CN110922392A - 一种苯基为末端桥链的咔唑共敏剂及其制备方法 - Google Patents
一种苯基为末端桥链的咔唑共敏剂及其制备方法 Download PDFInfo
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052717 sulfur Chemical group 0.000 claims abstract description 6
- 239000011593 sulfur Chemical group 0.000 claims abstract description 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 12
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- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
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- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
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- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 5
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- 229920003944 DuPont™ Surlyn® 1702 Polymers 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- YIYFFLYGSHJWFF-UHFFFAOYSA-N [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YIYFFLYGSHJWFF-UHFFFAOYSA-N 0.000 description 1
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- METIGIXCFPEQNM-UHFFFAOYSA-M amino-(2-bromoethyl)-dimethylazanium;bromide Chemical compound [Br-].C[N+](C)(N)CCBr METIGIXCFPEQNM-UHFFFAOYSA-M 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
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- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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Abstract
本发明公开了一种苯基为末端桥链的咔唑共敏剂及其制备方法，该共敏剂的结构式如下：
Description
技术领域
本发明属于有机共敏剂技术领域，具体涉及以烷基取代咔唑为电子供体、以苯基为末端桥链、以氰基乙酸为吸电子基团的有机共敏剂。
背景技术
能源危机与环境污染对全球可持续发展提出的挑战日益加剧，开发清洁可再生新能源已经成为世界各国规划中的重大方向。与石化燃料、核能、水能、风能等相比，太阳能具有独特的优势，因其总量大、安全且不受地理条件限制。自1954年美国贝尔实验室成功研制第一个实用硅太阳能电池并用于人造卫星电源以来，太阳能电池研究取得了巨大的进展，现已发展到第三代太阳能电池。其中，染料敏化太阳能电池(DSSCs)的制造工艺简单、成本低、光电转化效率高，是当前太阳能电池领域的一个研究热点。
DSSCs的组件包括光阳极、光敏染料、电解质和对电极，而光敏染料主要担负着捕获光子和向TiO2导带注入电子等重要作用，因此它的性能直接影响着DSSCs的光电转化效率。目前，以N719为代表的钌-络合物的DSSCs光电转化效率达到了11％，最近，利用锌-卟啉络合物和三苯胺有机染料共敏化的DSSCs光电转化效率达到了13％。
一个理想的光敏染料分子应该能够吸收尽可能多的光电子从而实现全光谱吸收，例如，钌-络合物N749(黑染料)能够捕获920nm以下的光子，其光电转换效率高达11.1％。但是设计一个在整个光谱范围都有吸收的全光谱光敏染料是一项非常困难的工作，此外，通过降低HOMO能级来拓宽光敏染料在近红外区的吸收光谱会使电子注入变得困难，从而降低光电转换效率。
发明内容
本发明所要解决的技术问题在于克服上述光敏染料的缺点，提供一种吸收光谱互补的共敏剂，其与N719共敏后，达到同时提高短路电流密度和开路电压的效果，从而进一步提高太阳能电池的光电转换效率；并为该染料提供一种操作简单、收率高的制备方法。
解决上述技术问题所采用的技术方案是该共敏剂的结构式如下所示：
式中，R为C1～C10的烷基；X为氧或硫。
本发明优选R代表C6烷基(正己基)，X代表硫。
上述苯基为末端桥链的咔唑共敏剂的制备方法为：
1、制备式3化合物
以甲苯与水的体积比为5:1的混合液为溶剂，将式2化合物、对醛基苯硼酸、四(三苯基膦)钯、碳酸钾按摩尔比为1:1～1.2:0.03～0.05:1.5～2.0反应，100～120℃反应8～12小时，分离纯化产物，得到式3化合物，其化学反应方程式如下：
式中X代表氧或硫。
2、制备式5化合物
以甲苯与水的体积比为5:1的混合液为溶剂，将式3化合物、式4化合物、四(三苯基膦)钯、碳酸钾按摩尔比为1:1～1.2:0.03～0.05:1.5～2.0反应，100～120℃反应8～12小时，分离纯化产物，得到式4化合物，其化学反应方程式如下：
式中R代表C1～C10的烷基。
3、制备苯基为末端桥链的咔唑共敏剂
以冰乙酸为溶剂，将式5化合物、氰基乙酸、乙酸铵按摩尔比为1:1～1.2:1.5～2.0，100～120℃反应3～5小时，分离纯化产物，得到苯基为末端桥链的咔唑共敏剂，其化学反应方程式如下：
本发明中的苯基为末端桥链的咔唑共敏剂与钌染料N719共敏后，可达到提高短路电流密度和开路电压的双重效果：一方面，苯基为末端桥链的咔唑共敏剂可拓宽敏化太阳电池的吸收谱带范围，从而提高短路电流密度；另一方面，苯基为末端桥链的咔唑共敏剂可抑制注入电子与电解质的复合，从而提高开路电压。短路电流密度和开路电压的同时提高进一步提高了高钌染料N719敏化的太阳能电池的光电转换效率。一种苯基为末端桥链的咔唑共敏剂制备方法简单，成本低，具有广阔的应用前景。
具体实施方式
下面以实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。
实施例1
以制备结构式如下的苯基为末端桥链的咔唑共敏剂为例，其制备方法为：
1、向三口圆底烧瓶中加入200mL甲苯和40mL水，再加入4.80g(20mmol)式3化合物、3.00g(20mmol)式4化合物、462mg(0.4mmol)四(三苯基膦)钯、4.14g(30mmol)碳酸钾，110℃反应10小时，降至室温，分液，有机相用无水硫酸镁干燥，过滤，蒸除溶剂，剩余物用柱层析分离(洗脱剂为石油醚)，得到式3化合物2.82g，收率53％。其化学反应方程式如下：
2、制备式5化合物
向三口圆底烧瓶中加入100mL甲苯和20mL水，再加入2.66g(10mmol)式3化合物、3.77g(10mmol)式4化合物、231mg(0.2mmol)四(三苯基膦)钯、2.07g(15mmol)碳酸钾，110℃反应10小时，降至室温，分液，有机相用无水硫酸镁干燥，过滤，蒸除溶剂，剩余物用柱层析分离(洗脱剂为石油醚)，得到式5化合物3.15g，收率72％。其化学反应方程式如下：
2、制备苯基为末端桥链的咔唑共敏剂
向三口圆底烧瓶中加入10mL冰乙酸，再加入437mg(1mmol)式5化合物、102mg(1.2mmol)氰基乙酸、115mg(1.5mmol)乙酸铵，110℃反应4小时，降至室温，向烧瓶中加入20mL二氯甲烷和20mL水，分液，水相用二氯甲烷萃取两次，合并有机相，用无水硫酸镁干燥，蒸除溶剂，剩余物用柱层析纯化(洗脱剂为石油醚:乙酸乙酯＝3:1的混合液，另加混合液体积1％的乙酸)，蒸除洗脱剂，得到苯基为末端桥链的咔唑共敏剂413mg，收率82％。其化学反应方程式如下：
所制备的苯基为末端桥链的咔唑共敏剂的波谱数据为：1HNMR(500MHz,DMSO-d6)δ:8.53(d,J＝1.5Hz,1H),8.31(s,1H),8.26(d,J＝7.5Hz,1H),8.10(d,J＝8.5Hz,2H),7.88(d,J＝8.5Hz,2H),7.78–7.76(m,2H),7.61–7.58(m,3H),7.50(t,J＝8.0Hz,1H),7.26(t,J＝8.0Hz,1H),4.38(t,J＝7.0Hz,2H),1.76–1.73(m,2H),1.26–1.18(m,6H),0.80(t,J＝7.0Hz,3H)ppm.
所制备的苯基为末端桥链的咔唑共敏剂在乙腈中溶液中(10–5M)的最大吸收峰位于412nm，摩尔消光系数为34400M–1cm–1。
所制备的末端桥链的咔唑共敏剂用于N719染料敏化太阳能电池，具体制备方法如下：
将FTO导电玻璃片(14Ω/sq，可见光区的透光率>90％)按以下次序超声清洗：清洁剂、丙酮、去离子水，然后用丝网印刷方法于其上涂一层TiO2浆料，按以下程序烧结制备纳米多孔TiO2工作电极：300℃烧5min、400℃烧5min、450℃烧30min。待降至室温后，将所得纳米多孔TiO2工作电极浸入0.3mmol/L钌染料N719的乙醇溶液中，室温下敏化20h，再置于0.3mmol/L末端桥链的咔唑共敏剂敏化2h。在FTO导电玻璃片上用丝网印刷涂铂浆料，并于400℃下烧结15min，制得对电极。密封层(25μm，Surlyn1702)置于两电极中间将染料敏化过的TiO2光阳极和对电极组装成封装的DSSCs电池，采用真空-倒吸法将电解质溶液通过对电极上的小孔灌注到电池中，电解质溶液的组成为：0.6mol/L碘化1-丁基-3-甲基咪唑(BMII)、0.1mol/LLiI、0.03mol/LI2、0.5mol/L4-叔丁基吡啶和0.1mol/L硫腈胍酸的乙腈溶液。最后，灌注孔用盖玻片和密封层密封，制备成染料敏化太阳能电池。
电池的光电流密度-电压(J-V)特性曲线在AM1.5G模拟太阳光强下测得，模拟器为300W氙灯(94022A，NewportCo.，美国)，入射光强用标准硅太阳能电池校准到100mW/cm2，电流密度-电压特性曲线数据用电脑控制的数据源表(Keithley2400)采集，电池的工作面积为0.25cm2。采用本发明实施例1的苯基为末端桥链的咔唑共敏剂与N719共同敏化所制备电池的光电转化效率为8.35％、短路电流为17.3mA/cm2、开路电压为703mV、填充因子为0.687。按照该方法测得N719单独敏化染料太阳能电池的光电转化效率为7.33％、短路电流为14.7mA/cm2、开路电压为687mV、填充因子为0.726。对比测试结果表明，采用本发明的实施例1制备得太阳能电池的光电转化效率高于相同条件下N719染料敏化太阳能电池光电转化效率。
实施例2
以制备结构式如下的苯基为末端桥链的咔唑共敏剂为例，其制备方法为：
在实施例1的制备式1化合物步骤2中，所用的9-己基咔唑-3-硼酸酯(式4化合物)用等摩尔的9-甲基咔唑-3-硼酸酯替换，该步骤的其它步骤与实施例1相同，其它步骤与相应的实施例相同，制备成苯基为末端桥链的咔唑共敏剂。
按照实施例1的方法将本实施例的苯基为末端桥链的咔唑共敏剂与N719共敏制备成染料敏化太阳能电池，经测试其光电转化效率为8.27％、短路电流为17.4mA/cm2、开路电压为695mV、填充因子为0.684。其光电转化效率高于相同条件下N719敏化染料太阳能电池光电转化效率。
实施例3
以制备结构式如下的苯基为末端桥链的咔唑共敏剂为例，其制备方法为：
在实施例1的制备式1化合物步骤2中，所用的9-己基咔唑-3-硼酸酯(式4化合物)用等摩尔的9-奎基咔唑-3-硼酸酯替换，该步骤的其它步骤与实施例1相同，其它步骤与相应的实施例相同，制备成苯基为末端桥链的咔唑共敏剂。
按照实施例1的方法将本实施例的苯基为末端桥链的咔唑共敏剂与N719共敏制备成染料敏化太阳能电池，经测试其光电转化效率为8.30％、短路电流为17.1mA/cm2、开路电压为716mV、填充因子为0.678。其光电转化效率高于相同条件下N719敏化染料太阳能电池光电转化效率。
实施例4
以制备结构式如下的苯基为末端桥链的咔唑共敏剂为例，其制备方法为：
在实施例1的制备式1化合物步骤1中，所用的2,5-二溴噻吩(式2化合物)用等摩尔的2,5-二溴呋喃替换，该步骤的其它步骤与实施例1相同，其它步骤与相应的实施例相同，制备成苯基为末端桥链的咔唑共敏剂。
按照实施例1的方法将本实施例的苯基为末端桥链的咔唑共敏剂与N719共敏制备成染料敏化太阳能电池，经测试其光电转化效率为8.06％、短路电流为16.7mA/cm2、开路电压为709mV、填充因子为0.681。其光电转化效率高于相同条件下N719敏化染料太阳能电池光电转化效率。
Claims (2)
1.一种苯基为末端桥链的咔唑共敏剂，其特征在于，该共敏剂的结构式如下所示：
式Ⅰ中，R为C1～C10的烷基；X为氧或硫。
2.根据权利要求1所述的苯基为末端桥链的咔唑共敏剂的制备方法，其特征在于，包括如下步骤：
(1)制备式Ⅲ化合物
以甲苯与水的体积比为5:1的混合液为溶剂，将式Ⅱ化合物、对醛基苯硼酸、四(三苯基膦)钯、碳酸钾按摩尔比为1:1～1.2:0.03～0.05:1.5～2.0反应，100～120℃反应8～12小时，分离纯化产物，得到式Ⅲ化合物；
其中式Ⅱ化合物的结构为：
X代表氧或硫；
(2)制备式Ⅴ化合物
以甲苯与水的体积比为5:1的混合液为溶剂，将式Ⅲ化合物、式Ⅳ化合物、四(三苯基膦)钯、碳酸钾按摩尔比为1:1～1.2:0.03～0.05:1.5～2.0反应，100～120℃反应8～12小时，分离纯化产物，得到式Ⅴ化合物；
其中式Ⅳ化合物的结构为：
R代表C1～C10的烷基；
(3)制备苯基为末端桥链的咔唑共敏剂
以冰乙酸为溶剂，将式Ⅴ化合物、氰基乙酸、乙酸铵按摩尔比为1:1～1.2:1.5～2.0，100～120℃反应3～5小时，分离纯化产物，得到苯基为末端桥链的咔唑共敏剂。
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