染料敏化太阳能电池中离子液体和敏化染料的合成及表征
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摘要
1991年Gratzel研究小组首次利用纳米技术使染料敏化太阳能电池的转化效率有了大幅度的提高而受到广泛的关注,染料敏化太阳能电池为利用太阳能提供了一种新的途径。
染料敏化太阳能电池(DSSC)主要由导电玻璃、多孔纳米TiO2薄膜、染料、对电极和电解质五部分组成。本文主要分两部分对染料敏化太阳能电池的电解质和染料合成作简单综述和研究。
一、本文以咪唑类离子液体为研究对象。首先以咪唑和硫酸二甲酯为原料合成了甲基咪唑,并使产率有所提高,然后合成了四种碘代烷及四种相应的碘化咪唑盐。最后利用核磁对[i-PMIm]I、[n-PMIm]I、[i-BuMI]I、[i-C5MI]I结构进行表征。
二、在染料敏化太阳能电池中,敏化染料起着吸收太阳光和传输电子的作用,是太阳能电池光电转化效率高低的重要决定因素。
在参阅文献基础上,通过Vilsmerier甲酰化、witting反应、Heck反应及Knoevenagel缩合反应成功合成了全有机染料Ⅰ,并设计合成了染料Ⅱ以及染料Ⅲ,又用氰乙酸甲酯代替氰乙酸得到了染料Ⅳ和染料Ⅴ,目的是探索染料分子结构与吸收光谱的关系,为今后设计新的敏化染料提供参考。所有合成的染料分子结构都通过IR和1HNMR进行确证。
People pay extensive attention to dye-sensitized solar cells because its conversion efficiency had been greatly enhanced by Gratzel research team using firstly nanotechnology in 1991, dye-sensitized solar cells provide a new approach to utilization of solar energy.
Dye-sensitized solar cells (DSSC) is mainly composed of conductive glass, porousnano-TiO2 thin films, dyes, counter-electrode and electrolytes. In this paper, the dye and the electrolyte were made a brief summary and studied.
1. In this paper, imidazolium ionic liquids were investigated. First of all we synthesized N-methylimidazole using imidazole and dimethyl sulfate as substrates, with improved productivity, then we synthesized four iodoalkanes and four corresponding imidazole iodizes. The structures of [i- PMIm]I, [n-PMIm]I, [i-BuMI] I, [i-C5MI]I have been characterized by proton nuclear magnetic resonance (1HNMR) technology.
2. In dye-sensitized solar cells, sensitized dyes play a role of harvesting light and transmitting electron, and is of paramount importance to photovoltaic conversion efficiency.
After referring to extensive literature, we successfully synthesized the pure organic dyeⅠthrough Vilsmerier formylation, witting reaction, Heck reaction and Knoevenagel condensation reaction, then we designed and synthesized dyesⅡ～Ⅲ. Then replacing cyanoacetate with methyl cyanoacetate, we synthesized dyesⅣ～Ⅴto explore the relationship of the molecular structure and absorption spectra and provide a reference for the design of new sensitized dyes in the future. The structures have been characterized by IR and proton nuclear magnetic resonance (1HNMR) technology.
染料敏化太阳能电池(DSSC)主要由导电玻璃、多孔纳米TiO2薄膜、染料、对电极和电解质五部分组成。本文主要分两部分对染料敏化太阳能电池的电解质和染料合成作简单综述和研究。
一、本文以咪唑类离子液体为研究对象。首先以咪唑和硫酸二甲酯为原料合成了甲基咪唑,并使产率有所提高,然后合成了四种碘代烷及四种相应的碘化咪唑盐。最后利用核磁对[i-PMIm]I、[n-PMIm]I、[i-BuMI]I、[i-C5MI]I结构进行表征。
二、在染料敏化太阳能电池中,敏化染料起着吸收太阳光和传输电子的作用,是太阳能电池光电转化效率高低的重要决定因素。
在参阅文献基础上,通过Vilsmerier甲酰化、witting反应、Heck反应及Knoevenagel缩合反应成功合成了全有机染料Ⅰ,并设计合成了染料Ⅱ以及染料Ⅲ,又用氰乙酸甲酯代替氰乙酸得到了染料Ⅳ和染料Ⅴ,目的是探索染料分子结构与吸收光谱的关系,为今后设计新的敏化染料提供参考。所有合成的染料分子结构都通过IR和1HNMR进行确证。
People pay extensive attention to dye-sensitized solar cells because its conversion efficiency had been greatly enhanced by Gratzel research team using firstly nanotechnology in 1991, dye-sensitized solar cells provide a new approach to utilization of solar energy.
Dye-sensitized solar cells (DSSC) is mainly composed of conductive glass, porousnano-TiO2 thin films, dyes, counter-electrode and electrolytes. In this paper, the dye and the electrolyte were made a brief summary and studied.
1. In this paper, imidazolium ionic liquids were investigated. First of all we synthesized N-methylimidazole using imidazole and dimethyl sulfate as substrates, with improved productivity, then we synthesized four iodoalkanes and four corresponding imidazole iodizes. The structures of [i- PMIm]I, [n-PMIm]I, [i-BuMI] I, [i-C5MI]I have been characterized by proton nuclear magnetic resonance (1HNMR) technology.
2. In dye-sensitized solar cells, sensitized dyes play a role of harvesting light and transmitting electron, and is of paramount importance to photovoltaic conversion efficiency.
After referring to extensive literature, we successfully synthesized the pure organic dyeⅠthrough Vilsmerier formylation, witting reaction, Heck reaction and Knoevenagel condensation reaction, then we designed and synthesized dyesⅡ～Ⅲ. Then replacing cyanoacetate with methyl cyanoacetate, we synthesized dyesⅣ～Ⅴto explore the relationship of the molecular structure and absorption spectra and provide a reference for the design of new sensitized dyes in the future. The structures have been characterized by IR and proton nuclear magnetic resonance (1HNMR) technology.
引文
[1]K.R.Seddon.Ionic liquids for clean technology[J].Journal of Chemical Technology and Biotech nology,1997,68:351～356
[2]Wilkes J S,Zaworotko M J.Air and water stable 1-ethye-3-methylimidazolium base ionic liquids[J].Journal of Chemical Society, Chemical Communications,1992,965～967
[3]Hermann W A, Bohm V P W.Heck reaction catalyzed by phospha-pallada-cycles in non-aqueous ionic liquids[J] J.Organometallic Chem.,1999,572:141～145
[4]Bohm V P W, Herrmann, W A.Coordination Chemistry and Mechanisms of Metal C-atalyzed C-C Coupling Reactions,Part 12 Nonaqueous Ionic Liquids:Superior Reaction Media for the Catalytic Heck-Vinylation of Chloroa-renes[J]. Chem.Eur.J.,2000,6(6):1017～1025
[5]Xu L,Chen W,Ross J.et al.Palladium-Catalyyzed Ragioselective Arylation of an Electron-Rich Olefin by Aryl Halides in Ionic Liquids[J]. Org.lett.,2001,3(2):295～297
[6]Hagiwara H,Shimizu Y,Hoshi T.et al. Heterogeneous Heck reaction catalyzed by Pd/C in ionic liquid[J].Tetrahedron Lett.,2001,42(26):4349～4351
[7]Mathews C J,Smith P J,Welton T.et al.Palladium catalysed Suzuki cross-coupling reactions in ambient temperature ionic liquids[J].Chem.Commun.,2000,14:1249～1250
[8]McNulty J,Capretta A,Wilson J.et al. Suzuki cross-coupling reactions of aryl halides in phosphonium salt ionic liquid under mild conditions[J].Chem.Commun.2002,17:1986～1987
[9]Dell'Anna M.M,Gallo V, Mastrorilli.et al.Metal cataly sed Michael additions in ionic liquids [J].Chem Commun,2002(5):434～435
[10]Gallo V,Mastrorilli P,Nobil C F.et al. How does the presence of impurities change the performance of catalytic systems in ionic liquids?A case study:the Michael addition of acety-lacetone to methyl vinyl ketone[J].J.Chem.Soc.,Dalton Trans.,2002,23:4339～4342
[11]彭家建,邓友全.离子液体系中催化环已烷酮肟重排已内酰胺[J].石油化工,2001,30(2)：91～92
[12]Peng J,Deng Y,Catalytic Beckmann rearrangement of ketoximes in ionic liquids [J]. Tetrahedron Lett.,2001,42(3):403～405
[13]Ren R X,Zueva L D,Ou W. Formation of ε-caprolactam via catalytic Beckmann rearrange ment using P2O5 in ionin liquids[J].Tetrahedron Lett.,2001,42(48):8441～8443
[14]Harjani J R,Nara S J and Salunkhe M M.Fries rearrangement in ionic melts [J].Tetrahedron Lett.2001,42(10):1979～1981
[15]Zulfiqar F,and Kitazume T. Lewis acid-catalysed sequential reaction in ionic liquids[J].Green Chem.,2000,2 (6):296～297
[16]O'Regan B,Gratzel M. A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 Films [J]. Nature.1991,353 (24):737～739
[17]Papageorgiou N,Athanassov Y,Armand M.et al.The performance and stability of amperatue molten salts for solar cell applications[J].Journal of the Electronchemical Society,1996,143, 3099～3108
[18]王淼,林原,肖绪瑞.离子液体在TiO2钠晶染料敏化太阳能电池中的应用[J].化学通报,2004,4,266～270
[19]Wang P,Zakeeruddin S,Moser J,et al.A New Ionic Liquid Electrolyte Enhances the Conversion Efficiency of Dye-Sensitized Solar Cell[J]. Journal of Physical Chemistry B,2003,107,13280～13285
[20]张静,习成成,曹祎明等.共熔室温离子液体及其制法和应用[P].中国专利,CN101232080A.2008-07-30
[21]Gratzel M.Mesoscopic solar cells for electricity and hydrogen Production from sunlight[J]. Chem. Lett.,2005,34 (1):8～13
[22]Becquerel C. Memoire sur les effets electriques produits sousl'influence des rayons solaires [J].C.R.Acad. Sci.Paris,1839,9:561～567.
[23]Chapin D M,Fuller C S,Pearson G L.A New Silicon p-n Junction Photocell for Converting Solar Radiation Into Electric Power[J]. J.Appl.Phys.,1954,25 (5):676～677
[24]O'Regan B,Gratzel M. A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 Films[J].Nuture,1991,353 (6346):737～740
[25]Md K Nazeeruddin,F D Angelis,S Fantacci A.et al. Combined experimental and DFT-TDDFTcomputational study of Photoelectrochemical cell ruthenium sensitizers[J]. J.Am.Chem.Soc.,2005,127 (48):16835～1684
[26]Wang Kongjia(王孔嘉),Dai Songyuan(戴松元).染料敏化太阳电池及其进展[J].Physics(物理),2007,36(11)：853～861
[27]Li X H, Gui J, Yang H.et al.A new Carbazole-Based Phenanthrenyl Ruthenium Complex as Sensitizer for a Dye-Sensitized Solar Cell [J]. Inorganica Chimica Acta,2008,361 (9～ 10):2835～2840.
[28]Kuang D B, Ito S, Wenger B. et al.High Molar Extinction Coefficient Heteroleptic Ruthenium Complexes for Thin Film Dye-Sensitized Solar Cells[J].Journal of the American Chemical Society,2006,128 (12):4146～4154
[29]Hara K,Wang Z S,Sato T.et al.Oligothiophene-Containing Coumarin Dyes for Efficient Dye-Sensitized Solar Cells[J].Journal of Physical Chemistry B,2005,109 (32):15476～ 15482
[30]Kim D, Song K, Kang M S. et al. Efficient Organic Sensitizers Containing Benzo[cd]Indole: Effect of Molecular Isomerization for Photovoltaic Properties [J]. Journal of Photochemistry and Photobiology A: Chemistry,2009,201 (2～3):102～110
[31]Ito S, Miura H, Uchida S.et al. High-Conversion-Efficiency Organic Dye-Sensitized Solar Cells with a Novel Indoline Dye [J].Chemical Communications,2008 (41):5194-5196.
[32]Palomares E, Clifford J N, Haque S A. et al. Control of ChargRecombinat- ion Dynamics in Dye Sensitized Solar Cells by the Use of Conformally Deposited Metal Oxide Blocking Layers[J]. J Am Chem Soc,2003,125:475
[33]K Sayama, S Tsukagoshi.et al. Photoelectrochemical properties of Jaggregates of benzothiazole merocyanine dyes on a nanostructured TiO2 film [J]. Phys. Chem.B.,2002,106, 1363
[34]Kuang D, Klein C, Gratzel M, et al.High molar extinction coefficient ion-coordinating ruthenium sensitizer for efficient and stable mesoscopic dye-sensitized solar cells[J]. Adv. Funet.Mater.,2007 17:154—160.
[35]Chen C, Clien J, Wu S, etal.Multifunetionalized ruthenium-based supersensitizers for highly effieient dye-sensitized solar cells[J].Angew.Chem.Int.Ed.,2008,47 (38):7342—7345
[36]Sayama K, Hara K, Arakawa H.Photosensitization of a porous TiO2 electrode with merocyanine dyes containing a carboxyl group and a long alkyl chain [J].Chem Commun.,2000,1173～1174
[37]Wang Z, Li F, Huang C, et al.Photoelectric conversion properities of nanocrystalline TiO2 electrodes sensitized with hemicyanine derivatives [J].J.Phys.Chem.B,2000,104:9676～9682
[38]Wang Z, Li F,Huang C.Photocurrent enhancement of hemicyanine dyes containing RSO3-group through treating TiO2 films with hydrochloric acid [J].J.Phys.Chem. B,2001,105: 9210～9217
[39]Horiuehi T, Miura H,Uehida S.Highly-efficient metal-free organic Dyes for dye-sensitized solar cells[J].Chem.Conunun.,2003,3036～3037
[40]Koumura N, Wang Z, Mori S,et al. Alkyl-functionalized organic dyes for efficient molecular photovoltaics[J].J.Am.Chem.Soc.,2008,130 (12):4202～4203
[41]Wang Z,Koumura N,Cui Y,et al.Hexylthiophene-functionalized carbazole dyes for efficient molecular photovoltaics:Tuning of solar cell performance by structural modification [J].Chem.Mater.,2008,20(12):3993～4003
[42]Kim S, Lee J. Kang S,et al.Molecular engineering of organic sensitizers for solar cell applications[J].J.Am.Chem.Soc.,2006,128 (51):16701～16707
[43]Hagherg D, Edvinsson T, Sun L, et al.A novel organic chromophore for dye-sensitized nanostructure solar cells[J].Chem.Commun.,2006,2245～247
[44]Hagherg D, Yum J, Lee H, et al.Molecular engineering of organic sensitized solar cell applications[J].J.Am.Chem.Soc.,2008,130 (19):6259～6266
[45]A. HERCOUET and M. LE CORRE. A convenient Synthesis of Alkylphosph- onium Salts [J]. Phosphorus, Sulfur, and Silicon,1990,48:279～280
[46]Jose, R, et al. Relationship between the molecular orbital structure of the dyes and photocurrent density in the dye-sensitized solar cells[J]. Applied Physics Letters,2008,93 (2):023125/1～023125/3
[2]Wilkes J S,Zaworotko M J.Air and water stable 1-ethye-3-methylimidazolium base ionic liquids[J].Journal of Chemical Society, Chemical Communications,1992,965～967
[3]Hermann W A, Bohm V P W.Heck reaction catalyzed by phospha-pallada-cycles in non-aqueous ionic liquids[J] J.Organometallic Chem.,1999,572:141～145
[4]Bohm V P W, Herrmann, W A.Coordination Chemistry and Mechanisms of Metal C-atalyzed C-C Coupling Reactions,Part 12 Nonaqueous Ionic Liquids:Superior Reaction Media for the Catalytic Heck-Vinylation of Chloroa-renes[J]. Chem.Eur.J.,2000,6(6):1017～1025
[5]Xu L,Chen W,Ross J.et al.Palladium-Catalyyzed Ragioselective Arylation of an Electron-Rich Olefin by Aryl Halides in Ionic Liquids[J]. Org.lett.,2001,3(2):295～297
[6]Hagiwara H,Shimizu Y,Hoshi T.et al. Heterogeneous Heck reaction catalyzed by Pd/C in ionic liquid[J].Tetrahedron Lett.,2001,42(26):4349～4351
[7]Mathews C J,Smith P J,Welton T.et al.Palladium catalysed Suzuki cross-coupling reactions in ambient temperature ionic liquids[J].Chem.Commun.,2000,14:1249～1250
[8]McNulty J,Capretta A,Wilson J.et al. Suzuki cross-coupling reactions of aryl halides in phosphonium salt ionic liquid under mild conditions[J].Chem.Commun.2002,17:1986～1987
[9]Dell'Anna M.M,Gallo V, Mastrorilli.et al.Metal cataly sed Michael additions in ionic liquids [J].Chem Commun,2002(5):434～435
[10]Gallo V,Mastrorilli P,Nobil C F.et al. How does the presence of impurities change the performance of catalytic systems in ionic liquids?A case study:the Michael addition of acety-lacetone to methyl vinyl ketone[J].J.Chem.Soc.,Dalton Trans.,2002,23:4339～4342
[11]彭家建,邓友全.离子液体系中催化环已烷酮肟重排已内酰胺[J].石油化工,2001,30(2)：91～92
[12]Peng J,Deng Y,Catalytic Beckmann rearrangement of ketoximes in ionic liquids [J]. Tetrahedron Lett.,2001,42(3):403～405
[13]Ren R X,Zueva L D,Ou W. Formation of ε-caprolactam via catalytic Beckmann rearrange ment using P2O5 in ionin liquids[J].Tetrahedron Lett.,2001,42(48):8441～8443
[14]Harjani J R,Nara S J and Salunkhe M M.Fries rearrangement in ionic melts [J].Tetrahedron Lett.2001,42(10):1979～1981
[15]Zulfiqar F,and Kitazume T. Lewis acid-catalysed sequential reaction in ionic liquids[J].Green Chem.,2000,2 (6):296～297
[16]O'Regan B,Gratzel M. A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 Films [J]. Nature.1991,353 (24):737～739
[17]Papageorgiou N,Athanassov Y,Armand M.et al.The performance and stability of amperatue molten salts for solar cell applications[J].Journal of the Electronchemical Society,1996,143, 3099～3108
[18]王淼,林原,肖绪瑞.离子液体在TiO2钠晶染料敏化太阳能电池中的应用[J].化学通报,2004,4,266～270
[19]Wang P,Zakeeruddin S,Moser J,et al.A New Ionic Liquid Electrolyte Enhances the Conversion Efficiency of Dye-Sensitized Solar Cell[J]. Journal of Physical Chemistry B,2003,107,13280～13285
[20]张静,习成成,曹祎明等.共熔室温离子液体及其制法和应用[P].中国专利,CN101232080A.2008-07-30
[21]Gratzel M.Mesoscopic solar cells for electricity and hydrogen Production from sunlight[J]. Chem. Lett.,2005,34 (1):8～13
[22]Becquerel C. Memoire sur les effets electriques produits sousl'influence des rayons solaires [J].C.R.Acad. Sci.Paris,1839,9:561～567.
[23]Chapin D M,Fuller C S,Pearson G L.A New Silicon p-n Junction Photocell for Converting Solar Radiation Into Electric Power[J]. J.Appl.Phys.,1954,25 (5):676～677
[24]O'Regan B,Gratzel M. A low-cost, high-efficiency solar cell based on dye-sensitized colloidal TiO2 Films[J].Nuture,1991,353 (6346):737～740
[25]Md K Nazeeruddin,F D Angelis,S Fantacci A.et al. Combined experimental and DFT-TDDFTcomputational study of Photoelectrochemical cell ruthenium sensitizers[J]. J.Am.Chem.Soc.,2005,127 (48):16835～1684
[26]Wang Kongjia(王孔嘉),Dai Songyuan(戴松元).染料敏化太阳电池及其进展[J].Physics(物理),2007,36(11)：853～861
[27]Li X H, Gui J, Yang H.et al.A new Carbazole-Based Phenanthrenyl Ruthenium Complex as Sensitizer for a Dye-Sensitized Solar Cell [J]. Inorganica Chimica Acta,2008,361 (9～ 10):2835～2840.
[28]Kuang D B, Ito S, Wenger B. et al.High Molar Extinction Coefficient Heteroleptic Ruthenium Complexes for Thin Film Dye-Sensitized Solar Cells[J].Journal of the American Chemical Society,2006,128 (12):4146～4154
[29]Hara K,Wang Z S,Sato T.et al.Oligothiophene-Containing Coumarin Dyes for Efficient Dye-Sensitized Solar Cells[J].Journal of Physical Chemistry B,2005,109 (32):15476～ 15482
[30]Kim D, Song K, Kang M S. et al. Efficient Organic Sensitizers Containing Benzo[cd]Indole: Effect of Molecular Isomerization for Photovoltaic Properties [J]. Journal of Photochemistry and Photobiology A: Chemistry,2009,201 (2～3):102～110
[31]Ito S, Miura H, Uchida S.et al. High-Conversion-Efficiency Organic Dye-Sensitized Solar Cells with a Novel Indoline Dye [J].Chemical Communications,2008 (41):5194-5196.
[32]Palomares E, Clifford J N, Haque S A. et al. Control of ChargRecombinat- ion Dynamics in Dye Sensitized Solar Cells by the Use of Conformally Deposited Metal Oxide Blocking Layers[J]. J Am Chem Soc,2003,125:475
[33]K Sayama, S Tsukagoshi.et al. Photoelectrochemical properties of Jaggregates of benzothiazole merocyanine dyes on a nanostructured TiO2 film [J]. Phys. Chem.B.,2002,106, 1363
[34]Kuang D, Klein C, Gratzel M, et al.High molar extinction coefficient ion-coordinating ruthenium sensitizer for efficient and stable mesoscopic dye-sensitized solar cells[J]. Adv. Funet.Mater.,2007 17:154—160.
[35]Chen C, Clien J, Wu S, etal.Multifunetionalized ruthenium-based supersensitizers for highly effieient dye-sensitized solar cells[J].Angew.Chem.Int.Ed.,2008,47 (38):7342—7345
[36]Sayama K, Hara K, Arakawa H.Photosensitization of a porous TiO2 electrode with merocyanine dyes containing a carboxyl group and a long alkyl chain [J].Chem Commun.,2000,1173～1174
[37]Wang Z, Li F, Huang C, et al.Photoelectric conversion properities of nanocrystalline TiO2 electrodes sensitized with hemicyanine derivatives [J].J.Phys.Chem.B,2000,104:9676～9682
[38]Wang Z, Li F,Huang C.Photocurrent enhancement of hemicyanine dyes containing RSO3-group through treating TiO2 films with hydrochloric acid [J].J.Phys.Chem. B,2001,105: 9210～9217
[39]Horiuehi T, Miura H,Uehida S.Highly-efficient metal-free organic Dyes for dye-sensitized solar cells[J].Chem.Conunun.,2003,3036～3037
[40]Koumura N, Wang Z, Mori S,et al. Alkyl-functionalized organic dyes for efficient molecular photovoltaics[J].J.Am.Chem.Soc.,2008,130 (12):4202～4203
[41]Wang Z,Koumura N,Cui Y,et al.Hexylthiophene-functionalized carbazole dyes for efficient molecular photovoltaics:Tuning of solar cell performance by structural modification [J].Chem.Mater.,2008,20(12):3993～4003
[42]Kim S, Lee J. Kang S,et al.Molecular engineering of organic sensitizers for solar cell applications[J].J.Am.Chem.Soc.,2006,128 (51):16701～16707
[43]Hagherg D, Edvinsson T, Sun L, et al.A novel organic chromophore for dye-sensitized nanostructure solar cells[J].Chem.Commun.,2006,2245～247
[44]Hagherg D, Yum J, Lee H, et al.Molecular engineering of organic sensitized solar cell applications[J].J.Am.Chem.Soc.,2008,130 (19):6259～6266
[45]A. HERCOUET and M. LE CORRE. A convenient Synthesis of Alkylphosph- onium Salts [J]. Phosphorus, Sulfur, and Silicon,1990,48:279～280
[46]Jose, R, et al. Relationship between the molecular orbital structure of the dyes and photocurrent density in the dye-sensitized solar cells[J]. Applied Physics Letters,2008,93 (2):023125/1～023125/3