CN102617647B - 三联吡啶类钌配合物、制备方法及其应用 - Google Patents
三联吡啶类钌配合物、制备方法及其应用 Download PDFInfo
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 150000001875 compounds Chemical class 0.000 title abstract 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000011737 fluorine Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
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- 238000000034 method Methods 0.000 claims description 8
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims description 7
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 7
- 238000001953 recrystallisation Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
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- 239000003446 ligand Substances 0.000 abstract description 20
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- 229910052794 bromium Inorganic materials 0.000 description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 3
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 2
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- 125000000217 alkyl group Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
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- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 2
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- JPHKMYXKNKLNDF-UHFFFAOYSA-N 3,4-difluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1F JPHKMYXKNKLNDF-UHFFFAOYSA-N 0.000 description 1
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 description 1
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- 101150090068 PMII gene Proteins 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
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- ZZTURJAZCMUWEP-UHFFFAOYSA-N diaminomethylideneazanium;hydrogen sulfate Chemical compound NC(N)=N.OS(O)(=O)=O ZZTURJAZCMUWEP-UHFFFAOYSA-N 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
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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
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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
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
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- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
本发明公开了三联吡啶类钌配合物、制备方法及其应用,该三联吡啶类钌配合物是以硫氰酸为强给电子配体,羧基联吡啶为含吸附基团的配体,三联吡啶衍生物为辅助配体的钌配合物,该配合物作为光敏染料应用于染料敏化太阳电池。本发明的三联吡啶类钌配合物仅仅通过简单的取代基修饰,达到优化染料结构及提高性能的目的,本发明的配合物在性能方面由于其具有三齿螯合、刚性平面以及稳定性的特点,三联吡啶的金属配合物表现出良好的光、电等化学物理性质,在制备工艺方面容易合成和修饰。本发明设计合成的三联吡啶类钌配合物具有制备成本低,提纯容易,效率较高的优越性。
Description
技术领域
本发明涉及三联吡啶类钌配合物、制备方法及其作为光敏染料在制备染料敏化太阳电池中的应用。
背景技术
染料敏化太阳电池作为一种新型的光伏电池,由于成本低、效率高等优点,有着广泛的应用前景。由于光敏染料在染料敏化太阳电池中起着收集能量的作用,其性能直接影响到电池的光电转换效率。
钌最外层具有4d75s1结构,其离子常见价态为Ru(I)、Ru(II)和Ru(III),并易于形成六配位的配合物。钌配合物由于具有热力学稳定性好、光化学光物理信息丰富、激发态反应活性高和寿命长及发光性能良好等特性。钌染料敏化太阳电池不仅具有较高的光电转换效率,而且与硅伏电池相比,造价较为低廉,因此目前得到了广泛的研究。
为了更大地提高钌染料敏化太阳电池的光电转换效率,文献中多采取增加长的烷基链、增加共轭基团以及引入给电子基团等方法修饰优化染料的结构,但是这些方法势必增加染料的合成与纯化的难度。
发明内容
本发明的目的在于提供三联吡啶类钌配合物、制备方法及其作为光敏染料在制备染料敏化太阳电池中的应用。
本发明所采取的技术方案为:
三联吡啶类钌配合物,是以硫氰酸为强给电子配体,羧基联吡啶为含吸附基团的配体,三联吡啶衍生物为辅助配体的钌配合物,其化学结构通式如下:
式中,R1~R3中的至少一个为取代基团,其余的为氢。
优选的,所述R1为取代基团,R2 和R3独立地为氢或取代基团,且当R1~R3中有多个取代基团,其取代基团均相同。
优选的,所述取代基团为卤素、硝基、烷基中的一种。
优选的,所述取代基团为氟、氯、溴、硝基、甲基中的一种。
优选的,所述R1为氟,R2 和R3独立地为氢或氟,或R1为氯、溴、硝基、甲基中的一种,R2和R3为氢。
上述的三联吡啶类钌配合物的制备方法,步骤如下:
1)
将含取代基的苯甲醛溶解于乙醇中制成溶液,向该溶液中依次加入2-乙酰吡啶、氢氧化钾和氨水,搅拌,过滤,洗涤,重结晶,得三联吡啶衍生物;
2)
将三联吡啶衍生物溶解于乙醇中制成溶液,搅拌下向该溶液中加入RuCl3·3H2O,回流反应,过滤,洗涤,干燥,得到产物1;
3)
向反应器中加入产物1、4,4-二羧基-2,2-联吡啶、氯化锂、DMF,得混合物,将混合物升温至130~150 ℃,在氮气保护下搅拌,再加入硫氰酸铵,回流反应,冷却至室温,旋干溶剂,加水,过滤,固体干燥后重结晶,得三联吡啶类钌配合物。
优选的,含取代基的苯甲醛为含卤素取代基的苯甲醛、含硝基取代基的苯甲醛、含烷基取代基的苯甲醛。
优选的,含取代基的苯甲醛为对氟苯甲醛、3, 4-二氟苯甲醛、3,4,5-三氟苯甲醛、对硝基苯甲醛、对氯苯甲醛、对溴苯甲醛、对甲基苯甲醛中的任一种。
优选的,步骤1)含取代基的苯甲醛、2-乙酰吡啶摩尔比为1:1~4;
步骤2)三联吡啶衍生物、RuCl3·3H2O的摩尔比为1:1~3;
步骤3)产物1、4,4-二羧基-2,2-联吡啶和硫氰酸铵的摩尔比为1:1~2:20~50。
上述的三联吡啶类钌配合物在染料敏化太阳电池中的应用。
上述三联吡啶类钌配合物制备方法中,步骤1)的反应式如下:
步骤2)的反应式如下:
步骤3)的反应式如下:
本发明设计合成的三联吡啶类钌配合物,硫氰酸为强给电子配体,羧基联吡啶为含吸附基团的配体的钌配合物,三联吡啶衍生物为辅助配体,R1、R2、R3中的取代基为辅助配体的修饰基团,在制备染料敏化太阳电池中,羧基联吡啶作为含吸附基团的配体,与TiO2键合,提供电子通道。
本发明的有益效果为:
本发明的三联吡啶类钌配合物仅仅通过简单的取代基修饰(F、Cl等),达到优化染料结构及提高性能的目的,本发明的配合物在性能方面由于其具有三齿螯合、刚性平面以及稳定性的特点,三联吡啶的金属配合物表现出良好的光、电等化学物理性质,在制备工艺方面容易合成和修饰。本发明设计合成的三联吡啶类钌配合物具有制备成本低,提纯容易,效率较高的优越性。
本发明的三联吡啶类钌配合物应用于染料敏化太阳电池。
具体实施方式
下面结合具体的实施例对本发明作进一步的说明,但并不局限如此。
实施例中所用的DMF(N,N-二甲基甲酰胺)经布劳恩SPS-800型有机溶剂净化系统(MBRAUN MB SPS-800
system)纯化处理,其他的试剂均为分析纯,未经任何处理直接使用;实施例中的百分比均为质量百分比。
实施例
1
三联吡啶类钌配合物,是以硫氰酸为强给电子配体,4,4-二羧基-2,2-联吡啶为含吸附基团的配体,三联吡啶衍生物为辅助配体,氟为辅助配体的修饰基团的钌配合物,其结构式如下:
上述三联吡啶类钌配合物(简称RuTPy-1F)的制备方法,包括如下步骤:
1) TPy-1F的合成:将5 mmol对氟苯甲醛用50 mL无水乙醇溶解,再依次加入10 mmol 2-乙酰吡啶、氢氧化钾(0.8 g,纯度85%)和氨水( 1 mL,含氨量29%),常温下搅拌反应4 h后,生成大量固体,过滤,用无水乙醇洗涤,得白色粗产品,再用甲醇和二氯甲烷重结晶得到氟修饰的三联吡啶衍生物(简称:TPy-1F),产率:80%;
TPy-1F的氢谱数据:1H-NMR
(300 MHz, DMSO-d6, δ ppm): 8.75 (s, 2H), 8.71 (d, 2H), 8.67(d, 2H), 8.32(m,
2H), 8.00 (d, 2H), 7.86 (d, 2H), 7.30(d, 2H).
2) Ru(TPy-1F)Cl3的合成:将0.4 mmol
TPy-1F 用100 mL的无水乙醇溶解,搅拌下再加入0.4 mmol
RuCl3·3H2O,回流反应1 h,生成大量红棕色固体,过滤,乙醇洗涤并干燥,得到产物Ru(TPy-1F)Cl3,产率80%;
3)
RuTPy-1F的合成: 向反应瓶中加入0.3 mmol Ru(TPy-1F)Cl3、0.3 mmol 4,4-二羧基-2,2-联吡啶(dcbpyH2)及0.5 mmol氯化锂,在氮气保护下再加入100 mL DMF,得混合物,将混合物加热到150℃,在氮气保护下搅拌反应12 h,再加入过量的硫氰酸铵10 mmol,回流反应12 h,冷却至室温,旋干溶剂,加入150 mL水,析出大量红棕色沉淀,过滤,固体干燥后用甲醇重结晶,得到三联吡啶类钌配合物RuTPy-1F,产率:40%。
本实施例所得三联吡啶类钌配合物的质谱分析结果为:MS (ESI, m/z):
728.71([M-SCN-2H]-), found, 728.73([M-SCN-2H]-) Anal.
Calcd for RuTPy-1F·3CH3OH: C, 51.58; H, 3.87; N, 11.08. Found: C, 52.06, H,
4.326; N, 11.17.
实施例
2
三联吡啶类钌配合物,是以硫氰酸为强给电子配体,4,4-二羧基-2,2-联吡啶为含吸附基团的配体,三联吡啶衍生物为辅助配体,氟为辅助配体的修饰基团的钌配合物,其结构式如下:
上述三联吡啶类钌配合物(简称RuTPy-2F)的制备方法,包括如下步骤:
1)
TPy-2F的合成:将3mmol3, 4-二氟苯甲醛用50 mL乙醇溶解,再依次加入12mmol 2-乙酰吡啶、氢氧化钾(0.8 g,纯度85%)和氨水( 1 mL,含氨量29%),常温下搅拌反应4 h后,生成大量固体,过滤,用乙醇洗涤,得白色粗产品,再用甲醇和二氯甲烷重结晶得到氟修饰的三联吡啶衍生物(简称:TPy-2F),产率:70%;
TPy-2F的氢谱数据:1H-NMR (300 MHz,
DMSO-d6, δ ppm): 8.74(td, 2H), 8.63(s, 2H), 8.62(t, 1H), 8.04-8.00(m, 3H),
7.77(m, 1H), 7.61(t, 1H), 7.55-7.38(td, 2H).
2)
Ru(TPy-2F)Cl3的合成:将0.2mmol TPy-2F 用100 mL的乙醇溶解,搅拌下再加入0.4 mmol RuCl3·3H2O,回流反应1 h,生成大量红棕色固体,过滤,乙醇洗涤并干燥,得到产物Ru(TPy-2F)Cl3,产率75%;
3)
RuTPy-2F的合成:向反应瓶中加入0.2 mmol Ru(TPy-2F)Cl3、0.3 mmol 4,4-二羧基-2,2-联吡啶(dcbpyH2)及0.5 mmol氯化锂,在氮气保护下再加入100 mL DMF,得混合物,将混合物加热到140℃,在氮气保护下搅拌反应12 h,再加入过量的硫氰酸铵4 mmol,回流反应12 h,冷却至室温,旋干溶剂,加入150 mL水,析出大量红棕色沉淀,过滤,固体干燥后用甲醇重结晶,得到三联吡啶类钌配合物RuTPy-2F,产率:37%。
本实施例所得三联吡啶类钌配合物的质谱分析结果为:MS (ESI, m/z):
746.70([M-SCN-2H]-), found, 746.87([M-SCN-2H]-) Anal.
Calcd for RuTPy-2F·4CH3OH: C, 50.10; H, 3.99; N, 10.49. Found: C, 50.43, H,
4.39; N, 11.00.
实施例
3
三联吡啶类钌配合物,是以硫氰酸为强给电子配体,4,4-二羧基-2,2-联吡啶为含吸附基团的配体,三联吡啶衍生物为辅助配体,氟为辅助配体的修饰基团的钌配合物,其结构式如下:
上述三联吡啶类钌配合物(简称RuTPy-3F)的制备方法,包括如下步骤:
1)
TPy-3F的合成:将7 mmol 3,4,5-三氟苯甲醛用50 mL乙醇溶解,再依次加入7 mmol 2-乙酰吡啶、氢氧化钾(0.8 g,纯度85%)和氨水( 1 mL,含氨量29%),常温下搅拌反应4 h后,生成大量固体,过滤,用乙醇洗涤,得白色粗产品,再用甲醇和二氯甲烷重结晶得到氟修饰的三联吡啶衍生物(简称:TPy-3F),产率:75%;
TPy-3F的氢谱数据:1H-NMR (300 MHz,
DMSO-d6, δ
ppm): 8.75-8.74(td, 2H), 8.65(d, 3H), 8.63(t, 1H), 8.02(t, 2H), 7.95(t, 2H),
7.52(td, 2H).
2) Ru(TPy-3F)Cl3的合成:将0.4 mmol TPy-3F 用100 mL的乙醇溶解,搅拌下再加入1.2 mmol RuCl3·3H2O,回流反应1 h,生成大量红棕色固体,过滤,乙醇洗涤并干燥,得到产物Ru(TPy-2F)Cl3,产率76%;
3)
RuTPy-3F的合成:向反应瓶中加入0.3 mmol Ru(TPy-3F)Cl3、0.6 mmol 4,4-二羧基-2,2-联吡啶(dcbpyH2)及0.5 mmol氯化锂,在氮气保护下再加入100 mL DMF,得混合物,将混合物加热到130 ℃,在氮气保护下搅拌反应12 h,再加入过量的硫氰酸铵15 mmol,回流反应12 h,冷却至室温,旋干溶剂,加入150 mL水,析出大量红棕色沉淀,过滤,固体干燥后用甲醇重结晶,得到三联吡啶类钌配合物RuTPy-3F,产率:35%。
本实施例所得三联吡啶类钌配合物的质谱分析结果为:MS (ESI, m/z):
767.69([M-SCN-2H]-), found, 767.33([M-SCN-2H]-) Anal.
Calcd for RuTPy-3F·3CH3OH: C, 49.56; H, 3.50; N, 10.65. Found: C, 50.00; H,
4.10; N, 11.21.
实施例
4
三联吡啶类钌配合物,以硫氰酸为强给电子配体,4,4-二羧基-2,2-联吡啶为含吸附基团的配体,三联吡啶衍生物为辅助配体,硝基为辅助配体的修饰基团的钌配合物,其结构式如下:
上述化合物(简称RuTPy-NO2)的制备方法,步骤如下:
1)
将5 mmol对硝基苯甲醛用50 mL乙醇溶解,再依次加入10 mmol 2-乙酰吡啶、氢氧化钾(0.8 g,纯度85%)和氨水( 1 mL,含氨量29%),常温下搅拌反应4 h后,生成大量固体,过滤,用乙醇洗涤,得白色粗产品,再用甲醇和二氯甲烷重结晶得到三联吡啶衍生物;
2)
将0.4 mmol 三联吡啶衍生物用100 mL的乙醇溶解,搅拌下再加入0.4 mmol RuCl3·3H2O,回流反应1 h,生成大量红棕色固体,过滤,乙醇洗涤并干燥,得到产物1;
3)
向反应瓶中加入0.3 mmol产物1、0.3 mmol 4,4-二羧基-2,2-联吡啶(dcbpyH2)及催化量的氯化锂,在氮气保护下再加入100 mL DMF,得混合物,将混合物加热到150℃,在氮气保护下搅拌反应12 h,再加入过量的硫氰酸铵10 mmol,回流反应12 h,冷却至室温,旋干溶剂,加入150 mL水,析出大量红棕色沉淀,过滤,固体干燥后用甲醇重结晶,得到三联吡啶类钌配合物RuTPy-NO2。
实施例
5
三联吡啶类钌配合物,以硫氰酸为强给电子配体,4,4-二羧基-2,2-联吡啶为含吸附基团的配体,三联吡啶衍生物为辅助配体,氯原子为辅助配体的修饰基团的钌配合物,其结构式如下:
上述化合物(简称RuTPy-Cl)的制备方法同实施例4,只是用对氯苯甲醛代替对硝基苯甲醛。
实施例
6
三联吡啶类钌配合物,以硫氰酸为强给电子配体,4,4-二羧基-2,2-联吡啶为含吸附基团的配体,三联吡啶衍生物为辅助配体,溴原子为辅助配体的修饰基团的钌配合物,其结构式如下:
上述化合物(简称RuTPy-Br)的制备方法同实施例4,只是用对溴苯甲醛代替对硝基苯甲醛。
实施例
7
三联吡啶类钌配合物,以硫氰酸为强给电子配体,4,4-二羧基-2,2-联吡啶为含吸附基团的配体,三联吡啶衍生物为辅助配体,甲基为辅助配体的修饰基团的钌配合物,其结构式如下:
上述化合物(简称RuTPy-CH3)的制备方法同实施例4,只是用对甲基苯甲醛代替对硝基苯甲醛。
紫外
-
可见吸收光谱和发射光谱:
将实施例1~7的三联吡啶类钌配合物RuTPy-1F、RuTPy-2F、RuTPy-3F、RuTPy-NO2、RuTPy-Cl、RuTPy-Br、RuTPy-CH3分别进行紫外-可见吸收光谱/荧光光谱检测,配置浓度为2×10-5
M的各钌配合物DMF(N,
N-二甲基甲酰胺)溶液,测试仪器:Shimadzu UV-2450紫外可见分光光度计,Hitachi F4500荧光光谱仪。三联吡啶类钌配合物的紫外-可见最大吸收波长和最大荧光发射波长(nm)数据统计见表1。
电化学性能测试:
采用三电极的方法对实施例1~7的配合物进行循环伏安的测试,工作电极FTO玻璃,Ag/AgCl 饱和氯化钾作为参比电极,Pt作为对电极。1 mmol/L的配合物的DMF溶液中加入六氟磷酸四丁基铵(0.1 M) 作为支持电解质,二茂铁作为内标,以100 mV·s-1的速度在−1.0~2.0 V范围内扫描。实验中的各配合物的氧化电位与二茂铁的氧化峰半波电位的差值得E OX(vs Fc/Fc+),即各染料相对于二茂铁的氧化电位,再有公式E HOMO = 4.8 + E OX
(vs Fc/Fc+) 得到染料HOMO的能级值,最低空轨道能级值E LUMO由E HOMO和E 0-0 的差值得到。各染料的电化学参数及前线轨道能级值见表2。由表2的参数可知,本发明的七种配合物的LUMO能级都高于TiO2的导带能级(−4.4 eV vs NHE),从热力学角度可判定激发态染料可以有效的将电子注入半导体的导带中;同时,各染料的HOMO能级均低于电解液中还原电对I-/I3 -的电位(- 0.48eV vs NHE),说明由于受光照射后激发失去电子而处于氧化态的染料可以被I3 -还原而重生。本发明通过不同取代基的修饰的三联吡啶类钌配合物都满足了染料敏化太阳电池对染料的基本要求。
本发明的三联吡啶类钌配合物作为光敏染料用于制备染料敏化太阳电池:
染料敏化太阳电池的组装包括三个部分:对电极、电解液和工作电极的制作,过程如下:
对电极:在1.2cm×1.0cm干净的导电玻璃FTO的导电面铺一层氯铂酸溶液,400 ℃处理15 min,冷却;
电解液:电解液组成:0.6 M PMII(1-丙基-3-甲基咪唑碘),0.03 M I2,0.05 M LiI,0.1 M GuSCN(胍硫酸盐),和0.5 M 4-叔丁基吡啶的乙腈和戊腈溶液(乙腈和戊腈的体积比85:15);
工作电极:工作电极的制备分为两个环节,首先是TiO2膜/FTO的制作,其次是用作测试的吸附染料的TiO2膜/FTO的制作,也就是最终的工作电极:
(1)
TiO2膜/FTO的制作
TiO2浆料的制备:由合成的纳米材料二氧化钛颗粒、冰醋酸、松油醇、乙基纤维素以及乙醇按照合适的比例用玛瑙研钵研磨30 min,得到TiO2浆料,超声处理,排除气泡并均匀分散;
丝网印刷:选择合适孔径的丝网,采用丝网印刷的方法将上述准备好的浆料均匀的刷到FTO的导电面上,并用Profilometer
(Ambios, XP-1)台阶仪检测厚度,得到合适的TiO2膜/FTO,本实验中的用到的网面积均为0.16cm2;
马弗炉中煅烧:得到的TiO2膜/FTO置于马弗炉中500℃高温煅烧,冷却后可以切割成合适大小,用于后面的使用;
(2)
染料的敏化过程
将得到的TiO2膜/FTO用40 mM四氯化钛水溶液浸泡,并于70 ℃环境下放置30 min取出,依次用水、乙醇洗涤,干燥后520 ℃高温处理,冷却至80 ℃,浸泡到0.5 mmoL/L的本发明三联吡啶类钌配合物的乙醇溶液中,16 h后取出,并用乙醇洗涤,干燥,得到工作电极。
按上述方法,将实施例1~7的三联吡啶类钌配合物分别进行染料敏化太阳电池的组装,各电池所用的TiO2膜/FTO厚度一致,再按照工作电极、电解液和对电极的顺序,由上到下组装好,夹子固定,利用太阳光模拟器Keithley 2400 source
meter (69920, 1 kW Xe lamp with optical filter, Oriel) 进行测试。检测的电池性能参数见表3。
由表3的参数可知,含氟取代基团钌配合物的电池性能参数(短路电流、开路电压以及最终的光电转换效率)均由RuTPy-3F < RuTPy-2F
< RuTPy-1F的顺序递增;Cl、Br、NO2和CH3修饰的钌配合物的电池性能参数(短路电流、开路电压、光电转换率)均小于RuTPy-1F,优越性由大到小排列为:RuTPy-1F > RuTPy-Cl > RuTPy-CH3 > RuTPy-NO2
> RuTPy-Br,可见本发明的含单氟取代基团钌配合物具有最高的光电转换效率,优于其他各种修饰。
Claims (2)
1.三联吡啶类钌配合物的制备方法,包括如下步骤:
1)将5 mmol对氟苯甲醛用50 mL无水乙醇溶解,再依次加入10 mmol 2-乙酰吡啶、0.8 g的纯度为85%的氢氧化钾和1 mL的含氨量为29%的氨水,常温下搅拌反应4 h后,生成大量固体,过滤,用无水乙醇洗涤,得白色粗产品,再用甲醇和二氯甲烷重结晶得到氟修饰的三联吡啶衍生物,产率:80%;
此步骤的产物的氢谱数据:1H-NMR (300 MHz, DMSO-d6, δ ppm): 8.75 (s, 2H), 8.71 (d,
2H), 8.67(d, 2H), 8.32(m, 2H), 8.00 (d, 2H), 7.86 (d, 2H), 7.30(d, 2H);
2)将0.4 mmol 第一步所得产物用100 mL的无水乙醇溶解,搅拌下再加入0.4
mmol RuCl3·3H2O,回流反应1 h,生成大量红棕色固体,过滤,乙醇洗涤并干燥,得到产物,产率80%;
3)向反应瓶中加入0.3 mmol 上步得到的产物、0.3 mmol 4,4-二羧基-2,2-联吡啶及0.5 mmol氯化锂,在氮气保护下再加入100 mL DMF,得混合物,将混合物加热到150℃,在氮气保护下搅拌反应12 h,再加入过量的硫氰酸铵10 mmol,回流反应12 h,冷却至室温,旋干溶剂,加入150 mL水,析出大量红棕色沉淀,过滤,固体干燥后用甲醇重结晶,得到三联吡啶类钌配合物,产率:40%;
所得产物的结构式为:
。
2.按照权利要求1的方法制备的三联吡啶类钌配合物在染料敏化太阳电池中的应用。
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