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联吡啶钌类染料的合成和表征

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2024年3月29日发(作者:平冷玉)

第四章结论

第四章结论

自1991年M.Gratzel教授为首的研究小组以纳米多孔Ti02,膜为半导体电

极,以过渡金属Ru以及有机化合物作染料,并选用适当的氧化还原电解质为主要

材料,发展出一种纳米晶化学太阳电池以来,引发了太阳能电池的革命。尽管制

约染料敏化太阳能电池的因素很多,但染料敏化剂是其中重要的一部分,因此合

成新型染料敏化剂具有重大意义。

本论文正是顺应太阳能电池的最新发展趋势,抓住影响太阳能电池的因素染

料敏化剂,不仅成功合成了“明星染料N3”,而且设计并合成了四种新型染料配

体以及一种新型联吡啶钌类染料。通过一年的努力得到了以下结果。

(1)合成出了可以用于比较其他联吡啶钌类染料光敏性能的高纯度N3染料。

(2)从增加染料疏水性和提高染料激发态电荷分离程度这两方面出发设计并

合成了烷氧基和苯氧基取代的联吡啶配体。

(3)合成YJ顿---异硫氰酸根.(4,4’.二(对甲苯氧基).2,2’.联吡啶).(4,4’一二

羧基-2,2’.联吡啶)钌(II)(Dye-1)它是在N3的基础上,由4,4’.二对甲苯氧

基一2,2’.联吡啶取代其中一个4.4’.二羧基一2,2’.联吡啶配体形成的。紫外可见吸收

光谱显示Dye-1的摩尔消光系数为1.06×104M。lcm‘1(535nm)。经循环伏安测

定Dye-1染料的LUM0能级为-4.02eV,与Ti02的导带能级相匹配,电子注入是

热力学允许的。其敏化太阳能电池的开路电压V。。=640mV,短路电流密度

I。=5.84mA

cm。1,填充因子FF=0.54,转换效率n=2.02%。

通过Dye-1与N3的比较,对甲苯氧基的引入可对联吡啶钌类染料造成以下

几点影响(1)增加染料的疏水性,提高电池在工作中的稳定性(2)由于氧原子的存

在无法形成有效的共轭平面,造成了染料摩尔消光系数下降(3)苯环的离域作用

使氧原子的供电性减弱,可能无法有效增加染料激发态的电荷分离程度造成短

路电流密度较小。

总之,虽然染料敏化纳米晶太阳能电池目前还有许多问题需要解决,但是我

们相信,在不久的将来,随着技术的进一步发展,这种太阳能电池将会有着十分

广阔的应用前景。

47

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大学,2006

51

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4,4’一二羧基-2,2’联吡啶氢核磁共振谱图

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致谢

致谢

本论文的工作是在我的导师李祥高教授的悉心指导下完成的。李老师渊博的

专业知识,严谨的治学态度,精益求精的工作作风,诲人不倦的高尚师德,严以

律己、宽以待人的崇高风范,朴实无华、平易近人的人格魅力对我影响深远。不

仅使我树立了远大的学术目标、掌握了基本的研究方法,还使我明白了许多待人

接物与为人处世的道理。本论文从选题到完成,每一步都是在导师的指导下完成

的,倾注了导师大量的心血。在此,谨向导师表示崇高的敬意和衷心的感谢!

本论文的顺利完成,离不开各位老师、同学和朋友的关心和帮助。特别感谢

王世荣教授在学习上给予我的指导和帮助。在两年的学习期间,得到本课题组吕

海军,高金良师兄和尤静师姐的关心和帮助,在此向他们表达我的感激之情。特

别要感谢王巧平同学和南开大学的纪伟伟同学对于本论文研究工作给予了的热

情帮助,没有她们的帮助和支持是没有办法完成我的硕士学位论文的,同窗之间

的友谊永远长存。

联吡啶钌类染料的合成和表征

作者:

学位授予单位:

王宏为

天津大学

本文链接:/Thesis_

2024年3月29日发(作者:平冷玉)

第四章结论

第四章结论

自1991年M.Gratzel教授为首的研究小组以纳米多孔Ti02,膜为半导体电

极,以过渡金属Ru以及有机化合物作染料,并选用适当的氧化还原电解质为主要

材料,发展出一种纳米晶化学太阳电池以来,引发了太阳能电池的革命。尽管制

约染料敏化太阳能电池的因素很多,但染料敏化剂是其中重要的一部分,因此合

成新型染料敏化剂具有重大意义。

本论文正是顺应太阳能电池的最新发展趋势,抓住影响太阳能电池的因素染

料敏化剂,不仅成功合成了“明星染料N3”,而且设计并合成了四种新型染料配

体以及一种新型联吡啶钌类染料。通过一年的努力得到了以下结果。

(1)合成出了可以用于比较其他联吡啶钌类染料光敏性能的高纯度N3染料。

(2)从增加染料疏水性和提高染料激发态电荷分离程度这两方面出发设计并

合成了烷氧基和苯氧基取代的联吡啶配体。

(3)合成YJ顿---异硫氰酸根.(4,4’.二(对甲苯氧基).2,2’.联吡啶).(4,4’一二

羧基-2,2’.联吡啶)钌(II)(Dye-1)它是在N3的基础上,由4,4’.二对甲苯氧

基一2,2’.联吡啶取代其中一个4.4’.二羧基一2,2’.联吡啶配体形成的。紫外可见吸收

光谱显示Dye-1的摩尔消光系数为1.06×104M。lcm‘1(535nm)。经循环伏安测

定Dye-1染料的LUM0能级为-4.02eV,与Ti02的导带能级相匹配,电子注入是

热力学允许的。其敏化太阳能电池的开路电压V。。=640mV,短路电流密度

I。=5.84mA

cm。1,填充因子FF=0.54,转换效率n=2.02%。

通过Dye-1与N3的比较,对甲苯氧基的引入可对联吡啶钌类染料造成以下

几点影响(1)增加染料的疏水性,提高电池在工作中的稳定性(2)由于氧原子的存

在无法形成有效的共轭平面,造成了染料摩尔消光系数下降(3)苯环的离域作用

使氧原子的供电性减弱,可能无法有效增加染料激发态的电荷分离程度造成短

路电流密度较小。

总之,虽然染料敏化纳米晶太阳能电池目前还有许多问题需要解决,但是我

们相信,在不久的将来,随着技术的进一步发展,这种太阳能电池将会有着十分

广阔的应用前景。

47

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大学,2006

51

附录

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附图2.14,4’一二羧基一2,2’联吡啶红外光谱图

60

4000200010000

a一

附图2.2

4,4’一二羧基-2,2’联吡啶氢核磁共振谱图

:l曼参*s:

12'0

52

20PPM

4,4L二投基一2.2’联吡啶氢梭磁共振谱局部放大图

!I

If

6P{3

,i

二L

附图2-3台成N3氢核磁共振谱图

I黯l‘l

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l|l…

厂_———彳———百———1————r———了———1———1一—丙

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合成N3氢核磁共振谱局部放大图

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4,4’一二对甲苯氧基-2,2’.联吡啶的红外光谱图

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附图3-2

4,4’.二对甲苯氧基一2,2’.联吡啶的氢核磁共振谱图

56

4,4’一二对甲苯氧基-2,2'-联毗啶的氢核磁共振谱局部放大图

附图3-3

4,4’一二对甲苯氧基-2卫’-联毗啶的质谱图

附躅34

4,4'-二对甲苯氧基一2.2'-鞋吡啶的HPLC

附图3-5

4,4’.二苯氧基一2,2’.联吡啶红外光谱图

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4,4'-二苯氧基一2,2’.联吡啶的氢核磁共振谱图

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4,4’一二乙氧基一2,2’.联吡啶氢核磁共振谱图

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65

致谢

致谢

本论文的工作是在我的导师李祥高教授的悉心指导下完成的。李老师渊博的

专业知识,严谨的治学态度,精益求精的工作作风,诲人不倦的高尚师德,严以

律己、宽以待人的崇高风范,朴实无华、平易近人的人格魅力对我影响深远。不

仅使我树立了远大的学术目标、掌握了基本的研究方法,还使我明白了许多待人

接物与为人处世的道理。本论文从选题到完成,每一步都是在导师的指导下完成

的,倾注了导师大量的心血。在此,谨向导师表示崇高的敬意和衷心的感谢!

本论文的顺利完成,离不开各位老师、同学和朋友的关心和帮助。特别感谢

王世荣教授在学习上给予我的指导和帮助。在两年的学习期间,得到本课题组吕

海军,高金良师兄和尤静师姐的关心和帮助,在此向他们表达我的感激之情。特

别要感谢王巧平同学和南开大学的纪伟伟同学对于本论文研究工作给予了的热

情帮助,没有她们的帮助和支持是没有办法完成我的硕士学位论文的,同窗之间

的友谊永远长存。

联吡啶钌类染料的合成和表征

作者:

学位授予单位:

王宏为

天津大学

本文链接:/Thesis_

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