CN110606937B - 一种含4-乙烯基苯胺衍生物合Zn(II)的聚合配合物及其制备方法与用途 - Google Patents
一种含4-乙烯基苯胺衍生物合Zn(II)的聚合配合物及其制备方法与用途 Download PDFInfo
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
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- -1 zinc (II) ions Chemical class 0.000 claims abstract description 5
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Abstract
本发明涉及一种以4‑乙烯基苯胺与锌(II)离子形成的配体作为辅助受体A的D‑A‑π‑A型聚合配合物(如下式)的发明及制备方法，其用途为用于染料敏化太阳能电池中作染料敏化剂。该聚合配合物以二噻吩‑苯并二噻吩衍生物(BDTT)为给体(D)，以4‑乙烯基苯胺与锌(II)离子形成的配体作为辅助受体(A)，以8‑羟基喹啉作为π桥，以氰基丙烯酸为电子受体(A)和锚定基团，将Zn(II)配合物与二噻吩‑苯并二噻吩衍生物通过Heck聚合反应而制备得到的一种新型聚合配合物PBDTT‑VZn，该聚合配合物表现出良好的光电转化等光伏性能和高的热稳定性，光电转化效率达到7.61%，热分解温度达315℃，这将在染料敏化太阳能电池的开发应用方面具有一定的前景。
Description
技术领域
本发明涉及一种以4-乙烯基苯胺衍生物合Zn(II)为辅助电子受体A的D-A-π-A型聚合配合物染料及其制备方法和用于染料敏化太阳能电池中作染料敏化剂，属于新材料中光电材料领域。
背景技术
染料敏化太阳能电池是Grätzel和O’Regan在1991年研究发明的。其光伏原理如下：在光照下，吸附在电池FTO玻璃极板上薄膜TiO2颗粒表面的染料敏化剂分子吸收光，由基态变为激发态，由于染料激发态与TiO2 导带的能级差，激发态电子注入TiO2 导带，电子通过敏化的TiO2薄膜转移到FTO玻璃电极后，电子通过外电路传输到电池的对（正）电极，然后再通过电池内的氧化还原电解质转移到染料敏化剂分子的激发态，使其回到基态，而氧化还原电解质所失去的电子由注入对电极的电子所补充，从而形成整个光生电子的循环回路。
染料敏化剂是染料敏化太阳能电池中最关键的组成部分，它起着吸收太阳光产生电子并通过与TiO2的紧密结合而有效传递电子等核心作用。已有研究表明，金属配合物与聚合金属配合物将是最有发展潜力的染料，其结构有D-A型、D-π-A型和D-A-π-A型等。给体（D）与受体（A）相结合的构型，即D-A型，为比较早期研究的染料敏化剂构型，随着对敏化剂不断的深入研究，发现在D与A之间引入一个π桥能够有利于电子在D与A间的转移，并得到更好的光谱吸收。最近几年，提出了一类新型高效稳定的D-A-π-A型染料敏化剂，这是在D-π-A型染料敏化剂基础上，增加一个辅助电子受体A，以增强光吸收、降低电荷复合和加强电子传递，可以提高电池的光电转化效率和光伏性能。以4-乙烯基苯胺衍生物合Zn(II)作为辅助吸电子基团，这一设计思想是基于以下理念：第一，所采用的配合物中的过渡金属具有空轨道，使得配体具有可调节的吸电子能力；第二，敏化剂所采用的金属配体采用的四配位具有良好的平面性，这有利于敏化剂分子具有良好的共轭性，利于分子内的电子传输，有助于提高染料光电转化效率和使用寿命。因此，本发明研究开发一种以4-乙烯基苯胺衍生物合Zn(II)配合物为辅助电子受体A的D-A-π-A型聚合金属配合物作染料敏化太阳能电池的染料敏化剂。
发明内容
本发明的目的：在于提供一种以4-乙烯基苯胺衍生物合Zn(II)配合物为辅助电子受体的D-A-π-A型聚合配合物染料敏化剂PBDTT-VZn及其制备方法。通过Heck聚合反应将4-乙烯基苯胺衍生物合Zn(II)配合物电子受体部分与二噻吩-苯并二噻吩衍生物(BDTT)给体部分聚合，形成D-A-π-A结构的聚合配合物功能染料，并应用于染料敏化太阳能电池中作染料敏化剂。
本发明的技术方案是：一种含4-乙烯基苯胺衍生物合Zn(II)的聚合配合物。其特征在于，该化合物是以4-乙烯基苯胺衍生物合Zn(II)配合物作辅助电子受体A，具有D-A-π-A型的分子结构,其通式如式1：
式1 一种含4-乙烯基苯胺衍生物合Zn(II)的聚合配PBDTT-VZn的结构通式。
一种含4-乙烯基苯胺衍生物合Zn(II)的聚合配PBDTT-VZn的制备方法：
（1）．对硝基苄基三苯基溴化磷的制备：将 4-苄溴甲基硝基苯与三苯基磷在惰性条件下加入到CHCl3 中，搅拌0.5~1.0 h后将混合物倒入到无水乙醚中，析出白色固体，过滤，取沉淀物质在烘箱中干燥，得到白色粉末固体对硝基苄基三苯基溴化磷；
（2）．对硝基苯乙烯的制备：对硝基苄基三苯基溴化磷与甲醛悬浮液，剧烈搅拌，再将Na2CO3 溶于水中，每次在深红磷盐中间体消失后加Na2CO3溶液加完后继续搅拌4~8 h，用乙醚萃取，旋去乙醚，再用石油醚做洗脱剂硅胶过柱，得到浅黄色液体对硝基苯乙烯；
（3）．对4-氨基苯乙烯的制备：将对硝基苯乙烯溶解在干燥的二氧六环中，加水，搅拌10 min后加Zn粉，升温至70℃后反应7~8 h。反应结束后减压除去溶剂，水层用乙酸乙酯萃取，有机层为粗产物，再用硅胶过柱，洗脱剂为石油醚：乙酸乙酯=5：1，得到浅黄色固体对4-氨基苯乙烯；
（4）．含Zn(II)配合物(VZn)的合成：分别称取4-氨基苯乙烯和2-氰基-3-(8-羟基喹啉-5-基)丙烯酸，称量完成后将他们先后加入到盛有四氢呋喃的三口圆底烧瓶中搅拌，不断将溶解有Zn (CH3COO)2·H2O的甲醇溶液通过恒压滴液漏斗将其缓慢滴加到反应体系中，滴加完成后升温至回流反应12~24 h，反应结束后将体系冷却至室温后将析出的固体过滤，并先后用去离子水和无水乙醇洗涤2次，再将粗产物用无水甲醇重结晶两次，在真空条件下干燥数天后得到棕黄色固体VZn；
（5）．聚合金属配合物(PBDTT-VZn)的制备：聚合物(PBDTT-VZn)是根据Heck偶联反应而合成的，将Zn(II)配合物VZn，2,6-二溴-4,8-二(5-(2-乙基己基)噻吩基-2-基)-苯并[1,2-b:4,5-b']二噻吩(BDTT)加入到单口瓶中，之后加入醋酸钯，三(邻甲苯基)膦，将新蒸馏的精制干燥后的DMF溶液和三乙胺依次加入单口瓶，之后在氮气氛围下升温到90℃反应36~72 h，反应结束冷却至室温后将体系过滤，所得滤渣用大量的甲醇清洗，最终得到棕色沉淀PBDTT-VZn。
一种含4-乙烯基苯胺衍生物合Zn(II)的聚合配合物PBDTT-VZn的用途：在染料敏化太阳能电池中用作染料敏化剂。
发明的主要优势在于：一种含4-乙烯基苯胺衍生物合Zn(II)的聚合配合物，以4-乙烯基苯胺衍生物合Zn(II)配合物作辅助电子受体，并且将有机金属配合物聚合化，以扩大配合物分子的共轭π体系，提高其吸光性能和载流子传输能力，因而提高其作为染料敏化剂的光伏性能。
附图说明
图1本发明实施例合成的对4-氨基苯乙烯的核磁共振氢谱（1HNMR)（400MHz，CDCl3，TMS）；
图2本发明实施例合成的化合物VZn、PBDTT-VZn的红外光谱（IR）（KBr晶体压片，4000~450 cm-1）；
图3本发明实施例合成的聚合金属配合物PBDTT-VZn的热重分析(TGA)曲线；
图4本发明实施例合成的聚合金属配合物PBDTT-VZn的紫外-可见光吸收光谱(UV-vis)；
图5本发明实施例合成的聚合金属配合物PBDTT-VZn作染料敏化剂的染料敏化太阳能电池的电流密度-电压（J-V）曲线；
图6本发明实施例合成的聚合金属配合物PBDTT-VZn作染料敏化剂的染料敏化太阳能电池的外量子效率（IPCE）曲线。
具体实施方式
本发明的化合物的制备合成反应路线为：
下面结合具体实施例对本发明做进一步的说明。
实施例1
一种含4-乙烯基苯胺衍生物合Zn(II)的聚合配合物PBDTT-VZn。
一种以二噻吩-苯并二噻吩衍生物(BDTT)作为给体D，以 4-乙烯基苯胺衍生物合Zn(II)配合物为辅助电子受体A的聚合金属配合物PBDTT-VZn，其分子结构式为：
上述聚合配合物PBDTT-VZn的合成：
A．对硝基苄基三苯基溴化磷的制备：将 4-苄溴甲基硝基苯5.00 g (9.26 mmol)，与6.15 g (9.26 mmol)三苯基磷在惰性条件下加入到50 mL CHCl3 中，搅拌0.5~1 h后将混合物倒入到约40 mL无水乙醚中，析出白色固体，过滤，取沉淀物质在烘箱中干燥，得到白色粉末固体8.90g，产率56.0%，1H-NMR (CDCl3, δ, ppm): 7.62-7.88 (m, 15H), 7.61-7.62 (d, 2H), 7.43-7.44 (d, 2H), 5.86-5.90 (d, 2H)。
B．对硝基苯乙烯的制备：对硝基苄基三苯基溴化磷3.75 g (7.85 mmol), 15 mL37%甲醛悬浮液，剧烈搅拌，1.50 g Na2CO3 溶于10 mL水中，每次在深红磷盐中间体消失后加Na2CO3溶液加完后继续搅拌4~8 h，用乙醚萃取，旋去乙醚，再用石油醚做洗脱剂硅胶过柱，得到浅黄色液体0.79 g，产率68.0%，1H-NMR (CDCl3, δ, ppm): 8.17-8.19 (d, 2H),7.52-7.54 (d, 2H), 6.74-6.81 (q, 1H), 5.90-5.95 (d, 1H), 5.48-5.51 (d, 1H)。
C．对4-氨基苯乙烯的制备：将对硝基苯乙烯3.73 g (25.00 mmol)溶解在20 mL干燥的二氧六环中，加5 mL 水，搅拌10 min后加Zn粉4.88 g (75.00 mmol)，升温至70℃后反应7~8 h。反应结束后减压除去溶剂，水层用75 mL乙酸乙酯萃取，有机层为粗产物，再用硅胶过柱，洗脱剂为石油醚：乙酸乙酯=5：1，得到浅黄色固体1.37 g，产率46.0%，1H-NMR(CDCl3, δ, ppm): 7.21-7.25 (d, 2H), 6.63-6.64 (d, 2H), 6.64-6.64 (q, 1H),5.52-5.56 (d, 1H), 5.02-5.05 (d, 1H), 3.70-3.72 (m, 2H)。
D．含Zn(II)配合物(VZn) 的制备：分别称取0.95 g (8 mmol) 4-氨基苯乙烯和0.96 g (4 mmol) 2-氰基-3-(8-羟基喹啉-5-基)丙烯酸，称量完成后将他们先后加入到盛有100 mL四氢呋喃的250 mL三口圆底烧瓶中搅拌，不断将溶解有Zn(CH3COO)2·2H2O(0.96g，4.40mmol)的30 mL甲醇溶液通过恒压滴液漏斗将其缓慢滴加到反应体系中，滴加完成后升温至回流反应12~24 h，反应结束后将体系冷却至室温后将析出的固体过滤，并先后用去离子水和无水乙醇洗涤2次，再将粗产物用无水甲醇重结晶两次，在真空条件下干燥数天后得到的产物为棕黄色固体1.43 g，产率为59.0%，FT-IR (KBr, cm-1): 3408 (-OH),2216 (C≡N), 1623(C=C), 1564 (C=N), 1105 (C-O-Zn), 513 (N-Zn). Anal. Calcd.for [C31H28N4O4Zn]: C, 63.54; H, 4.82; N, 9.56. Found: C, 64.82; H, 4.88; N,9.52%。
E．聚合金属配合物(PBDTT-VZn)的制备：聚合物(PBDTT-VZn)是根据Heck偶联反应而合成的。将0.2912 g (0.40 mmol) Zn(II)配合物VZn，0.2958 g (0.40 mmol) 单体2,6-二溴-4,8-二(5-(2-乙基己基)噻吩基-2-基)-苯并[1,2-b:4,5-b']二噻吩(BDTT)加入到单口瓶中，之后加入醋酸钯0.0036 g (0.0167 mmol)，，三(邻甲苯基)膦0.0304 g (0.10mmol)，，将新蒸馏的精制干燥后的15 mL DMF溶液和4 mL三乙胺依次加入单口瓶，之后在氮气氛围下升温到90℃反应36~72 h。反应结束冷却至室温后将体系过滤，所得滤渣用大量的甲醇清洗，最终获得棕色固体产物0.2680 g，产率57.0%，FT-IR (KBr, cm-1): 3392 (-OH),2933, 2866 (C-H), 2209 (C≡N), 1656 (C=O), 1611 (C=C), 1551 (C=N), 1098 (C-O-Zn), 508 (N-Zn). Anal. Calcd. for [C68H76N4O4S2Zn]: C, 71.46; H, 6.70; N, 4.90;S, 5.61. Found: C, 72.14; H, 6.71; N, 4.87; S, 5.64%. Mn=10.61 Kg/mol, PDI=2.28。（其红外光谱（IR）表征如图2所示）。
实施例2：
测定聚合配合物染料PBDTT-VZn的热失重曲线(TGA)，方法：使用的是美国PA公司生产的型号为Q50热重分析仪的仪器，在氮气(N2)氛围下，以20℃/min的程序升温速率，测试25~800℃温度的范围内聚合金属配合物的热失重情况，测试结果如图3。
实施例3：
测定聚合配合物染料PBDTT-VZn的紫外-可见吸收光谱(UV-Vis)，方法：测试使用的紫外可见光谱仪为PE Lamada100型，在室温下以N,N-二甲基甲酰胺做溶剂将测试样品配制成1×10-5 mol/L浓度的溶液进行测试，测试结果如图4。
实施例4：
电流密度-电压(J-V)曲线是通过制备的电池器件在AM 1.5 G模拟太阳光下，以100 mW/cm2 光强通过Keithley 2400系统测试记录获得，外量子效率(IPCE)曲线，通过系统Oriel-74125进行测试得到，其中染料敏化太阳能电池（DSSCs）的有效工作面积为0.25cm2，测定以聚合配合物PBDTT-VZn为染料敏化剂的染料敏化太阳能电池（DSSCs）的性能参数和光电转换效率，其电池电流密度-电压(J-V)曲线如图5，电池外量子效率(IPCE)曲线如图6，表1是它们的光伏性能和光电转换效率测试结果。
表1 基于聚合金属配合物染料敏化剂的DSSCs的光伏性能数据
| polymer | solvent | Jsc(mA/cm-2) | Voc(V) | FF(%) | PCE (%) |
| PBDTT-VZn | DMF | 14.37 | 0.76 | 69.8 | 7.61 |
注: solvent:溶解染料敏化剂以制膜的溶剂；
Jsc:短路电流密度；
Voc:开路电压；
FF:填充因子；
PCE:太阳能电池的光电转换效率。
Claims (3)
1.一种含4-乙烯基苯胺衍生物合Zn(II)的聚合配合物PBDTT-VZn,其特征在于该类化合物具有含4-乙烯基苯胺衍生物合Zn(II)配合物为电子辅助受体A的D-A-π-A结构，其通式如式1：
式1含4-乙烯基苯胺衍生物合Zn(II)的聚合配合物PBDTT-VZn的结构通式。
2.如权利要求1所述的一种含4-乙烯基苯胺衍生物合Zn(II)的聚合配合物PBDTT-VZn的制备方法：
(1).对硝基苄基三苯基溴化磷的制备：将4-苄溴甲基硝基苯与三苯基磷在惰性条件下加入到CHCl3中，搅拌0.5～1.0h后将混合物倒入到无水乙醚中，析出白色固体，过滤，取沉淀物质在烘箱中干燥，得到白色粉末固体对硝基苄基三苯基溴化磷；
(2).对硝基苯乙烯的制备：对硝基苄基三苯基溴化磷与甲醛悬浮液，剧烈搅拌，再将Na2CO3溶于水中，每次在深红磷盐中间体消失后加Na2CO3溶液加完后继续搅拌4～8h，用乙醚萃取，旋去乙醚，再用石油醚做洗脱剂硅胶过柱，得到浅黄色液体对硝基苯乙烯；
(3).对4-氨基苯乙烯的制备：将对硝基苯乙烯溶解在干燥的二氧六环中，加水，搅拌10min后加Zn粉，升温至70℃后反应7～8h，反应结束后减压除去溶剂，水层用乙酸乙酯萃取，有机层为粗产物，再用硅胶过柱，洗脱剂为石油醚：乙酸乙酯＝5：1，得到浅黄色固体对4-氨基苯乙烯；
(4).含Zn(II)配合物VZn的合成：分别称取4-氨基苯乙烯和2-氰基-3-(8-羟基喹啉-5-基)丙烯酸，称量完成后将它们 先后加入到盛有四氢呋喃的三口圆底烧瓶中搅拌，不断将溶解有Zn(CH3COO)2·H2O的甲醇溶液通过恒压滴液漏斗将其缓慢滴加到反应体系中，滴加完成后升温至回流反应12～24h，反应结束后将体系冷却至室温后将析出的固体过滤，并先后用去离子水和无水乙醇洗涤2次，再将粗产物用无水甲醇重结晶两次，在真空条件下干燥数天后得到棕黄色固体VZn；
(5).聚合金属配合物PBDTT-VZn的制备：聚合物PBDTT-VZn是根据Heck偶联反应而合成的，将Zn(II)配合物VZn，2,6-二溴-4,8-二(5-(2-乙基己基)噻吩基-2-基)-苯并[1,2-b:4,5-b']二噻吩(BDTT)加入到单口瓶中，之后加入醋酸钯，三(邻甲苯基)膦，将新蒸馏的精制干燥后的DMF溶液和三乙胺依次加入单口瓶，之后在氮气氛围下升温到90℃反应36～72h，反应结束冷却至室温后将体系过滤，所得滤渣用大量的甲醇清洗，最终得到棕色沉淀PBDTT-VZn。
3.根据权利要求1所述的一种含4-乙烯基苯胺衍生物合Zn(II)的聚合配合物PBDTT-VZn的用途，在染料敏化太阳能电池中用作染料敏化剂。
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| CN108084448A (zh) * | 2017-11-30 | 2018-05-29 | 湘潭大学 | 一种含4,5-二甲基-1,2-苯二胺衍生物合镉聚合配合物及制备方法与用途 |
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