CN103073923A - Purification method for ruthenium complex photosensitive dye raw product and ruthenium complex photosensitive dye product - Google Patents
Purification method for ruthenium complex photosensitive dye raw product and ruthenium complex photosensitive dye product Download PDFInfo
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- CN103073923A CN103073923A CN201210580708XA CN201210580708A CN103073923A CN 103073923 A CN103073923 A CN 103073923A CN 201210580708X A CN201210580708X A CN 201210580708XA CN 201210580708 A CN201210580708 A CN 201210580708A CN 103073923 A CN103073923 A CN 103073923A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The invention discloses a purification method for a ruthenium complex photosensitive dye raw product and a ruthenium complex photosensitive dye product obtained by using the method. The purification method comprises the following steps: step (A) the reaction of the ruthenium complex photosensitive dye raw product and alkali is carried out in an organic solvent to generate salt to be filtered, and the organic solvent is removed by evaporation and is diluted with water; step (B) acidification processing is carried out; step (C) freezing crystallization is carried out; and step (D) thawing, filtrating and drying are carried out, wherein the acidification processing in the step (B) is realized by using diluted acid to adjust the pH value of the solution to be 4.0-5.3. According to the purification method provided by the invention, as the pH value of the ruthenium complex photosensitive dye solution is adjusted to be 4.0-5.3 through acidification, the ratio of the alkali and the ruthenium complex are optimized, so that a high-quality ruthenium complex photosensitive dye product is obtained by separation, which can be used in dye-sensitized solar cell to obtain higher photoelectric conversion efficiency.
Description
Technical field
The present invention relates to the purification process of the thick product of a kind of ruthenium complex light-sensitive coloring agent and the ruthenium complex light-sensitive coloring agent product that obtains.
Background technology
In view of the day by day exhaustion of conventional energy resources, multiple substituting renewable energy source is explored.In recent years, by
Proposed a kind of dye sensitization solar battery (Dye-Sensitized Solar Cell, DSSC) with O'Regan, can more effectively utilize sun power and receive much concern.Wherein, sensitizing dye, a kind of material that can effectively absorb near the light the visible light such as ruthenium (Ru) complex compound etc., has become at present one of considerable exploitation direction in the DSSC association area.
Ruthenium (Ru) complex compound light-sensitive coloring agent, its common trait is, all contains 2,2 '-dipyridyl-4,4 '-dicarboxylic acid (2,2 '-bipyridyl-4,4 '-dicarboxylic acid), be also referred to as 4,4 '-dicarboxyl-2, and 2 '-dipyridyl (4,4 '-dicarboxylate-2,2 '-bipyridyl, dcbpy) part.Be commonly referred to as respectively N3, suitable-two (isothiocyano)-two (2 of N719,2 '-dipyridyl-4,4 '-dicarboxylic acid) closes ruthenium (II) complex compound (cis-di (thiocyanato)-bis (2,2 '-bipyridyl-4,4 '-dicarboxylate) ruthenium (II)), suitable-two (isothiocyano)-two (2,2 '-dipyridyl-4,4 '-dicarboxylic acid) closes ruthenium (II) two-TBuA complex compound (cis-di (thiocyanato)-bis (2,2 '-bipyridyl-4,4 '-dicarboxylate) ruthenium (II) bis-tetrabuty lammonium) be exactly wherein two.Zhan Wenhai etc. have optimized their synthesis technique in patent documentation CN101851255A, make its cost decrease.But because of lower stability, weather resistance and the electricity conversion of all these rutheniums (Ru) complex compound light-sensitive coloring agent, their widespread uses in DSSC have been limited.
Afterwards, the researchist had synthesized the new ruthenium complexes light-sensitive coloring agent that contains a dcbpy part and a novel second bipyridine derivative ligand in a series of molecules.Common feature of these novel light-sensitive coloring agents is, has excellent extinction ability, has higher specific absorbance (Absorption coefficient), thereby can more effectively sunlight be absorbed and change into electric current output.
(the document Chia-Yuan Chen et al. such as Chia-Yuan Chen, Angew.Chem.Int.Ed., 2006,45 (35), 5822-5825) a kind of contain a dcbpy part and one 4 have been synthesized, 4 '-two (5-(5-octyl group thiophene-2-yl) thiophene-2-yl)-2,2 '-dipyridyl (4,4 '-bis (5-(5-octylthiophen-2-yl) thiophen-2-yl)-2,2 '-bipiridine), abtpy) new ruthenium complexes light-sensitive coloring agent, i.e. suitable-two (isothiocyano)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid)-(4,4 '-two (5-(5-octyl group thiophene-2-yl) thiophene-2-yl)-2,2 '-dipyridyl) closes ruthenium (II) complex compound (cis-di (thiocyanato)-(2,2 '-bipyridyl-4,4 '-dicarboxylate) (4,4 '-bis (5-(5-octyl-thiophen-2-yl) thiophen-2-yl)-2,2 '-bipiridine) ruthenium (II)), its structural formula is suc as formula shown in (1).
Owing to have higher current density (Photocurrent density) and an electricity conversion, this code name is that the light-sensitive coloring agent of Z991 or CYC-B1 is gathered around in DSSC and had a wide range of applications.
Recently, the researchist has synthesized again CYC-B11(document Michael
Et al., Nano., 2009,10,3103-3109.), CYC-B7(document Jheng-Ying Li et al., J.Mater.Chem., 2010,20,7158-7164.) and CYC-B5, CYC-B6S, pre-CYC-B12(patent documentation CN101585972A) etc. series of new ruthenium complex light-sensitive coloring agent.
But these synthetic light-sensitive coloring agent purity are all lower, only have by after purifying, and could satisfy the demand of preparation DSSC.Wherein, the acidification process directly has influence on the quality of light-sensitive coloring agent and the performance of final DSSC.The document that comprises above-mentioned document all fails to propose preferably solution with regard to this key factor of acidification process of dyestuff, thereby has limited the space that the DSSC performance further promotes.
Although patent documentation US2010/0275391A1 provides a kind of and has purified suc as formula the method for the light-sensitive coloring agents such as Z907 shown in (2) with Prep.HPLC.Also related to simultaneously the method with acidification behind the alkali dissolution.But the ratio of alkali and Z907 is not optimized.
Therefore, further optimize acidization, regulate the ratio of alkali and dyestuff in the finished product, thereby further improve the photoelectric transformation efficiency of DSSC, become one of problem that instantly needs to be resolved hurrily.
Summary of the invention
The present invention is in order to solve above-mentioned problem, and purpose is to provide a kind of purification process of can optimization regulating alkali and ruthenium complex light-sensitive coloring agent ratio in the ruthenium complex light-sensitive coloring agent the finished product.
The purification process of the thick product of ruthenium complex light-sensitive coloring agent of the present invention comprises the steps:
Steps A) the thick product of ruthenium complex light-sensitive coloring agent and alkali react salify in organic solvent, filter, and steam except organic solvent, and thin up obtains ruthenium complex light-sensitive coloring agent solution;
Step B) the ruthenium complex light-sensitive coloring agent solution that acidification steps A) obtains produces in a large number precipitation;
Step C) with step B) the ruthenium complex light-sensitive coloring agent precipitation solution that obtains carries out freezingly, makes its sufficient crystallising; And
Step D) thaws, filter, dry to get ruthenium complex light-sensitive coloring agent product;
Wherein: the acidification step B) is with diluted acid pH to be transferred to 4.0 ~ 5.3.
Steps A) can make the thick product of ruthenium complex be transformed into the salts solution of solubility, remove insoluble impurities, be convenient to follow-up acidification.
According to above-mentioned steps B) the acidification ruthenium complex light-sensitive coloring agent product that can guarantee to obtain in alkali and the mol ratio of ruthenium complex be 1:1 ~ 1.5:1, with the ruthenium complex light-sensitive coloring agent product of acquisition higher quality, thus the photoelectric transformation efficiency of raising DSSC.
Preferably, steps A) the mol ratio consumption of described ruthenium complex light-sensitive coloring agent and alkali is 1:1 ~ 2.
More preferably, step B) acidification is with diluted acid pH to be transferred to 4.8 ~ 5.2, and preferred pH value transfers to 5.0.
Step B) the used diluted acid of acidification can for any organic acid or mineral acid, be rare nitric acid, dilute hydrochloric acid or dilute phosphoric acid; The concentration of used diluted acid is counted 0.1 ~ 1M with monoprotic acid.
Step B) acidification is at 0 ~ 40 ℃, carries out under preferred 10 ~ 30 ℃, and the acidification time is 2 ~ 4 hours.By such formation, can guarantee that acidifying carries out fully.
Steps A) alkali described in is to be arbitrarily organic bases or mineral alkali; Described organic bases can be the alkali shown in the formula (3);
Formula (3)
Wherein, R
1, R
2, R
3With R
4Independent respectively is H or C
nH
2n+1, n=1 ~ 20 wherein;
Described mineral alkali can be arbitrarily mineral alkali, preferred sodium hydroxide and/or potassium hydroxide cheap and easy to get.
Described organic solvent is acetonitrile; The amount ratio of ruthenium complex light-sensitive coloring agent and described organic solvent is 1g:10 ~ 50mL.
Step C) freezing and crystallizing described in can descend preferred-20 ~-10 ℃ of lower freezing and crystallizings 3 ~ 72 hours, preferred 3 ~ 24 hours at-30 ~-5 ℃.By such formation, can guarantee the high-quality complete precipitated crystal of ruthenium complex light-sensitive coloring agent product, and make follow-up filtration procedure become more simple to operation.
Step D) bake out temperature in can be 40 ~ 70 ℃, preferred 40 ~ 45 ℃.By such formation, can avoid the reduction of ruthenium complex light-sensitive coloring agent product quality in drying course.
The purification process of the thick product of ruthenium complex light-sensitive coloring agent of the present invention is applicable to all and contains carboxyl (the thick product of ruthenium complex light-sensitive coloring agent of acidic-group such as COOH) in molecular structure.
Preferably, the purification process of the thick product of ruthenium complex light-sensitive coloring agent of the present invention is used for purifying according to document (Chia-Yuan Chen et al., Angew.Chem.Int.Ed., 2006,45 (35), the thick product of ruthenium complex light-sensitive coloring agent that the one kettle way in 5822-5825) is synthetic.
Another object of the present invention is to provide a kind of ruthenium complex light-sensitive coloring agent product that utilizes the purification process acquisition of the thick product of ruthenium complex light-sensitive coloring agent of the present invention.
Preferably, utilize in the ruthenium complex light-sensitive coloring agent product that purification process of the present invention obtains, the mol ratio of alkali and ruthenium complex is 1:1 ~ 1.5:1, preferred 1.2:1.
Positive progressive effect of the present invention is: purification process of the present invention is owing to the pH value to 4.0 of adjusting ruthenium complex light-sensitive coloring agent solution through acidifying ~ 5.3, optimized the ratio of alkali and ruthenium complex, obtained high-quality ruthenium complex light-sensitive coloring agent product thereby separate, be used for dye sensitization solar battery, can obtain higher photoelectric transformation efficiency.
Description of drawings
Fig. 1 is the graph of a relation of different pH values and battery efficiency in the thick product acidifying of the Z991 treating processes among the embodiment 1 ~ 10;
Fig. 2 is HPLC spectrogram and the data of the Z991 product that obtains of embodiment 1 ~ 10;
Fig. 3 is the Z991 product that embodiment 1 ~ 10 obtains
1The HNMR spectrogram; And
Fig. 4 is the MS spectrogram of the Z991 product that obtains of embodiment 1 ~ 10.
Embodiment
In an embodiment of the present invention, the ruthenium complex light-sensitive coloring agent that adopts is suitable-two (isothiocyano)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid)-(4,4 '-two (5-(5-octyl group thiophene-2-yl) thiophene-2-yl)-2,2 '-dipyridyl) closes ruthenium (II) complex compound (cis-di (thiocyanato)-(2,2 '-bipyridyl-4,4 '-dicarboxylate) (4,4 '-bis (5-(5-octyl-thiophen-2-yl) thiophen-2-yl)-2,2 '-bipirid ine) ruthenium (II)), its code name is CYC-B1 or Z991, also can be expressed as Ru (dcbpy) (abtpy) (NCS)
2, its structural formula is suc as formula shown in (1).
These suitable-two (isothiocyano)-(2,2 '-dipyridyl-4,4 '-dicarboxylic acid)-(4,4 '-two (5-(5-octyl group thiophene-2-yl) thiophene-2-yl)-2,2 '-dipyridyl) closes the thick product of ruthenium (II) complex compound light-sensitive coloring agent (Z991) according to document (Chia-Yuan Chen et al., Angew.Chem.Int.Ed., 2006,45 (35), the one kettle way in 5822-5825) is synthetic.
4-n-butyl ammonium hydroxide (Tetrabutyl ammonium hydroxide with the thick product of 200mg Z991 and 0.5mL10%, being designated hereinafter simply as " TBAOH ") aqueous solution joins in the 5mL acetonitrile organic solvent, is heated to the dissolving in 30 minutes of 40 ~ 45 ℃ of stirring reactions.Filter, steam except organic solvent, add the 30mL deionized water and dilute.
Then use the at room temperature acidifying of rare nitric acid of 0.1M.Transfer to 4.0 through 3 hours pH values with the Z991 aqueous solution, have a large amount of solid precipitations to produce.
Product solution after the acidifying is put into-10 ~-20 ℃ refrigerator and cooled freeze and spend the night, make its abundant precipitated crystal.
After thawing, filter, put into 40 ℃ of oven for drying, can obtain 99.6mg Z991 product.
Method according to embodiment 1 is processed the thick product of Z991.Difference is, the pH value of the Z991 aqueous solution is transferred to 4.5.Obtain at last 98.7mg Z991 product.
Method according to embodiment 1 is processed the thick product of Z991.Difference is, the pH value of the Z991 aqueous solution is transferred to 4.6.Obtain at last 97.4mg Z991 product.
Method according to embodiment 1 is processed the thick product of Z991.Difference is, the pH value of the Z991 aqueous solution is transferred to 4.7.Obtain at last 96.2mg Z991 product.
Method according to embodiment 1 is processed the thick product of Z991.Difference is, the pH value of the Z991 aqueous solution is transferred to 4.8.Obtain at last 94.8mg Z991 product.
Method according to embodiment 1 is processed the thick product of Z991.Difference is, the pH value of the Z991 aqueous solution is transferred to 4.9.Obtain at last 93.6mg Z991 product.
Method according to embodiment 1 is processed the thick product of Z991.Difference is, the pH value of the Z991 aqueous solution is transferred to 5.0.Obtain at last 91.5mg Z991 product.
Method according to embodiment 1 is processed the thick product of Z991.Difference is, the pH value of the Z991 aqueous solution is transferred to 5.1.Obtain at last 90.9mg Z991 product.
Method according to embodiment 1 is processed the thick product of Z991.Difference is, the pH value of the Z991 aqueous solution is transferred to 5.2.Obtain at last 89.3mg Z991 product.
Method according to embodiment 1 is processed the thick product of Z991.Difference is, the pH value of the Z991 aqueous solution is transferred to 5.3.Obtain at last 87.5mg Z991 product.
Effect embodiment
The Z991 product that respectively embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6, embodiment 7, embodiment 8, embodiment 9 and embodiment 10 is obtained is dissolved in acetonitrile: in the mixed solvent of the trimethyl carbinol=1:1, be made into the Z991 light-sensitive coloring agent solution of 0.4M.
Be particle diameter the commercially available TiO of 20nm
2Slurry is coated on the stannic oxide that the FTO(fluorine mixes with method for printing screen) conductive glass surface, be placed in the retort furnace 500 ℃ of lower sintering 2 hours, obtain the TiO of 18-20 μ m
2Film.TiO
2Electrode soaks in Z991 light-sensitive coloring agent solution respectively after 48 hours, with dry behind the solvent washing.
Stannic oxide in the doping of FTO(fluorine) surface drilling (diameter is 0.5mm) of conductive glass.Then H
2PtCl
6(2mg platinum/1mL methanol solution) is sprayed on the surface of FTO conductive glass, 410 ℃ of lower sintering 0.5 hour, obtains electrode.
Inserting thickness is the hot melt adhesive polymer layer of 60 μ m between two electrodes, and lower bonding firm at 120 ℃ to 140 ℃ whole device.
0.06M I
2, 0.3M LiI, 0.5M tert .-butylpyridine, be dissolved in and make electrolytic solution in the acetonitrile, by the aperture on the electrode is injected between two electrodes.After confirming that the space has all been filled up, aperture is sealed with hot melt adhesive.
The photoelectric transformation efficiency of dye sensitization solar battery (η) is tested under the standard light source of AM1.5.The result is as shown in table 1.
Table 1
As shown in Table 1, when when acidifying the pH value being transferred to 4.0 ~ 4.7, it is 7.7 ~ 7.9% that resulting light-sensitive coloring agent is applied to the battery efficiency that DSSC obtains; When the pH value transferred to 4.8 ~ 5.2, battery efficiency was 8.1 ~ 8.3%; When the pH value transferred to 5.3, battery efficiency had been reduced to 7.7% on the contrary.
By above data, can obtain such conclusion in conjunction with Fig. 1, the pH value of light-sensitive coloring agent in acidization transfers at 4.8 ~ 5.2 o'clock, and the light-sensitive coloring agent quality that obtains is higher, is applied on the DSSC, can reach higher battery efficiency.Wherein, acidization pH transfers at 5.0 o'clock, and the quality of the light-sensitive coloring agent that obtains is the highest, is applied on the DSSC, has reached the highest battery efficiency 8.3%.
In conjunction with Fig. 2, Fig. 3, Fig. 4 as can be known, pH transfers to 5.0 when acidifying, and the purity of the light-sensitive coloring agent product that obtains is higher, and the TBA in the light-sensitive coloring agent products molecule structure and the mol ratio of ruthenium complex are 1.2:1.
This has proved absolutely that in the acidification process pH value of the light-sensitive coloring agent aqueous solution transfers to 4.8 ~ 5.2, when guaranteeing in the light-sensitive coloring agent products molecule structure that the mol ratio of TBA and ruthenium complex is 1:1 ~ 1.5:1, is applied among the DSSC, can obtain higher battery efficiency.Be preferably, the pH value of the light-sensitive coloring agent aqueous solution transfers to 5.0, and the TBA in the light-sensitive coloring agent products molecule structure and the mol ratio of ruthenium complex are 1.2:1 simultaneously, and battery efficiency is the highest.
Claims (10)
1. the purification process of the thick product of ruthenium complex light-sensitive coloring agent, it comprises the steps:
Steps A) the thick product of ruthenium complex light-sensitive coloring agent and alkali react salify in organic solvent, filter, and steam except organic solvent, and thin up obtains ruthenium complex light-sensitive coloring agent solution;
Step B) the ruthenium complex light-sensitive coloring agent solution that acidification steps A) obtains produces in a large number precipitation;
Step C) with step B) the ruthenium complex light-sensitive coloring agent precipitation solution that obtains carries out freezingly, makes its sufficient crystallising; And
Step D) thaws, filter, dry to get ruthenium complex light-sensitive coloring agent product;
It is characterized in that: the acidification step B) is with diluted acid pH to be transferred to 4.0 ~ 5.3.
2. method according to claim 1, it is characterized in that: acidification step B) is with diluted acid pH to be transferred to 4.8 ~ 5.2; Steps A) mol ratio of described ruthenium complex light-sensitive coloring agent and alkali is 1:1 ~ 2.
3. method according to claim 2, it is characterized in that: acidification step B) is with diluted acid pH to be transferred to 5.0.
4. method according to claim 1, it is characterized in that: the used diluted acid of acidification step B) is rare nitric acid, dilute hydrochloric acid or dilute phosphoric acid; The concentration of used diluted acid is counted 0.1 ~ 1M with monoprotic acid; Acidification is carried out under 0 ~ 40 ℃, and the acidification time is 2 ~ 4 hours.
5. method according to claim 4, it is characterized in that: acidification step B) is carried out under 10 ~ 30 ℃.
6. method according to claim 1, it is characterized in that: the alkali steps A) is organic bases or mineral alkali; Described organic bases is the alkali shown in the formula (3);
Wherein, R
1, R
2, R
3With R
4Independent respectively is H or C
nH
2n+1, n=1 ~ 20 wherein;
Described mineral alkali is sodium hydroxide and/or potassium hydroxide;
Described organic solvent is acetonitrile; The amount ratio of ruthenium complex light-sensitive coloring agent and described organic solvent is 1g:10 ~ 50mL;
Step C) freezing and crystallizing described in is-20～-10 ℃ of freezing and crystallizings 3 ~ 72 hours;
Step D) bake out temperature in is 40 ~ 70 ℃.
7. method according to claim 1, it is characterized in that: described ruthenium complex is the ruthenium complex that contains carboxylic group.
8. the ruthenium complex light-sensitive coloring agent product that obtains of described method according to claim 1 ~ 7.
9. ruthenium complex light-sensitive coloring agent product according to claim 8, it is characterized in that: the mol ratio of alkali and ruthenium complex is 1:1 ~ 1.5:1 in the described product.
10. ruthenium complex light-sensitive coloring agent product according to claim 9, it is characterized in that: the mol ratio of alkali and ruthenium complex is 1.2:1 in the described product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554996A (en) * | 2013-10-11 | 2014-02-05 | 华中科技大学 | Positive ion-containing ruthenium complex dye and dye-sensitized solar cell prepared by same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103554996A (en) * | 2013-10-11 | 2014-02-05 | 华中科技大学 | Positive ion-containing ruthenium complex dye and dye-sensitized solar cell prepared by same |
| CN103554996B (en) * | 2013-10-11 | 2016-03-02 | 华中科技大学 | The ruthenium complex dye of cation and the dye sensitization solar battery of preparation thereof |
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Application publication date: 20130501 |