CN105244167B - A kind of application of Carboxylation cyanobiphenyl derivative - Google Patents
A kind of application of Carboxylation cyanobiphenyl derivative Download PDFInfo
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- CN105244167B CN105244167B CN201510552661.XA CN201510552661A CN105244167B CN 105244167 B CN105244167 B CN 105244167B CN 201510552661 A CN201510552661 A CN 201510552661A CN 105244167 B CN105244167 B CN 105244167B
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- carboxylation
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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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The present invention relates to a kind of application of Carboxylation cyanobiphenyl derivative, the chemical structure of general formula of the Carboxylation cyanobiphenyl derivative is, n is 2 ~ 10, it is characterised in that：Application of the Carboxylation cyanobiphenyl derivative as coadsorbent in DSSC.The aggregation of dye molecule can so be reduced, improve the extinction efficiency of dyestuff, and the light-reflecting property of coadsorbent in itself, add double absorption of the dyestuff to sunshine, there are dye molecule and the coadsorbent extinction in the range of whole sunshine complementary again, these both contribute to the extinction efficiency for improving dyestuff, improve the electricity conversion of battery.
Description
Technical field
The present invention relates to a kind of Carboxylation cyanobiphenyl derivative, and in particular to a kind of Carboxylation cyanobiphenyl derivative
Using.
Background technology
Compared with traditional silicon based photovoltaic device, DSSC so that it is cheap, easily make, it is flexible and high
The features such as photoelectric transformation efficiency, more and more paid close attention to by people.Recently, even more there is up to 13% photoelectric transformation efficiency quilt
Report comes out（Nat. Chem. 2014, 6, 242）, this is provided for it in terms of commercial application may.
DSSC is main by the light anode of absorption dyestuff, electrolyte, constituted to several parts of electrode, wherein
A core be just deposited on titanium deoxid film in light anode.Typically, separation of charge and compound all occur two
The interface of titanium oxide, dyestuff and electrolyte.The titanium dioxide of high-ratio surface can provide big interface, be noted beneficial to enough electronics
Enter.But, big interface also increases the possibility of charge recombination, thus can finally reduce the photoelectric transformation efficiency of battery.
Many be suggested to the method that titanium dioxide surface is modified solves the above problems.One of which is exactly heavy in titanium dioxide surface
One layer of inorganic insulating layer material of product, prevents Carrier recombination（Chem. Mater., 2002, 14, 2930；J. Am. Chem.
Soc., 2003, 125, 475）.But the thickness of this layer of inorganic insulation layer is whard to control, if it exceeds certain thickness will subtract
Few electron injection rate, so as to influence battery efficiency.It therefore, it can receive concern as the organic molecule of coadsorbent（Chemistry
Journal, 2010,14,1357）.The introducing of coadsorbent can reduce the aggregation of dye molecule, while dye molecule and eutectoid content
Dosage form is into compacted zone, and the compacted zone restrained effectively the compound of electronics and hole, the absorptivity of dyestuff be improved, so as to carry
The electricity conversion of high battery（Energy Environ. Sci., 2012, 5, 6057）.Existing coadsorbent species
It is less, and the lifting of DSSC battery efficiency is not greatly improved.
The content of the invention
A kind of answering for Carboxylation cyanobiphenyl derivative is provided the invention aims to overcome the deficiencies in the prior art
With.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：A kind of application of Carboxylation cyanobiphenyl derivative,
The chemical structure of general formula of the Carboxylation cyanobiphenyl derivative is, n is 2 ~ 10,
It is characterized in that：Application of the Carboxylation cyanobiphenyl derivative as coadsorbent in DSSC.
Optimally, it comprises the following steps：
（a）The Carboxylation cyanobiphenyl derivative is added in the mixed solution containing dyestuff, in 20 ~ 30 DEG C of lucifuges
Stirring 12 ~ 24 hours；
（b）Titanium dioxide porous film Jing Guo calcination processing is immersed into step（a）In obtained solution, 10 ~ 24 are stood
Hour takes out, and is dried up after ethanol cleaning with nitrogen.
Further, step（a）In, the mixed solution is by acetonitrile and the tert-butyl alcohol according to volume ratio 1：1 is formulated.
Further, step（a）In, the concentration of the dyestuff is 0.4 ~ 0.5mmol/L, and the Carboxylation cyanobiphenyl spreads out
The biological mol ratio with the dyestuff is 0.1 ~ 2：1.
Further, the dyestuff is Z907 or N719.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：The Carboxylation cyanogen of the present invention
The application of base biphenyl derivatives, structure be forCarboxylation cyanobiphenyl derivative
The aggregation of dye molecule can be so reduced as application of the coadsorbent in DSSC, improved
The extinction efficiency of dyestuff, and the light-reflecting property of coadsorbent in itself, add double absorption of the dyestuff to sunshine, then have
Dye molecule and the coadsorbent extinction in the range of whole sunshine are complementary, and these both contribute to the extinction efficiency for improving dyestuff,
Improve the electricity conversion of battery.
Brief description of the drawings
Accompanying drawing 1 is the synthesis technique figure of Carboxylation cyanobiphenyl derivative of the invention；
Accompanying drawing 2 be methyl -9- [（4'- cyano group（1,1'- biphenyl）- 4- bases）Epoxide] pelargonate nuclear magnetic spectrum；
Accompanying drawing 3 is the ultraviolet-visible spectrum of the light anode of the Carboxylation cyanobiphenyl derivative of the addition different proportion present invention
Figure；
Accompanying drawing 4 is the diffusing reflection collection of illustrative plates of the light anode of the Carboxylation cyanobiphenyl derivative of the addition different proportion present invention；
Accompanying drawing 5 is the current -voltage curve of the light anode of the Carboxylation cyanobiphenyl derivative of the addition different proportion present invention；
Accompanying drawing 6 is the current -voltage curve of Carboxylation cyanobiphenyl derivative in embodiment 1, embodiment 4 and embodiment 5
Comparison diagram.
Embodiment
The application of the Carboxylation cyanobiphenyl derivative of the present invention, the chemical constitution of the Carboxylation cyanobiphenyl derivative is led to
Formula is, n is 2 ~ 10, and the Carboxylation cyanobiphenyl derivative is used as coadsorbent
Application in DSSC, it can reduce the aggregation of dye molecule, improve the extinction efficiency of dyestuff, and
And the light-reflecting property of coadsorbent in itself, double absorption of the dyestuff to sunshine is added, then have dye molecule and coadsorbent
Extinction is complementary in the range of whole sunshine, and these both contribute to the extinction efficiency for improving dyestuff, and the photoelectricity for improving battery turns
Change efficiency.
Comprise the following steps that：（a）The Carboxylation cyanobiphenyl derivative is added in the mixed solution containing dyestuff,
Stirred 12 ~ 24 hours in 20 ~ 30 DEG C of lucifuges；（b）Titanium dioxide porous film Jing Guo calcination processing is immersed into step（a）Obtain
Solution in, stand 10 ~ 24 hours take out, ethanol cleaning after dried up with nitrogen.Step（a）In, the mixed solution is excellent
Choosing is by acetonitrile and the tert-butyl alcohol according to volume ratio 1：1 is formulated.Step（a）In, the concentration of the dyestuff is preferably 0.4 ~
0.5mmol/L, the mol ratio of the Carboxylation cyanobiphenyl derivative and the dyestuff is preferably 0.1 ~ 2：1.The dyestuff is excellent
Elect Z907 or N719 as.
Carboxylation cyanobiphenyl derivative（）Synthesis：As shown in figure 1, will
2mmol 18 is preced with six ethers, 47mmol potassium carbonate, 25.7mmol 4'- cyano group -4- xenols, the corresponding alkyl bromides of 33.7mmol
Acid esters is added in 250 milliliters of flasks, then adds 80mml acetone thereto, is stirred, is flowed back 16 hours, instead under the conditions of 45 DEG C
It is after should terminating, said mixture is outstanding dry, and recrystallizing methanol is used, obtain powder；
It will be added in obtained powder in 100ml, 3mol/L sodium hydroxide solution, while tetrahydrofuran is added, until
Stable, homogeneous suspension is formed, said mixture is stirred at room temperature 4 days, is sentenced simultaneously with column chromatography in course of reaction
Disconnected reaction product and extent of reaction；After hydrolysis completely, neutralized under the conditions of 0 DEG C with 5mol/L hydrochloric acid, obtain white thick
Product, is then filtered with ether, milli-Q water, and with ethyl alcohol recrystallization 2 times, obtains clean product, is finally placed in vacuum dry
Drying for standby in dry case.
The present invention is further described below in conjunction with accompanying drawing embodiment.
Embodiment 1
A kind of methyl -3- of the present embodiment offer [（4'- cyano group（1,1'- biphenyl）- 4- bases）Epoxide] propionic acid and its application, its
Preparation method is：
A) by 2 mM 18 be preced with six ethers, 47 mMs of potassium carbonate, 25.7 mMs of 4'- cyano group -4- xenols,
33.7 mMs of methyl -3- bromo-propionic acid esters are added in 250 milliliters of flasks, then add 80 milliliters of acetone thereto, Celsius 45
Stir, flow back 16 hours under the conditions of degree.It is after reaction terminates, said mixture is outstanding dry, and use recrystallizing methanol, obtain methyl-
3- [（4'- cyano group（1,1'- biphenyl）- 4- bases）Epoxide] propionic ester powder.
B) in the sodium hydroxide solution that 100 milliliters 3 moles every liter is added in the powder obtained, while adding tetrahydrofuran
Solvent, until forming stable, homogeneous suspension.Said mixture is stirred at room temperature 4 days, post is used simultaneously in course of reaction
Chromatography judges reaction product and extent of reaction.After hydrolysis completely, neutralized under the conditions of 0 DEG C with 5 moles every liter of hydrochloric acid,
White crude is obtained, is then filtered with ether, milli-Q water, and with ethyl alcohol recrystallization 2 times, obtain pure methyl -3-
[（4'- cyano group（1,1'- biphenyl）- 4- bases）Epoxide] propionic acid, finally it is placed in drying for standby in vacuum drying chamber.1H NMR (400
MHz, d6-DMSO): 7.85 (s, 4H), 7.69 (m, 2H), 7.04 (s, 2H), 4.02 (s, 2H), 2.60
(s, 2H).
Using specially：
By the coadsorbent of synthesis（Methyl -3- [（4'- cyano group（1,1'- biphenyl）- 4- bases）Epoxide] propionic acid）Be added to containing
In 0.4 mM of every liter of dyestuff Z907 acetonitrile, tert-butyl alcohol mixed solution（Volume ratio 1:1）, mole of coadsorbent and dyestuff
Than for 1:1, room temperature（25℃）Under the conditions of lucifuge stirring 12h, it is stand-by；
By the titanium dioxide porous film after 500 DEG C of calcination processings, 90 DEG C are naturally cooled to, above-mentioned mixing is immersed in
In solution, 24 hours are stood, then takes out, after being cleaned with ethanol, is dried up with nitrogen, that is, obtain the painting modified through coadsorbent
The light anode of titanium dioxide porous film is covered with, ultraviolet-visible, diffusing reflection, current-voltage test are carried out to light anode, as a result
As shown in Fig. 3 to 5.
Embodiment 2
The present embodiment and application in embodiment 1 are basically identical, unlike, the mol ratio of adsorbent and dyestuff is 2:1.
Embodiment 3
The present embodiment and application in embodiment 1 are basically identical, unlike, the mol ratio of adsorbent and dyestuff is 1:2.
Embodiment 4
The present embodiment and application in embodiment 1 are basically identical, unlike, add reaction is methyl -6- bromocaproic acids
Methyl esters, obtained product be methyl -9- [（4'- cyano group（1,1'- biphenyl）- 4- bases）Epoxide] n-nonanoic acid.1H NMR (400 MHz,
d6-DMSO): 7.85 (s, 4H), 7.69 (m, 2H), 7.04 (s, 2H), 4.00 (s, 2H), 2.51 (s,
2H), 2.22(s, 2H), 1.72 (m, 2H), 1.56 (m, 2H), 1.43 (m, 2H).
Embodiment 5
The present embodiment and application in embodiment 1 are basically identical, unlike, add reaction is methyl -9- bromine n-nonanoic acids
Methyl esters, obtained product be methyl -9- [（4'- cyano group（1,1'- biphenyl）- 4- bases）Epoxide] n-nonanoic acid.1H NMR (400 MHz,
d6-DMSO): 7.85 (s, 4H), 7.69 (m, 2H), 7.04 (s, 2H), 4.00 (s, 2H), 2.51 (s,
2H), 2.22(s, 2H), 1.72 (m, 2H), 1.56 (m, 2H), 1.42 (m, 4H), 0.9-1.2 (m, 4).Figure
6 illustrate the i-v curve of the light anode made based on coadsorbent in embodiment 1, embodiment 4 and embodiment 5.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention, all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (3)
1. a kind of application of Carboxylation cyanobiphenyl derivative, the chemical structure of general formula of the Carboxylation cyanobiphenyl derivative is, n is 2 ~ 10, it is characterised in that：The Carboxylation cyanobiphenyl derivative is as altogether
Application of the adsorbent in DSSC, it comprises the following steps：
（a）The Carboxylation cyanobiphenyl derivative is added in the mixed solution containing dyestuff, in 20 ~ 30 DEG C of lucifuge stirrings
12 ~ 24 hours；The mol ratio of the Carboxylation cyanobiphenyl derivative and the dyestuff is 0.5 ~ 2：1, the dyestuff is Z907
Or N719；
（b）Titanium dioxide porous film Jing Guo calcination processing is immersed into step（a）In obtained solution, 10 ~ 24 hours are stood
Take out, dried up after ethanol cleaning with nitrogen.
2. the application of Carboxylation cyanobiphenyl derivative according to claim 1, it is characterised in that：Step（a）In, it is described
Mixed solution is formed by mixed solvent and dyestuff configuration, and the mixed solvent is by acetonitrile and the tert-butyl alcohol according to volume ratio 1：1 prepares
Form.
3. the application of Carboxylation cyanobiphenyl derivative according to claim 2, it is characterised in that：Step（a）In, it is described
The concentration of dyestuff is 0.4 ~ 0.5mmol/L.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558066A (en) * | 2011-12-23 | 2012-07-11 | 苏州大学 | Cyanobiphenyl-functionalized benzimidazole compound, and preparation and application thereof |
| CN103413682A (en) * | 2013-07-26 | 2013-11-27 | 苏州大学 | Quasi-solid electrolyte for solar cell based on double-imidazole type ionic crystal |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4119267B2 (en) * | 2003-01-23 | 2008-07-16 | 株式会社東芝 | Photosensitized solar cell |
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- 2015-09-02 CN CN201510552661.XA patent/CN105244167B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558066A (en) * | 2011-12-23 | 2012-07-11 | 苏州大学 | Cyanobiphenyl-functionalized benzimidazole compound, and preparation and application thereof |
| CN103413682A (en) * | 2013-07-26 | 2013-11-27 | 苏州大学 | Quasi-solid electrolyte for solar cell based on double-imidazole type ionic crystal |
Non-Patent Citations (1)
| Title |
|---|
| Benzimidazolyl functionalized ionic liquids as an additive for high performance dye-sensitized solar cells;Jie Zhao et al.;《Chemical Communications》;20110923;第47卷;全文 * |
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