CN101007904A - Organic dye containing triphenylamine and its preparation method and uses - Google Patents
Organic dye containing triphenylamine and its preparation method and uses Download PDFInfo
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- CN101007904A CN101007904A CN 200710056487 CN200710056487A CN101007904A CN 101007904 A CN101007904 A CN 101007904A CN 200710056487 CN200710056487 CN 200710056487 CN 200710056487 A CN200710056487 A CN 200710056487A CN 101007904 A CN101007904 A CN 101007904A
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E10/549—Organic PV cells
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Abstract
The invention belongs to solar energy battery technology, which in detail relates to a novle triphenylamine organic dye and preparation and its application as photosensitizer in dye sensitization solar energy battery. Said organic dye possesses good light trapping capacity, and the D- pi-A molecule structure leads to electron effective transition inside molecule. The photoelectric conversion performance is high by applying organic photosensitizer to dye sensitization solar energy battery. The novle triphenylamine organic dye is characterized by new constructure, easy synthesis, low cost, outstanding electrooptic performance, and potential application prospect of noble metal- containing replacing dye sensitizer.
Description
[technical field]: the present invention relates to technical field of solar batteries, particularly a class is applied to the preparation and the application of the novel triphen amido organic dye in the beam material sensitization solar battery.Such triphen amido organic dye is the organic photosensitizing agent of a class excellent performance, is applied in the dye sensitization solar battery, can obtain higher photoelectric transformation efficiency.
[background technology]: along with becoming increasingly conspicuous of shortage of resources and problem of environmental pollution, sun power more and more receives common people's concern as a kind of clean reproducible energy.Current, carrying out opto-electronic conversion by solar cell is one of main path of human use's sun power.In solar cell, high and technology maturation has occupied the share of solar cell 90% to silicon solar cell because of its turnover ratio, however silicon be solar cell because of its complex process, cost an arm and a leg material requirements harshness and be difficult to popularize.How to improve the photoelectric transformation efficiency of solar cell and effectively reduce its manufacturing cost, become the target that many solar cell working persons constantly pursue.
From Switzerland Gr tzel in 1991 professor since making a breakthrough aspect dye sensitization solar battery (DSC) research (O ' Regan, B.; Grt zel M.Nature 1991,353,737.), such battery demonstrates powerful commercial application prospect owing to have efficient, low cost, less energy-consumption, advantages of environment protection, becomes the focus that countries in the world are studied gradually.For this reason, both at home and abroad at time anode, ionogen to DSC, continuous exploration has all been carried out in aspects such as production technique and battery structure.Wherein, play keying action as the dye sensitizing agent of DSC important component part, they catch sunlight, and produce excitation electron, are injected into then in the light anode, and its photoelectric properties are to the photoelectric transformation efficiency important influence of whole DSC.At present, the best dye sensitizing agent of performance is the organic sensitizing agent of metal that contains precious metal, as Ru Quito pyridine complex (Gr tzel, M.Journal of Photochemistry and Photobiology A:Chemistry2004,164,3), they to have a light capture ability strong, the advantage that photoelectric transformation efficiency is high, however its price finiteness high and the precious metal resource has limited its practical application.Compare with Ru Quito pyridine complex, the pure organic dye that does not contain precious metal has the advantage that cost is low, optical extinction coefficient is high and structure is various.Therefore, in recent years, the synthetic efficient organic dye sensitized dose of research focus that becomes this field that is used for alternative Ru Quito pyridine complex.
Triphenylamine and derivative thereof are the photoelectric materials of a class excellent performance owing to have good hole transport performance and strong electron donation, are expected to obtain efficiently organic dye sensitized dose of triphen amido by molecular designing.Yet, at present about the report that can be applicable to organic dye sensitized dose of triphen amido among the DSC also seldom (Hagberg, D.P.; Edvinsson, T.; Marinado, T.; Boschloo, G.; Hagfeldt.A.; Sun, L. Chem.Commun.2006,2245).Therefore, organic dye sensitized dose of over-all properties and reduction battery cost for the raising dye sensitization solar battery of the efficient triphen amido of synthesizing new has crucial meaning.
[summary of the invention]: the objective of the invention is to solve the problem that the existing organic photosensitizing agent that contains precious metal costs an arm and a leg and can't popularize, what provide that a class can be used as photosensitizer contains organic dye of trianilino group and preparation method thereof.
Another object of the present invention provides a class triphen amido organic dye as photosensitizer, is applied to dye sensitization solar battery.
Novel triphen amido organic dye provided by the invention has following chemical structure:
Wherein R is H, monoene, vinylbenzene.
A kind of preparation method of above-mentioned triphen amido organic dye is characterized in that through following step:
(1) triphenylamine list aldehyde (V)/triphenylamine dialdehyde (VI) is synthetic:
Add exsiccant N under the ice-water bath in the three-necked bottle of drying tube is housed, dinethylformamide (DMF) slowly drips phosphorus oxychloride (POCl
3), stirred 2 hours, obtain Wei Ersi Mel (Vilsmeier) reagent, wherein DMF and POCl
3Mol ratio be 10: 1.Triphenylamine is joined in the Vilsmeier reagent, reacted 2.5-8 hour down at 95-105 ℃, product is poured in the frozen water, regulates pH value to neutral with aqueous sodium hydroxide solution, obtains precipitation; Crude product makes triphenylamine list aldehyde through column chromatography for separation, and wherein the mol ratio of triphenylamine and Vismeier reagent is 1: 1.1.
The preparation method of triphenylamine dialdehyde is identical with the preparation method of triphenylamine list aldehyde, and wherein the mol ratio of triphenylamine and Vilsmeier reagent is 1: 10.
(2) synthetic (VII) of triphenylamine diene:
With iodate methyl triphenyl phosphine (Ph
3PCH
3I) be dissolved in the exsiccant tetrahydrofuran (THF) (THF), cryosel is bathed cooling, and nitrogen protection adds potassium tert.-butoxide (KOt-Bu) then, stirs under the room temperature and obtains ylide (ylide) reagent, wherein KOt-Bu and Ph half an hour
3PCH
3The I mol ratio is 1～1.1: 1.The triphenylamine dialdehyde that the last step was made joins in this ylide reagent, stirs under the room temperature and spends the night, and crude product extracts with anhydrous diethyl ether, makes the triphenylamine diene through column chromatography for separation, and wherein the mol ratio of triphenylamine dialdehyde and ylide reagent is 1: 3.
(3) synthetic (VIII) of substituting group triphenylamine list aldehyde:
With Ph
3PCH
3I or bromination Bian Ji triphenylphosphine (Ph
3PCH
2PhBr) be dissolved among the exsiccant THF, cryosel is bathed cooling, and nitrogen protection adds KOt-Bu then, stirs under the room temperature and obtains ylide reagent, wherein KOt-Bu and Ph half an hour
3PCH
3I or Ph
3PCH
2The mol ratio of PhBr is 1～1.1: 1.This ylide reagent is added drop-wise in the THF solution of triphenylamine dialdehyde, reaction is 5-10 hour under the room temperature, crude product extracts with anhydrous diethyl ether, prepares substituting group triphenylamine list aldehyde through column chromatography for separation, and wherein the mol ratio of triphenylamine dialdehyde and ylide reagent is 1: 1～1.5.
(4) substituting group triphenylamine monoene aldehyde (IX) is synthetic:
(a) substituting group is H: with Ph
3PCH
3I is dissolved among the exsiccant THF, and cryosel is bathed cooling, and nitrogen protection adds KOt-Bu then, stirs under the room temperature and obtains ylide reagent, wherein KOt-Bu and Ph half an hour
3PCH
3The I mol ratio is 1～1.1: 1.The triphenylamine list aldehyde that (1) step is made joins in this ylide reagent, stirs 24 hours under the room temperature, and crude product extracts with anhydrous diethyl ether, makes the triphenylamine monoene through column chromatography for separation, and wherein the mol ratio of triphenylamine list aldehyde and ylide reagent is 1: 2～3.
Add exsiccant N under the ice-water bath in the three-necked bottle of drying tube is housed, dinethylformamide (DMF) slowly drips phosphorus oxychloride (POCl
3), stirred 2 hours, obtain Vilsmeier reagent, wherein DMF and POCl
3Mol ratio be 10: 1.The triphenylamine monoene is joined in this Vilsmeier reagent, reacted under the room temperature 2～3 hours, product is poured in the frozen water, regulate pH value to neutral with aqueous sodium hydroxide solution, obtain precipitation, crude product makes triphenylamine monoene aldehyde through column chromatography for separation, and wherein the mol ratio of triphenylamine monoene and Vilsmeier reagent is 1: 5～6; Or
(b) substituting group is a monoene: triphenylamine diene and Vilsmeier reagent that (2) step makes at room temperature reacted 3 hours, product is poured in the frozen water, regulate pH value to neutral with aqueous sodium hydroxide solution, obtain precipitation, crude product makes monoene through column chromatography for separation and replaces triphenylamine monoene aldehyde, and the mol ratio of triphenylamine diene and Vilsmeier reagent is 1: 18～19; Or
(c) substituting group is a vinylbenzene: bathe under the cooling at cryosel, KOt-Bu is added Ph
3PCH
2In the exsiccant THF solution of PhBr, stir half an hour under the room temperature, obtain ylide reagent; The vinylbenzene replacement triphenylamine list aldehyde that (3) step is made is dissolved in THF, and join in this reagent, reaction is 24 hours under the room temperature, the mol ratio that vinylbenzene replaces triphenylamine list aldehyde and ylide reagent is 1: 2～3, crude product extracts with anhydrous diethyl ether, make vinylbenzene through column chromatography for separation and replace the triphenylamine monoene, replace triphenylamine monoene and exsiccant DMF and POCl by vinylbenzene
3At room temperature reacted 2 hours, product is poured in the frozen water, regulates pH value to neutral with aqueous sodium hydroxide solution, obtains precipitation, and crude product makes vinylbenzene through column chromatography for separation and replaces triphenylamine monoene aldehyde, and wherein vinylbenzene replaces triphenylamine monoene and POCl
3Mol ratio be 1: 5;
(5) (X) of triphenylamine diene aldehyde is synthetic
(2) are gone on foot triphenylamine diene and exsiccant DMF and the POCl that makes
3At room temperature reacted 3 hours, product is poured in the frozen water, regulates pH value to neutral with aqueous sodium hydroxide solution, obtains precipitation, and crude product makes triphenylamine diene aldehyde, triphenylamine diene and POCl through column chromatography for separation
3Mol ratio be 1: 18～19.
(6) triphen amido organic dye (I, II, III, V) synthetic
With substituting group triphenylamine list aldehyde (VIII)/substituting group triphenylamine monoene aldehyde (IX)/triphenylamine diene aldehyde (X), rhodanine-3-acetate and ammonium acetate add in the there-necked flask, glacial acetic acid is as reaction solvent, reflux conditions reacted 3-5 hour down, reaction finishes to be cooled to room temperature, pour in the frozen water, filtration, drying obtain solid matter, obtain triphen amido organic dye I/II/V through recrystallization or column chromatography purification, VIII/IX wherein, the mol ratio of rhodanine-3-acetate and ammonium acetate is 1: 1～1.1: 1～2; X, the mol ratio of rhodanine-3-acetate and ammonium acetate is 1: 2～2.1: 1～2;
Triphenylamine dialdehyde and rhodanine-3-acetate are added in the round-bottomed flask, dehydrated alcohol is as solvent, heating reflux reaction 24 hours, separate out red precipitate, suction filtration, solid matter is that eluent carries out column chromatography and obtains product III with the glacial acetic acid of ethyl acetate/ethanol (3: 1) and 1%, and the mol ratio of triphenylamine dialdehyde and rhodanine-3-acetate is 1: 2～2.1.
The application of a kind of above-mentioned novel triphen amido organic dye in dye sensitization solar battery, this battery comprises light anode, photocathode, thermoplastic barrier film and electrolytic solution, wherein:
Described smooth anode is a dye sensitization titanium dioxide dye sensitization titanium dioxide electrodes, and it comprises base material FTO conductive glass, the nano titanium dioxide film electrode, and above-mentioned novel triphen amido organic dye is as photosensitizer;
Described photocathode is a platinum electrode;
The prescription of described electrolytic solution is: in acetonitrile solvent, add 1 of 0.6M, and 2-dimethyl-3-propyl imidazole iodine, the lithium iodide of 0.1M and the iodine of 0.05M are made supporting electrolyte.
The following step of the preparation method of dye sensitization titanium dioxide photo anode process in the above-mentioned application:
Method by silk screen printing is coated in titania slurry on the FTO conductive glass equably, through 450 ℃ of high temperature sintering 30min, naturally cools to room temperature, uses 50mMTiCl
4Solution-treated 30min, with distilled water, alcohol flushing surface, nitrogen dries up; Through 450 ℃ of high temperature sintering 30min, obtain the titanium dioxide porous membrane that thickness is about 10～16 μ m again; The titanium dioxide film that obtains is soaked in the triphen amido organic dye solution subsequently, other adds the Chenodiol of 1mM as coadsorbent, and titanium dioxide film soaked in dye solution 24 hours, takes out the back and cleans with dehydrated alcohol, and nitrogen dries up.
The mass percent of above-mentioned titania slurry is formed: 16% titanium dioxide powder, 4% ethyl cellulose and 80% Terpineol 350.
In the above-mentioned application, the concentration of described triphen amido organic dye solution is 3 * 10
-4As solvent, III and IV are with methyl alcohol/DMF4: 1 mixed solvent is as solvent with methyl alcohol or 4: 1 mixed solvent of methyl alcohol/acetonitrile for M:I and II.
Advantage of the present invention and effect:
The invention has the advantages that described triphen amido organic dye preparation technology is simple, with low cost, productive rate is higher, is easy to purifying.This compounds can carry out modification by molecular designing, the photoelectric material of obtained performance excellence.Such organic dye is applied in the dye sensitization solar battery as photosensitizer, has good opto-electronic conversion performance, demonstrate potential and substitute the application prospect that contains the noble metal dye sensitizing agent.
The invention provides in the novel triphen amido of class organic dye, preparation and application, enriched the research contents of organic dye, expanded the mentality of designing of novel organic photosensitizing agent as photosensitizer.For the performance that improves dye sensitization solar battery important theory and practical significance are arranged.
[description of drawings]:
Fig. 1 is the ultraviolet-visible absorption spectroscopy of the triphen amido organic dye of embodiment 1-3 preparation;
Fig. 2 is the ultraviolet-visible absorption spectroscopy of the organic dye sensitized titanium dioxide electrodes of the triphen amido of embodiment 1-3 preparation;
Fig. 3 is the Electronic Speculum figure of the titanium dioxide film of embodiment 6 making: (a) film surface scan electronic microscope photos (b) cross section scanning electron microscope analysis;
Fig. 4 is the dye sensitization solar battery structural representation that embodiment 7 makes;
Fig. 5 is the I-V curve of the organic dye sensitized dye sensitization solar battery of the triphen amido of embodiment 1-3 preparation;
Fig. 6 is the I-V curve of dye sensitization solar battery under different light intensity of the vinyl substituted triphenylamine-rhodanine acetate D1b sensitization of embodiment 1 preparation.
[embodiment]:
Embodiment 1:
Synthetic route is as follows:
Synthetic method is:
Vinyl substituted triphenylamine list aldehyde 2b's is synthetic
Take by weighing 9.3mmol (3.76g) Ph
3PCH
3I adds in the 100ml three-necked bottle, adds 60ml exsiccant THF then, bathes cooling, nitrogen protection with cryosel.Add 9.4mmol (1.06g) KOt-Bu then, stir half an hour under the room temperature, obtain ylide reagent; Take by weighing 3.1mmol (0.93g) triphenylamine dialdehyde (1), add in the 250ml three-necked bottle, add 30ml exsiccant THF then; Under the nitrogen protection, ylide reagent slowly is added drop-wise in the three-necked bottle, stirs under the room temperature and spend the night.Reaction solution is washed with water, the anhydrous diethyl ether extraction, the organic phase anhydrous sodium sulfate drying that obtains revolves steaming.For eluent carries out column chromatography, obtain faint yellow oily product 2b, productive rate 60% with petrol ether/ethyl acetate (9: 1).
Styryl replaces the synthetic of triphenylamine list aldehyde 2c
Take by weighing 9.9mmol (4.3g) Ph
3PCH
2PhBr adds in the 100ml three-necked bottle, adds 60ml exsiccant THF then, bathes cooling, nitrogen protection with cryosel.Add 10mmol (1.12g) KOt-Bu then, stir half an hour under the room temperature, obtain ylide reagent; Take by weighing 6.6mmol (2g) triphenylamine dialdehyde, add in the 250ml three-necked bottle, add 50ml exsiccant THF then; Under the nitrogen protection, ylide reagent slowly is added drop-wise in the three-necked bottle, stirred 5 hours under the room temperature.Reaction solution is washed with water, the anhydrous diethyl ether extraction, the organic phase anhydrous sodium sulfate drying that obtains revolves to steam to remove and desolvates.For eluent carries out column chromatography, obtain faint yellow oily product 2c, productive rate 75% with petrol ether/ethyl acetate (9: 1).
Triphenylamine-rhodanine acetate D1a's is synthetic
In the 50ml round-bottomed flask, add 0.55mmol (150mg) triphenylamine list aldehyde (2a) successively, 0.57mmol (110mg) rhodanine-3-acetate, 100mg ammonium acetate, 15ml glacial acetic acid, stir, reflux 3 hours obtains red solution, pour in the water, cooling has red precipitate to separate out.Suction filtration, the solid matter ethyl alcohol recrystallization obtains red crystals D1a (188mg, productive rate 73.5%).
1H NMR(300MHz，CDCl
3)：δ(ppm)：4.92(2H，s，-CH
2COOH)，7.01(2H，d，J＝8.79 Hz， aromatic)，7.14-7.19(6H，m，aromatic)，7.31-7.37(6H，m，aromatic)，7.71(1H，s，-CH＝).ESI-MS：m/z 445([M-H]-).Anal.Calcd for C
24H
18N
2O
3S
2：C，64.57；N，6.27；H，4.0.Found：C，64.53；N，6.18；H，4.1.
Vinyl substituted triphenylamine-rhodanine acetate D1b's is synthetic
In the 50ml round-bottomed flask, add 0.55mmol (165mg) 2a successively, 0.57mmol (110mg) rhodanine-3-acetate, the 1001mg ammonium acetate, the 15ml glacial acetic acid stirs, and reflux 3 hours obtains red solution, pours in the water, and cooling has red precipitate to separate out.Suction filtration, solid matter for eluent carries out column chromatography, obtain red material D1b (146mg, productive rate 53.6%) with ethyl acetate/ethanol (3: 1).
1H NMR(300MHz，DMSO-d
6)：δ(ppm)：4.41(2H，s，-CH
2COOH)，5.23(1H，d，J＝11.5 Hz，-CH＝CH
2)，5.75(1H，d，J＝16.8 Hz，-CH＝CH
2)，6.71(1H，dd，J＝10.9，11.1Hz，-CH＝)，6.93(2H，q，J＝8.9 Hzaromatic)，7.08-7.24(5H，m，aromatic)，7.37-7.52(6H，m，aromatic)，7.66(1H，s，-CH＝).ESI-MS：m/z 471([M-H]
-).Anal.Calcd for C
26H
20N
2O
3S
2：C，66.10；N，5.93；H，4.24.Found：C，66.18；N，5.87；H，4.32.
Styryl replaces the synthetic of triphenylamine-rhodanine acetate D1c
In the 50ml round-bottomed flask, add 0.8mmol (300mg) 2a successively, 0.9mmol (171mg) rhodanine-3-acetate, the 100mg ammonium acetate, the 15ml glacial acetic acid stirs, and reflux 3 hours obtains red solution, pours in the water, and cooling has red precipitate to separate out.Suction filtration, the solid matter ethyl alcohol recrystallization obtains red crystals D1c (355mg, productive rate 81%).
1H NMR(300MHz，DMSO-d
6)：δ(ppm)：4.43(2H，s，-CH
2COOH)，6.98(2H，m，-CH＝CH-)，7.11-7.29(9H，m，aromatic)，7.35-7.45(4H，m，aromatic)，7.51(2H，d，J＝8.7Hz，aromatic)，7.60(3H，t，J＝7.6Hz，aromatic)，7.67(1H，s，-CH＝).ESI-MS：m/z 547([M-H]
-).Anal.Calcd for C
32H
24N
2O
3S
2：C，70.00；N，5.11；H，4.38.Found：C，69.79；N，5.15；H，4.40.
Embodiment 2:
Synthetic route is as follows:
Synthetic method is:
Triphenylamine monoene aldehyde 4a's is synthetic
Take by weighing 3.7mmol (1.5g) Ph
3PCH
3I adds in the 100ml three-necked bottle, adds 60ml exsiccant THF then, bathes cooling, nitrogen protection with cryosel.Add 3.9mmol (0.44g) KOt-Bu then, stir half an hour under the room temperature, obtain ylide reagent; Add 3.0mmol (0.8g) triphenylamine list aldehyde again, stirred 24 hours under the room temperature.Reaction solution is washed with water, the anhydrous diethyl ether extraction, the organic phase anhydrous sodium sulfate drying that obtains revolves steaming.With sherwood oil is that eluent carries out column chromatography, obtains colourless triphenylamine monoene (3a), productive rate 85%.
Cryosel is bathed and add 10ml exsiccant DMF down in the three-necked bottle of drying tube is housed, and slowly is added dropwise to 6.5mmol (0.6ml) POCl
3, stirred 2 hours, add 1.1mmol (300mg) 3a and 5mlDMF, reaction is 2.5 hours under the room temperature.Cooling is poured mixture behind the reactant in the 50g frozen water into, stirs down to add 20% sodium hydroxide solution, and regulating pH value is 6～8, separates out yellow mercury oxide, and suction filtration obtains yellow solid, with the methylene dichloride dissolving, adds anhydrous sodium sulfate drying and spends the night.Revolve to steam to remove and desolvate, for eluent carries out column chromatography, obtain faint yellow oily product 4a, productive rate 83.2% with petrol ether/ethyl acetate (9: 1).
Triphenylamine-alkene-rhodanine acetate D2's is synthetic
In the 50ml round-bottomed flask, add 0.55mmol (165 mg) 4a successively, 0.57mmol (110mg) rhodanine-3-acetate, the 100mg ammonium acetate, the l5ml glacial acetic acid stirs, and reflux 3 hours obtains red solution, pours in the water, and cooling has red precipitate to separate out.Suction filtration, solid matter for eluent carries out column chromatography, obtain red material D2 (208mg, productive rate 76.2%) with ethyl acetate/ethanol (3: 1).
1H NMR(300MHz，DMSO-d
6)：δ(ppm)：4.38(2H，s，-CH
2COOH)，6.85-6.94{3H，m，(2H，aromaticand 1H，-CH＝)}，7.08-7.17(5H，m，aromatic)，7.28(1H，d，J＝14.9 Hz，-CH＝)，7.37(4H，t，J＝7.9 Hz，aromatic)，7.48(1H，d，J＝11.4 Hz，-CH＝)，7.57(2H，d，J＝8.7Hz，aromatic).ESI-MS：m/z 471([M-H]
-).Anal.Calcd for C
26H
20N
2O
3S
2：C，66.10；N，5.93；H，4.24.Found：C，66.05；N，5.97；H，4.33.
Embodiment 3:
Synthetic route is as follows:
Synthetic method is:
Two (rhodanine acetate) D3's of triphenylamine is synthetic
In the 50ml round-bottomed flask, add 0.50mmol (150mg) triphenylamine dialdehyde successively, 1.05mmol (200mg) rhodanine-3-acetate, 20ml ethanol, stir, reflux 24 hours is separated out red precipitate, suction filtration, solid matter is that eluent carries out column chromatography with the glacial acetic acid of ethyl acetate/ethanol (3: 1) and 1%, obtains red material D3 (206mg, productive rate 60.3%).
1H NMR(300MHz，DMSO-d
6)：δ(ppm)：4.40(4H，s，-CH
2COOH)，7.08(4H，d，J＝8.2 Hz，aromatic)，7.16(2H，d，J＝7.9 Hz，aromatic)，7.31(1H，t，J＝7.2 Hz，aromatic)，7.46(2H，t，J＝7.3 Hz，aromatic)，7.55(4H，d，J＝8.2 Hz，aromatic)，7.67(2H，s，-CH＝).ESI-MS：m/z 646([M-H]
-).Anal.Calcd forC
30H
21N
3O
6S
4：C，55.64；N，6.49；H，3.25.Found：C，55.57；N，6.43；H，3.30.
Synthesizing of vinyl substituted triphenylamine monoene aldehyde 6 and triphenylamine diene aldehyde 7
Take by weighing 7.4mmol (3.0g) Ph
3PCH
3I adds in the 100ml three-necked bottle, adds 60ml exsiccant THF then, bathes cooling, nitrogen protection with cryosel.Add 7.8mmol (0.88g) KOt-Bu then, stir half an hour under the room temperature, obtain ylide reagent; Add 3.0mmol (0.9g) triphenylamine dialdehyde again, stir under the room temperature and spend the night.Reaction solution is washed with water, the anhydrous diethyl ether extraction, the organic phase anhydrous sodium sulfate drying that obtains revolves steaming.With sherwood oil is that eluent carries out column chromatography, obtains colourless triphenylamine diene (5), productive rate 75%.
Cryosel is bathed and add 10ml exsiccant DMF down in the three-necked bottle of drying tube is housed, and slowly is added dropwise to 22.7mmol (2.1ml) POCl
3, stirred 2 hours, add 1.2mmol (655mg) 5 and 10mlDMF, reaction is 3 hours under the room temperature.Cooling is poured mixture behind the reactant in the 100g frozen water into, stirs down to add 20% sodium hydroxide solution, and regulating pH value is 6～8, separates out yellow mercury oxide, and suction filtration obtains yellow solid, with the methylene dichloride dissolving, adds anhydrous sodium sulfate drying and spends the night.Revolve to steam to remove and desolvate, carry out column chromatography for eluent, obtain yellow solid 6 and the 310mg yellow solid 7 of 235mg respectively with sherwood oil/dichloromethane/ethyl acetate (7: 3: 1).
Vinyl substituted triphenylamine-alkene-rhodanine acetate D4's is synthetic
In the 50ml round-bottomed flask, add 0.55mmol (179mg) 6 successively, 0.57mmo1 (110mg) rhodanine-3-acetate, the 100mg ammonium acetate, the 15ml glacial acetic acid stirs, and reflux 3 hours obtains red solution, pours in the water, and cooling has red precipitate to separate out.Suction filtration, solid matter for eluent carries out column chromatography, obtain red material D4 (153mg, productive rate 53.5%) with ethyl acetate/ethanol (3: 1).
1H NMR(300MHz，DMSO-d
6)：δ(ppm)：4.40(2H，s，-CH
2COOH)，5.20(1H，d，J＝11.7 Hz，-CH＝CH
2)，5.73(1H，d，J＝17.5 Hz，-CH＝CH
2)，6.69(1H，dd，J＝10.9，11.1 Hz，-CH＝)，6.84-6.95{3H，m，(2H，aromatic and 1H，-CH＝)}，7.04(4H，q，J＝8.7 Hz，aromatic)，7.16(1H，t，J＝7.3 Hz，aromatic)，7.28-7.40{4H，m，(3H，aromatic and 1H，-CH＝)}，7.43(1H，d，J＝8.6 Hz，aromatic)，7.47(1H，d，J＝11.5 Hz，-CH＝)，7.57(2H，d，J＝8.7 Hz，aromatic).ESI-MS：m/z 497([M-H]
-).Anal.Calcd for C
28H
22N
2O
3S
2：C，67.46；N，5.62；H，4.42.Found：C，67.41；N，5.73；H，4.36.
Two (alkene-rhodanine acetate) D5's of triphenylamine is synthetic
In the 50ml round-bottomed flask, add 0.50mmol (177mg) 7 successively, 1.05mmol (200mg) rhodanine-3-acetate, the 100mg ammonium acetate, the 15ml glacial acetic acid stirs, and reflux 3 hours obtains red solution, pours in the water, and cooling has red precipitate to separate out.Suction filtration, solid matter is that eluent carries out column chromatography with the glacial acetic acid of ethyl acetate/ethanol (3: 1) and 1%, obtains red material D5 (277mg, productive rate 75.2%).
1H NMR(300MHz，DMSO-d
6)：δ(ppm)：4.39(4H，s，-CH
2COOH)，6.85-7.01{6H，m，(4H，aromatic and2H，-CH＝)}，7.13(2H，d，J＝8.2Hz，aromatic)，7.22(2H，m，aromatic)，7.30(2H，d，J＝15.3 Hz，-CH＝)，7.40(2H，t，J＝7.6 Hz，aromatic)，7.47(2H，d，J＝11.5 Hz，-CH＝)，7.62(3H，d，J＝8.5 Hz，aromatic).ESI-MS：m/z 698([M-H]
-).Anal.Calcd for C
34H
25N
3O
6S
4：C，58.37；N，6.0；H，3.58.Found：C，58.42；N，6.05；H.3.51.
Embodiment 4: the spectrochemical property of triphenylamine radical dye characterizes
Such dye ligand is made as 1 * 10
-4The methanol solution of M adopts Japanese JascoV-550 ultraviolet-visible pectrophotometer to carry out absorption spectrum test (see figure 1); Adopt U.S. Cary Eclipse spectrophotofluorometer to carry out fluorometric investigation.Identical instrument is adopted in test to the ultra-violet absorption spectrum (see figure 2) of triphenylamine radical dye sensitization titanium dioxide electrodes (seeing embodiment 6).Listed the spectrochemical property of the prepared triphenylamine radical dye of embodiment 1-3 in the table 1.
The spectrochemical property of table 1 triphenylamine radical dye in solution
| ε/M -1cm -1 (Abs) a | λ max/nm(Abs) a | λ max/nm(Abs) b | λ max/nm (emission) a | λ max/nm (exciting) a | |
| D1a | 23700 | 458 | 475 | 540 | 380 |
| D1b | 36400 | 461 | 467 | 606 | 456 |
| D1c | 35900 | 467 | 483 | 541 | 385 |
| D2 | 22800 | 476 | 491 | 565 | 377 |
| D3 | 41200 | 481 | 485 | 602 | 449 |
| D4 | 25600 | 474 | 501 | 641 | 441 |
| D5 | 37700 | 501 | 511 | 640 | 427 |
A is the uv-absorbing and the fluorometric investigation of dye solution; B is the uv-absorbing test of triphenylamine radical dye sensitization titanium dioxide electrodes.
Embodiment 5: the electrochemical properties of triphenylamine radical dye characterizes
Adopt the oxidation potential (E of differentiated pulse method test dye
Ax), used instrument is U.S. PARSTAT 2273 electrochemical workstations.Three-electrode system is adopted in test: glass-carbon electrode is as working electrode; Platinum wire electrode is as counter electrode; Ag/AgNO
3As reference electrode, the correction of this electrode is undertaken by the redox-potential of measuring ferrocene in the acetonitrile glacial acetic acid (7/1) (acetonitrile).The redox-potential that obtains is converted to the value (vs NHE) with respect to standard hydrogen electrode.Testing used electrolytic solution is the solvent of acetonitrile glacial acetic acid (7/1), with the tertiary butyl ammoniumper chlorate of 0.1M as supporting electrolyte.Listed the electrochemical data of the prepared triphenylamine radical dye of embodiment 1-3 in the table 2.λ wherein
IntIntersection point place wavelength for absorption spectrum and emmission spectrum; E
0-0According to E
0-0=1240/ λ
IntCalculate; Reduction potential E
Red/ Vvs NHE is according to E
Red=E
Ax-E
0-0Calculate.
The electrochemical properties of table 2 triphenylamine radical dye
| λ int/nm | E 0-0/eV | E ax/VvsNHE | E
red/ | |
| D1a | ||||
| 500 | 2.48 | 1.0 | -1.48 | |
| D1b | 509 | 2.44 | 1.03 | -1.41 |
| D1c | 530 | 2.35 | 1.01 | -1.34 |
| D2 | 526 | 2.36 | 0.94 | -1.42 |
| D3 | 503 | 2.46 | 1.06 | -1.40 |
| D4 | 547 | 2.27 | 0.97 | -1.30 |
| D5 | 568 | 2.18 | 1.14 | -1.04 |
Embodiment 6: the preparation of the titanium dioxide electrodes of triphenylamine radical dye sensitization (light anode)
The method that adopts silk screen printing is titania slurry (prescription: 16wt% titanium dioxide powder (P25 type, the production of Germany Degussa company), 4wt% ethyl cellulose, 80wt% Terpineol 350) be coated in equably on the FTO conductive glass, through 450 ℃ of high temperature sintering 30min, naturally cool to room temperature, use 50mM TiCl
4Solution-treated 30min, towards Xian surface, nitrogen dries up, again through 450 ℃ of high temperature sintering 30min with distilled water, ethanol.Obtain the poriferous titanium dioxide film (Fig. 3) that thickness is about 12 μ m.The titanium dioxide film that obtains being soaked in triphen amido organic dye concentration subsequently is 3 * 10
-4In the solution of M (D1a, D1b, D2 and D4 with methyl alcohol as solvent, D3 and D5 with methyl alcohol/DMF (4: 1) as solvent, D1c with methyl alcohol/acetonitrile (4: 1) as solvent), other adds the Chenodiol (DCA) of 1mM as coadsorbent.Titanium dioxide film soaked in dye solution 24 hours, took out the back and cleaned with dehydrated alcohol, and nitrogen dries up.
The assembling of embodiment 7:DSC battery
Add sealing membrane (for example " surlyn " thermoplastic polymer film) between the titanium dioxide electrodes (light anode) of the triphenylamine radical dye sensitization that will make according to embodiment 6 and the platinum electrode (photocathode), under dull and stereotyped pressing machine, be heated to 100 ℃, heated sealant 20min, two electrodes are bonded together fully, dorsal pore at platinum electrode utilizes vacuum or manual method to inject electrolyte solution then, and sealing.Electrolyte prescription is: in acetonitrile solvent, add 1 of 0.6M, the 2-diformazan-lithium iodide of 3-propyl imidazole iodine 0.1M and the iodine of 0.05M are as supporting electrolyte, and being formulated in the dry glove box of electrolytic solution finished.The structure iron of this cell apparatus is seen Fig. 4.The number in the figure meaning is: 1, conductive glass; 2, titanium dioxide film; 3, photosensitizer; 4, ionogen; 5, platinum layer; 6, conductive glass; 7, barrier film.The effective illuminating area of this battery is: 0.16cm
2, at AM1.5-100mW/cm
2Light intensity under test, adopt U.S. Keith1ey 2400 digital source tables to gather photoelectric current, photovoltage, obtain short-circuit current (J
Sc), open circuit voltage (V
Oc), packing factor (FF) and photoelectric transformation efficiency.Listed the photoelectric property test data of the DSC of the prepared triphenylamine radical dye sensitization of embodiment 1-3 in the table 3, Fig. 5 is photoelectric current (I)-photovoltage (V) graphic representation of these DSC.The I-V curve of the data of associative list 3 and Fig. 5 is as can be seen: triphen amido organic dye of the present invention has good opto-electronic conversion performance as the photosensitizer of DCS, and wherein the photoelectric properties of D1a-c are best.
The photoelectric properties of the DCSs of table 3 triphenylamine radical dye sensitization
| V oc(mV) | J sc(mA/cm 2) | FF | η(％) | |
| D1a | 564 | 13.0 | 0.59 | 4.32 |
| D1b | 563 | 18.2 | 0.57 | 5.84 |
| D1c | 570 | 16.0 | 0.59 | 5.38 |
| D2 | 476 | 2.2 | 0.60 | 0.63 |
| D3 | 563 | 8.6 | 0.64 | 3.1 |
| D4 | 456 | 4.5 | 0.62 | 1.27 |
| D5 | 449 | 2.0 | 0.62 | 0.57 |
Embodiment 8:
Fig. 6 be the DCS of D1b sensitization under different light intensity (100,80,60,40,20mW/cm
2) the I-V graphic representation.As can be seen from the figure: of the present inventionly make the DSC of photosensitizer at 100mW/cm with D1b
2Light intensity under obtained 5.84% photoelectric transformation efficiency.Under low light intensity, can obtain higher photoelectric transformation efficiency: at 40mW/cm
2The time photoelectric transformation efficiency reached 6.9%.The I-V test of the DCS of other several triphenylamine radical dye sensitization under different light intensity also shows similar character.
By triphen amido organic dye being carried out spectrochemical property, electrochemical properties and photoelectric properties test, as can be seen: novel triphen amido organic dye of the present invention has good light capture ability, be applied among the DCS can obtain the photoelectric transformation efficiency more than 6% as photosensitizer.This comes from effective transfer of the intramolecularly electronics that D-π-A structure that the strong electron donation of triphenylamine, non-coplanar space structure and dyestuff have causes.Novel triphen amido organic dye novel structure provided by the invention is easy to synthesize, and is with low cost, and photoelectric properties are outstanding, can carry out modification by molecular designing, demonstrates potential and substitutes the application prospect that contains the noble metal dye sensitizing agent.
Claims (6)
1, a kind of novel triphen amido organic dye is characterized in that having following chemical structure:
Wherein R is H, monoene, vinylbenzene.
2, the preparation method of the described triphen amido of a kind of claim 1 organic dye is characterized in that through following step:
(1) triphenylamine list aldehyde (V)/triphenylamine dialdehyde (VI) is synthetic:
Add exsiccant N under the ice-water bath in the three-necked bottle of drying tube is housed, dinethylformamide (DMF) slowly drips phosphorus oxychloride (POCl
3), stirred 2 hours, obtain Wei Ersi Mel (Vilsmeier) reagent, wherein DMF and POCl
3Mol ratio be 10～20: 1; Triphenylamine is joined in the Vilsmeier reagent, reacted 2.5-8 hour down at 95-105 ℃, product is poured in the frozen water, regulates pH value to neutral with aqueous sodium hydroxide solution, obtains precipitation; Crude product makes triphenylamine list aldehyde or triphenylamine dialdehyde through column chromatography for separation, and wherein the mol ratio of triphenylamine and Vilsmeier reagent is to make triphenylamine list aldehyde at 1: 1.1～2 o'clock; The mol ratio of triphenylamine and Vilsmeier reagent is to make the triphenylamine dialdehyde at 1: 10～15 o'clock;
(2) synthetic (VII) of triphenylamine diene:
With iodate methyl triphenyl phosphine (Ph
3PCH
3I) be dissolved in the exsiccant tetrahydrofuran (THF) (THF), cryosel is bathed cooling, and nitrogen protection adds potassium tert.-butoxide (KOt-Bu) then, stirs under the room temperature and obtains ylide (ylide) reagent, wherein KOt-Bu and Ph half an hour
3PCH
3The I mol ratio is 1～1.1: 1; The triphenylamine dialdehyde that the last step was made joins in this ylide reagent, stirs under the room temperature and spends the night, and crude product extracts with anhydrous diethyl ether, makes the triphenylamine diene through column chromatography for separation, and wherein the mol ratio of triphenylamine dialdehyde and ylide reagent is 1: 3;
(3) synthetic (VIII) of substituting group triphenylamine list aldehyde:
With Ph
3PCH
3I or bromination Bian Ji triphenylphosphine (Ph
3PCH
2PhBr) be dissolved among the exsiccant THF, cryosel is bathed cooling, and nitrogen protection adds KOt-Bu then, stirs under the room temperature and obtains ylide reagent, wherein KOt-Bu and Ph half an hour
3PCH
3I or Ph
3PCH
2The mol ratio of PhBr is 1～1.1: 1; This ylide reagent is added drop-wise in the THF solution that concentration is 20～50% triphenylamine dialdehydes, reaction is 5-10 hour under the room temperature, crude product extracts with anhydrous diethyl ether, prepares substituting group triphenylamine list aldehyde through column chromatography for separation, and wherein the mol ratio of triphenylamine dialdehyde and ylide reagent is 1: 1～1.5; Described substituting group triphenylamine list aldehyde is that monoene replaces triphenylamine list aldehyde or vinylbenzene replaces triphenylamine list aldehyde; (4) substituting group triphenylamine monoene aldehyde (IX) is synthetic:
(a) substituting group is H: with Ph
3PCH
3I is dissolved among the exsiccant THF, and cryosel is bathed cooling, and nitrogen protection adds KOt-Bu then, stirs under the room temperature and obtains ylide reagent, wherein KOt-Bu and Ph half an hour
3PCH
3The I mol ratio is 1～1.1: 1; The triphenylamine list aldehyde that (1) step is made joins in this ylide reagent, stirs 24 hours under the room temperature, and crude product extracts with anhydrous diethyl ether, makes the triphenylamine monoene through column chromatography for separation, and wherein the mol ratio of triphenylamine list aldehyde and ylide reagent is 1: 2～3;
Add exsiccant N under the ice-water bath in the three-necked bottle of drying tube is housed, dinethylformamide (DMF) slowly drips phosphorus oxychloride (POCl
3), stirred 2 hours, obtain Vilsmeier reagent, wherein DMF and POCl
3Mol ratio be 10: 1; The above triphenylamine monoene that makes is joined in this Vilsmeier reagent, reacted under the room temperature 2～3 hours, product is poured in the frozen water, regulate pH value to neutral with aqueous sodium hydroxide solution, obtain precipitation, crude product makes triphenylamine monoene aldehyde through column chromatography for separation, and wherein the mol ratio of triphenylamine monoene and Vilsmeier reagent is 1: 5～6; Or
(b) substituting group is a monoene: triphenylamine diene and above-mentioned Vilsmeier reagent that (2) step is made at room temperature reacted 3 hours, product is poured in the frozen water, regulate pH value to neutral with aqueous sodium hydroxide solution, obtain precipitation, crude product makes monoene through column chromatography for separation and replaces triphenylamine monoene aldehyde, and the mol ratio of triphenylamine diene and Vilsmeier reagent is 1: 18～19; Or
(c) substituting group is a vinylbenzene: bathe under the cooling at cryosel, KOt-Bu is added Ph
3PCH
2In the exsiccant THF solution of PhBr, stir half an hour under the room temperature, obtain ylide reagent; The vinylbenzene replacement triphenylamine list aldehyde that (3) step is made is dissolved in THF, and join in this reagent, reaction is 24 hours under the room temperature, the mol ratio that vinylbenzene replaces triphenylamine list aldehyde and ylide reagent is 1: 2～3, crude product extracts with anhydrous diethyl ether, make vinylbenzene through column chromatography for separation and replace the triphenylamine monoene, replace triphenylamine monoene and exsiccant DMF and POCl by vinylbenzene
3At room temperature reacted 2 hours, product is poured in the frozen water, regulates pH value to neutral with aqueous sodium hydroxide solution, obtains precipitation, and crude product makes vinylbenzene through column chromatography for separation and replaces triphenylamine monoene aldehyde, and wherein vinylbenzene replaces triphenylamine monoene and POCl
3Mol ratio be 1: 5;
(5) (X) of triphenylamine diene aldehyde is synthetic:
(2) are gone on foot triphenylamine diene and exsiccant DMF and the POCl that makes
3At room temperature reacted 3 hours, product is poured in the frozen water, regulates pH value to neutral with aqueous sodium hydroxide solution, obtains precipitation, and crude product makes triphenylamine diene aldehyde, triphenylamine diene and POCl through column chromatography for separation
3Mol ratio be 1: 18～19;
(6) triphen amido organic dye (I, II, III, V) synthetic:
With substituting group triphenylamine list aldehyde (VIII)/substituting group triphenylamine monoene aldehyde (IX)/triphenylamine diene aldehyde (X), rhodanine-3-acetate and ammonium acetate add in the there-necked flask, glacial acetic acid is as reaction solvent, reflux conditions reacted 3-5 hour down, reaction finishes to be cooled to room temperature, pour in the frozen water, filtration, drying obtain solid matter, obtain triphen amido organic dye I/II/V through recrystallization or column chromatography purification, VIII/IX wherein, the mol ratio of rhodanine-3-acetate and ammonium acetate is 1: 1～1.1: 1～2; X, the mol ratio of rhodanine-3-acetate and ammonium acetate is 1: 2～2.1: 1～2;
Triphenylamine dialdehyde and rhodanine-3-acetate are added in the round-bottomed flask, dehydrated alcohol is as solvent, heating reflux reaction 24 hours, separate out red precipitate, suction filtration, solid matter is that eluent carries out column chromatography and obtains product III with the glacial acetic acid of ethyl acetate/ethanol of 3: 1 and 1%, and the mol ratio of triphenylamine dialdehyde and rhodanine-3-acetate is 1: 2～2.1.
3, the application of the described novel triphen amido organic dye of a kind of claim 1 in dye sensitization solar battery, this battery comprises light anode, photocathode, thermoplastic barrier film and electrolytic solution, it is characterized in that:
Described smooth anode is the dye sensitization titanium dioxide electrodes, and it comprises base material FTO conductive glass, the nano titanium dioxide film electrode, and the described novel triphen amido organic dye of claim 1 is as photosensitizer;
Described photocathode is a platinum electrode;
The prescription of described electrolytic solution is: in acetonitrile solvent, add 1 of 0.6M, and 2-dimethyl-3-propyl imidazole iodine, the lithium iodide of 0.1M and the iodine of 0.05M are made supporting electrolyte.
4,, it is characterized in that the following step of preparation method's process of described dye sensitization titanium dioxide photo anode according to the application of the described triphen amido of claim 3 organic dye in dye sensitization solar battery:
Method by silk screen printing is coated in titania slurry on the FTO conductive glass equably, through 450 ℃ of high temperature sintering 30min, naturally cools to room temperature, uses 50mMTiCl
4Solution-treated 30min, with distilled water, alcohol flushing surface, nitrogen dries up; Through 450 ℃ of high temperature sintering 30min, obtain the titanium dioxide porous membrane that thickness is 10～16 μ m again; The titanium dioxide film that obtains is soaked in the triphen amido organic dye solution subsequently, other adds the Chenodiol of 1mM as coadsorbent, and titanium dioxide film soaked in dye solution 24 hours, takes out the back and cleans with dehydrated alcohol, and nitrogen dries up.
5, according to the application of the described triphen amido of claim 4 organic dye in dye sensitization solar battery, it is characterized in that the mass percent of described titania slurry is formed: 16% titanium dioxide powder, 4% ethyl cellulose and 80% Terpineol 350.
6,, it is characterized in that the concentration of described triphen amido organic dye solution is 3 * 10 according to the application of the described triphen amido of claim 4 organic dye in dye sensitization solar battery
-4As solvent, III and IV are with methyl alcohol/DMF4: 1 mixed solvent is as solvent with methyl alcohol or 4: 1 mixed solvent of methyl alcohol/acetonitrile for M: I and II.
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