83.8％，熔点为127-129℃。
1H NMR(THF-d8,400MHz,ppm):δ8.24(s,1H),8.13–8.09(m,2H),7.87(d,J＝8.0Hz,2H),7.69–7.64(m,3H),7.53–7.45(m,5H),7.04(d,J＝8.0Hz,4H),6.95(d,J＝8.0Hz,2H),6.84(d,J＝8.0Hz,4H),3.99–3.92(m,4H),3.88–3.84(m,2H),3.70–3.64(m,2H),1.81–1.74(m,4H),1.52–1.46(m,4H),1.40–1.34(m,8H),1.25–1.14(m,10H),1.09–1.00(m,8H),0.95–0.90(m,6H),0.81–0.73(m,9H),0.65–0.61(m,3H).
实施例2
对实施例1得到的染料进行紫外-可见吸收光谱测试，其紫外-可见吸收光谱如图1所示。
溶剂：4-叔丁醇/乙腈混合溶液(v/v＝1/1)
浓度：2×10-5M
温度：室温
仪器：Shimadzu UV-2450紫外可见分光光度计
从图1中可以看出在4-叔丁醇/乙腈混合溶液(v/v＝1/1)中不同于大部分纯有机染料，染料isoDPP仅表现为一个吸收峰，但呈现出较宽的覆盖范围。在400–490nm的范围内都超过了10,000M-1cm-1，这表明染料具有良好的光捕获能力。
实施例3
本发明中染料敏化太阳电池的制作如下：
(1)导电玻璃(FTO)的预处理：将裁好的FTO(2×5cm)超声清洗，并用去离子水冲 洗4次。再置于KOH的饱和乙醇溶液中浸泡24h。再依次用去离子水、丙酮、去离子水和乙醇超声清洗，干燥后保存待用；
(2)光阳极的制备：室温下，将15mL Ti(OBu)2和20mL EtOH的混合液剧烈搅拌下加入50mL乙酸和去离子水并继续搅拌1h。将此混合液移入内衬特氟隆(聚四氟乙烯)的高压釜于230℃处理12h后自然冷却至室温。将所得的悬浊液过滤，依次用去离子水和乙醇洗涤4次(，于烘箱中50℃下烘6h，至干后得到TiO2纳晶颗粒。向制备的TiO2纳晶颗粒中分别加入1mL乙醇、0.5mL乙酸、1.2mL松油醇、1.6mL乙基纤维素后，将该混合物充分研磨得到泥浆状物质。经超声得到所需的白色粘性TiO2纳晶浆料。
将处理好的导电玻璃导电面朝上，将丝网板置于玻璃上方，控制1cm的网距，将制备好的TiO2纳晶浆料置于丝网上进行印刷。根据需要控制TiO2膜厚度，本章所采用的约为17μm(面积为4×4mm)。将制备的光阳极需放入烘箱于125℃干燥。再放于马弗炉中依次在不同的温度下处理(325℃烘焙5min，375℃烘焙5min，450℃烘焙15min，500℃烘焙15min)，以充分除去膜上的有机物质。然后浸于制备好的0.2M的TiCl4水溶液中处理半小时。处理结束用去离子水和乙醇冲洗干净，置于马弗炉中升温500℃再次烘焙30min。冷至70℃后备用；
(3)染料溶液的配制：将实施例1制备得到的异吡咯并吡咯二酮染料溶于氯仿/甲醇(v：v＝1：1)的混合溶剂中，配制成2×10-4mol·L-1染料溶液；
(4)电解质溶液的配制：0.6M 1-甲基-3-丙基碘化咪唑鎓(PMII)，0.05M硫氰酸胍，0.05M LiI，0.03M I2和0.25M叔丁基吡啶(TBP)溶于乙腈混合后得到均一稳定的溶液；
(5)光阳极的敏化：将步骤(2)制备的光阳极浸泡于步骤(3)配制的染料溶液中在阴暗避光环境中染浴15小时后，取出并用氯仿/甲醇(v/v＝1/1)的混合溶剂冲洗表面除去残留或物理吸附于膜表面的染料，吹干后保存于干燥避光环境以待封装，备用；
(6)用打孔器将胶带制成合适的内孔塑料，将此绝缘薄膜置于完成敏化的光阳极，使光阳极恰好处于绝缘薄膜内孔里。向TiO2膜表面滴加1～2滴(4)制备的电解液，并在光阳极上盖制备的铂对电极，两边用夹子固定即形成待测的开放性敏化染料太阳电池。
(7)电池性能测试：从电池的光阳极和光阴极分别引出导线，接到电池性能测试装置上，电池的工作面积为0.16cm2，用太阳光模拟器模拟太阳光，将光强度调节至100mW/cm2测试基于该染料敏化的电池的J-V曲线。
实施例4
染料敏化太阳电池性能测试：
按照实施例3中的电池制备步骤，分别以实施例1合成的染料组装成电池，分别从光阳极和光阴极引出导线，接到电池性能测试装置上，电池的工作面积为0.16cm2时，用太阳光模拟器模拟太阳光，将光强度调节至100mW/cm2分别测试基于该染料敏化的电池的J-V曲线。
将所测得的J-V曲线图(图2)，数据汇总于表1。
表1 实施例1染料用于染料敏化太阳电池性能数据
Figure PCTCN2015100048-appb-000008
从图2和表1的数据可以看出，染料isoDPP展现出较高的光电转换效率，拥有良好的短路电流和开路电压。这主要是由于染料具有较好的光捕获能力和很强的抑制聚集的能力。

Claims (3)

  1. 在π桥中引入异吡咯并吡咯二酮基团的纯有机染料，其特征在于，结构通式如下：
    Figure PCTCN2015100048-appb-100001
    其中：R1、R2为C1～C20的直链烷基、C1～C20的支链烷基或C1～C20的烷氧基，R1和R2可以相同或不同；A1、A2为噻吩、苯环、呋喃、3,4-二氧乙撑噻吩或吡咯，A1和A2可以相同或不同。
  2. 权利要求1所述在π桥中引入异吡咯并吡咯二酮基团的纯有机染料在染料敏化太阳电池中的应用，其特征在于：所述染料敏化太阳电池主要由导电玻璃基质、光阳极、敏化剂、电解质和对电极组成；其中光阳极基板工作区域一侧导电玻璃中间设有纳米多孔TiO2薄膜，可用以吸附染料；对电极也称光阴极，其基板工作区域一侧导电玻璃中间设有催化剂层，其中催化剂为Pt；光阳极和光阴极相对间隔设置，所述纳米多孔TiO2薄膜周边用密封材料密封形成密闭的腔体，腔体内填充有电解质和敏化剂即异吡咯并吡咯二酮染料。
  3. 根据权利要求2所述的在π桥中引入异吡咯并吡咯二酮染料在染料敏化太阳电池中的应用，其特征在于，制备步骤如下：
    (1)导电玻璃(FTO)的预处理：将裁好的FTO超声清洗，并用去离子水冲洗3～6次，再置于KOH的饱和乙醇溶液中浸泡16～36h，再依次用去离子水、丙酮、去离子水和乙醇超声清洗，干燥后保存待用；
    (2)光阳极的制备：室温下，将10～25mLTi(OBu)2和15～30mLEtOH的混合液剧烈搅拌下加入35～80mL乙酸和去离子水并继续搅拌30min～2h，将此混合液移入内衬特氟隆(聚四氟乙烯)的高压釜中，于200～280℃处理8～20h后自然冷却至室温，将所得的悬浊液过滤，依次用去离子水和乙醇洗涤3～6次，于烘箱中40～60℃下烘4～8h至干后得到TiO2纳晶颗粒，向制备好的TiO2纳晶颗粒中分别加入乙醇、乙酸、松油醇、乙基纤维素后，将该混合物充分研磨得到泥浆状物质，经超声得到所需的白色粘性TiO2纳晶浆料；
    将处理好的导电玻璃导电面朝上，将丝网板置于玻璃上方，控制0.5～3cm的网距，将制备好的TiO2纳晶浆料置于丝网上进行印刷；将制备好的光阳极放入烘箱中于100～150℃干燥，再放于马弗炉中依次在不同的温度下处理：300～350℃烘焙3～10min，300～400℃烘焙3～10min，400～500℃烘焙10～20min，450～550℃烘焙10～20min，以充分除去膜上的有机物质，然后浸于制备的0.1～0.3M的TiCl4水溶液中处理30min～1.5h，处理结束用去离子水和乙醇冲洗干净，置于马弗炉中升温到450～550℃再次烘焙25～40min，冷却至60～80℃后备用；
    (3)染料溶液的配制：将所述的异吡咯并吡咯二酮染料溶于氯仿/甲醇的混合溶剂中， 配制成1×10-4～3×10-4mol·L-1染料溶液，氯仿/甲醇的体积比为4/1～1/4；
    (4)电解质溶液的配制：0.5M～0.71-甲基-3-丙基碘化咪唑鎓(PMII)，0.03～0.07M硫氰酸胍，0.03～0.07M LiI，0.01～0.04M I2和0.15～0.40M叔丁基吡啶(TBP)溶于乙腈，并混合均匀得到澄清的溶液；
    (5)光阳极的敏化：将步骤(2)制备的光阳极浸泡于步骤(3)配制的染料溶液中，在阴暗避光环境中染浴10～20小时后，取出并用氯仿/甲醇的混合溶剂冲洗除去表面的残留或膜表面的染料，吹干后保存干燥避光环境以待封装，备用；氯仿/甲醇的体积比为4/1～1/4；
    (6)用打孔器将胶带制成合适的内孔塑料，将此绝缘薄膜置于已敏化的光阳极，使光阳极恰好处于绝缘薄膜内孔里，向TiO2膜表面滴加1～2滴步骤(5)制备的电解液，并在光阳极上盖制备的铂对电极，两边用夹子固定即形成待测的开放性敏化染料太阳电池。
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