CN104649949A - 一种纯有机D-π-A型光敏染料及其制备方法和应用 - Google Patents
一种纯有机D-π-A型光敏染料及其制备方法和应用 Download PDFInfo
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- C07D207/325—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
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Abstract
本发明公开了一种纯有机D-π-A型光敏染料及其制备方法和应用，该光敏染料是以1,2,5-三苯基吡咯作为供电子基团、以苯乙烯作为电子传递链、以氰基乙酸为吸电子基团的三苯基吡咯D-π-A型光敏染料，先在氩气保护下，将对醛基苯乙烯、1-(对溴苯基)-2,5-二苯基吡咯、醋酸钯、四丁基溴化铵、三(邻甲基苯基)磷加入到N,N’-二甲基甲酰胺和三乙胺的混合液中制得中间产物4-(4-(2,5-二苯基吡咯)苯乙烯基)苯甲醛，再通过中间产物制得。本发明的纯有机D-π-A型光敏染料合成路线简单，成本低廉；作为制备太阳能电池的染料敏化剂摩尔消光系数较高，不易脱吸附，有助于提高电池整体寿命。
Description
技术领域
本发明涉及太阳能电池制备原料和方法技术领域，具体说是一种纯有机D-π-A型光敏染料及其制备方法和应用。
背景技术
在过去二十年中，染料敏化太阳能电池(DSSCs)由于较低的制造成本和较高的能量转化效率，引起了工业界和学术界的广泛关注。在光电子转化成电流的过程中，染料敏化剂在决定太阳能电池的性能方面起着至关重要的作用。与稀有贵金属钌配合物染料相比，不含贵金属的光敏染料，更契合人们对经济环保光伏系统的追求。然而，开发出低成本、高性能的DSSCs纯有机染料，对我们来说仍是一个挑战。
近十年来，纯有机D–π–A型染料发展迅速，主要包括三苯胺类、香豆素类、多烯类、吲哚类、芴类、咔唑类等。纯有机Donor–π–Acceptor (D-π-A)型染料具有分子结构多样、摩尔消光系数高、合成和提纯简单、原料易得、成本低廉等诸多优点，有利于推动DSSCs的产业化，具有很好的发展前景。因为不同类型的染料敏化剂具有不同的能极差，所以面对新型的电解质和半导体氧化层，需要我们开发具有新型供电子基团的染料敏化剂。
发明内容
本发明的目的是针对上述现有技术中的不足，设计并合成了一种以1,2,5-三苯基吡咯作为供电子基团、苯乙烯作为电子传递链、以氰基乙酸为吸电子基团的纯有机D–π–A型光敏染料，并将其组装成染料敏化太阳能电池器件。
在已有的研究报道中，供电子基团含有吡咯基团的染料敏化剂报道很少。和三苯胺结构类似，1,2,5-三苯基吡咯也含有3个苯环稳定电子离域后形成的负电荷，促使电荷分离有效进行。目前还没有一例含有三苯基吡咯的染料运用于DSSCs中的报道。
本发明的目的是通过以下技术方案实现的：
一种纯有机D-π-A型光敏染料，是以1,2,5-三苯基吡咯作为供电子基团、以苯乙烯作为电子传递链、以氰基乙酸为吸电子基团的三苯基吡咯D-π-A型光敏染料，它具有如下分子结构：
。
一种制备权利要求1所述的纯有机D-π-A型光敏染料的方法，为按照如下合成路线进行的：
。
上述制备方法包括以下具体操作过程：
（1）在氩气保护下，将对醛基苯乙烯、1-(对溴苯基)-2,5-二苯基吡咯、醋酸钯、四丁基溴化铵、三(邻甲基苯基)磷按照物质的量比分别为1 ： 1 ：0.05 ：1 ：0.2的比例，加入到N,N’-二甲基甲酰胺和三乙胺的混合液中，在85~90℃恒温下反应20 ~ 30小时，冷却至室温后，过滤掉固体，减压蒸馏除去溶剂和三乙胺，得到中间产物，该中间产物为4-(4-(2,5-二苯基吡咯)苯乙烯基)苯甲醛。
（2）将步骤1得到的中间产物溶解到乙腈中，加入氰基乙酸和哌啶，在80-85℃温度下回流3小时，冷却至室温后，通过真空蒸馏除去溶剂，残余物经柱层析提纯后得到纯有机D-π-A型光敏染料。
进一步地设计方案中，步骤1中N,N’-二甲基甲酰胺和三乙胺的体积比为1-20:1，N,N’-二甲基甲酰胺和三乙胺组成的混合液的用量为20 ~ 150 mL/1g对醛基苯乙烯。
进一步地设计方案中，步骤2中乙腈和哌啶的体积比为10-100：1，每1g中间产物加入到10 ~ 60mL乙腈中；氰基乙酸的用量是中间产物物质的量的2-5倍。
本发明还提供了上述纯有机D-π-A型光敏染料作为制备太阳能电池的染料敏化剂的应用。
以商用P25二氧化钛为半导体氧化物，将其分散到适量表面活性剂和粘结剂中；搅拌均匀之后，通过丝网印刷多次制膜；再经过真空干燥和高温烧结后，就可以得到多孔TiO2纳米晶薄膜。
将上述纯有机D-π-A型光敏染料配制成溶液，把二氧化钛多孔性电极直接浸泡于上述染料溶液中进行染料敏化，然后清洗、烘干即完成工作电极的制备。在打孔导电玻璃上以蒸镀的方式镀上Pt制得对电极，用热封膜固定两片电极形成空腔，在空腔内注入电解质溶液，再封住Pt电极的电解液注孔，即制得染料敏化太阳能电池器件。
本发明具有以下突出的有益效果：
（1）三苯基吡咯D-π-A型光敏染料合成路线简单，成本低廉；（2）三苯基吡咯D-π-A型光敏染料的电子供体可以进一步进行取代，方便后期进行结构修饰，容易实现全可见光谱吸收；（3）三苯基吡咯D-π-A型光敏染料的短波长可见光的吸收能力较强，摩尔消光系数较高；（4）三苯基吡咯D-π-A型光敏染料在电池组装过程中性质稳定，不易脱吸附，有助于提高电池整体寿命。本发明为三苯基吡咯类光敏染料的分子设计与制备提供了新方法和新途径，同时为三苯基吡咯D-π-A型光敏染料在染料敏化太阳能电池的应用提供了可靠的技术支持。
附图说明
图1为三苯基吡咯D-π-A型光敏染料的合成路线；
图2为三苯基吡咯D-π-A型光敏染料的核磁共振氢谱图；
图3为三苯基吡咯D-π-A型光敏染料的电喷雾质谱图；
图4为三苯基吡咯D-π-A型光敏染料的紫外-可见光谱图；
图5为三苯基吡咯D-π-A型光敏染料的染料敏化太阳能电池器件结构示意图；
其中：1-FTO玻璃，2-TiO2电极，3-吸附在TiO2电极上的光敏染料层，4-电解液层，5-Pt对电极。
具体实施方式
下面结合附图及实施例对本发明作进一步说明:
以下实施例中：对醛基苯乙烯根据J. Org. Chem. 2005, 70, 3396-3424制得；1-(对溴苯基)-2,5-二苯基吡咯根据Med. Chem. Commun. 2013, 4, 1297-1304制得；其余原材料均为市场上购得。
实施例1、三苯基吡咯D-π-A型染料的合成方法，参见图1。
氩气保护下，在三颈瓶中加入11.2 mg醋酸钯 (0.05 mmol)、0.132 g对醛基苯乙烯 (1.0 mmol,)、0.374 g 1-(对溴苯基)-2,5-二苯基吡咯(1.0 mmol)、0.322 g四丁基溴化铵 (1.0 mmol)、60.4 mg三(邻甲基苯基)磷 (0.2 mmol)、8 mL N,N’-二甲基甲酰胺和5 mL三乙胺, 加热至90 ℃，维持该温度并搅拌24小时。冷却至室温后，过滤掉固体，减压蒸馏除去溶剂和三乙胺得到中间产物。将中间产物分散于10 mL无水CH3CN中，加入0.34 g氰基乙酸 (4.0 mmol)和0.1 mL哌啶，加热至80℃恒温回流3小时。冷却至室温后，通过真空蒸馏除去溶剂。残余物经柱层析(洗脱液为体积比为10:1的二氯甲烷和甲醇)提纯后得到0.205 g产品， 产率42%。1H NMR (DMSO–d 6 , 500 MHz): δ, [ppm]: 7.98 (s, 1H), 7.79 (d, J = 8.0 Hz, 2H), 7.05-7.35 (m, 16H), 7.02 (d, J = 8.0 Hz, 2H), 6.80 (d, J = 12.5 Hz, 1H), 6.68 (d, J = 12.5 Hz, 1H), 6.49 (d, J = 6.5 Hz, 2H)，参见图2。MS (ESI–MS): Calcd for C34H24N2O2, 492.57; found, 491.08{[M–H]–}，参见图3。从1H NMR及MS (ESI–MS)的检测结果可知，所得产物确证为三苯基吡咯D-π-A型光敏染料。
将实施例1制得的产品配置成0.02 mM的染料溶液，溶剂组成为CHCl3 : EtOH = 3:2。染料溶液的紫外可见吸收光谱通过Shimadzu UV–3600分光仪测量，记录300-700 nm间的光谱吸收。测定得到三苯基吡咯D-π-A型光敏染料的紫外-可见光谱，参见图4。可知：300-440 nm的吸收主要来自于分子内各基团内部的π–π*跃迁，以及分子内电子供体与受体间的电荷转移(ICT)。
实施例2、三苯基吡咯D-π-A型光敏染料作为制备太阳能电池的染料敏化剂的应用
三苯基吡咯D-π-A型光敏染料敏化的光阳极的制备方法：参见图5。FTO玻璃片1从大连七色光科技有限公司购买，FTO玻璃1的表面电阻为15 Ω·cm–2。使用前，FTO玻璃片1在清洁剂溶液中超声30分钟，用水和乙醇洗涤，然后浸泡在40 mM的TiCl4水溶液中，在70 ℃下浸泡30分钟，再用水和乙醇洗涤。通过丝网印刷6次制备得到TiO2纳米晶光电极2。TiO2浆料是由商用P25 TiO2纳米颗粒、乙基纤维素(作为粘结剂)和α–松油醇(作为溶剂)组成。TiO2通过丝网印刷到FTO玻璃片1上后在450 ℃下烧结1小时。2.0×2.0 cm2的TiO2薄膜的厚度为12 μm。冷却后，再用TiCl4处理：在70 ℃下浸泡30分钟，并在450 ℃下烧结30分钟。降温至85 ℃时，将所得TiO2电极2浸泡在0.4 mM光敏染料的溶液中，溶剂体积比为氯仿 : 乙醇 = 3 : 2，浸泡时间要超过24小时。用氯仿洗涤TiO2电极，洗去在TiO2电极上没有吸附的染料，即制得DSSCs光阳极。
Pt对电极5和热封膜从中国大连七色光科技有限公司购得。在两电极之间放置热封膜框，通过加热热封膜在两极间形成空腔，吸附了光敏染料3的TiO2电极2和Pt对电极5组装成一个密封的三明治型的电池。在对电极5的钻孔上滴一滴电解液，通过真空回填使电解液注入到电池中，形成电解液层4。最后，用热封膜和盖玻片(0.1mm厚)封住对电极5上的孔，制得DSSCs太阳能电池器件。注入到电池的电解液是由0.6 M BMII，50 mM LiI，30 mM I2，0.5 M 叔丁基吡啶和0.1 M GuNCS组成的溶液，溶剂为乙腈和戊腈(体积比为85:15)。
以上是本发明的较佳实施例，凡依本发明技术方案所作的改变，所产生的功能作用未超出本发明技术方案的范围时，均属于本发明的保护范围。
Claims (6)
1.一种纯有机D-π-A型光敏染料，其特征在于，该光敏染料是以1,2,5-三苯基吡咯作为供电子基团、以苯乙烯作为电子传递链、以氰基乙酸为吸电子基团的三苯基吡咯D-π-A型光敏染料，它具有如下分子结构：
。
2.一种制备权利要求1所述的纯有机D-π-A型光敏染料的方法，其特征在于，该制备方法为按照如下合成路线进行的：
。
3.根据权利要求2所述的制备方法，其特征在于，包括以下具体操作过程：
（1）在氩气保护下，将对醛基苯乙烯、1-(对溴苯基)-2,5-二苯基吡咯、醋酸钯、四丁基溴化铵、三(邻甲基苯基)磷按照物质的量比分别为1 ： 1 ：0.05 ：1 ：0.2的比例，加入到N,N’-二甲基甲酰胺和三乙胺的混合液中，在85~90℃恒温下反应20 ~ 30小时，冷却至室温后，过滤掉固体，减压蒸馏除去溶剂和三乙胺，得到中间产物；
（2）将步骤1得到的中间产物溶解到乙腈中，加入氰基乙酸和哌啶，在80-85℃温度下回流3小时，冷却至室温后，通过真空蒸馏除去溶剂，残余物经柱层析提纯后得到纯有机D-π-A型光敏染料。
4.根据权利要求3所述的制备方法，其特征在于，步骤1中N,N’-二甲基甲酰胺和三乙胺的体积比为1-20:1，N,N’-二甲基甲酰胺和三乙胺组成的混合液的用量为20 ~ 150 mL/1g对醛基苯乙烯。
5.根据权利要求3所述的制备方法，其特征在于，步骤2中乙腈和哌啶的体积比为10-100：1，每1g中间产物加入到10 ~ 60mL乙腈中；氰基乙酸的用量是中间产物物质的量的2-5倍。
6.权利要求1所述的纯有机D-π-A型光敏染料作为制备太阳能电池的染料敏化剂的应用。
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| CN106588789A (zh) * | 2016-12-07 | 2017-04-26 | 西京学院 | 一种以三唑为核心的染料敏化剂分子及其制备方法 |
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| EP3621945A4 (en) * | 2017-05-09 | 2021-03-03 | Ambient Photonics, Inc. | STYLE DERIVATIVES FOR THE TREATMENT OF THE CNS AND OTHER DISEASES |
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