CN107446373B - Small molecule organic dyestuff for dye-sensitized solar cells - Google Patents
Small molecule organic dyestuff for dye-sensitized solar cells Download PDFInfo
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- CN107446373B CN107446373B CN201710665504.9A CN201710665504A CN107446373B CN 107446373 B CN107446373 B CN 107446373B CN 201710665504 A CN201710665504 A CN 201710665504A CN 107446373 B CN107446373 B CN 107446373B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
The invention discloses a kind of small molecule organic dyestuff for dye-sensitized solar cells, (substitution) phenyl is introduced triphenylamine units by double bond or three keys, a series of small molecule organic dyestuff of conjugation expanding types is obtained, and pass through the optics of solar battery of the systematic research based on these dyestuffs, electrochemical properties and photovoltaic parameter, it was found that compared to traditional metallized dye, the dyestuff that the present invention synthesizes shows good performance, such as better molar extinction coefficient, higher circuit photocurrent density and higher photoelectric conversion efficiency, and the dyestuff is readily synthesized, it is low in cost, show the application prospect of potential substitution noble metal photosensitizer.
Description
Technical field
The present invention relates to the synthesis of dye-sensitized solar cells sensitizer and application fields, and in particular to a kind of conjugation is opened up
The small molecule organic dyestuff of exhibition type.
Background technique
With the rapid development of society, the mankind further increase the demand of the energy.Traditional energy, such as petroleum, naturally
A large amount of uses of gas, coal, the problems such as not only polluted global environment, also result in global warming and greenhouse effects.
Therefore, the exploitation of various new energy is come into being, in the scheme of various new energy developments, solar energy is environmentally friendly, renewable with it,
Energy contains various advantages such as big and shows huge superiority.Since the Institute of Technology, Lausanne, SUI federation (EPFL)Since research team developed dye-sensitized nano grade titanium dioxide solar battery in 1991, in this neck
A large amount of research is carried out in domain.During research and discovery, it has been found that DSSC have compared with traditional solar cell with
Under some advantages:
1. the service life is long: service life is up to 15-20；
2. structure is simple, easily fabricated, simple production process is easy to large-scale industrial production；
3. preparing battery less energy intensive, the energy recovery period is short；
4. lower production costs, only the 1/5~1/10 of silicon solar cell, it is contemplated that the cost of the battery at every peak watt is 10
Within member；
5. nontoxic and pollution-free in production process.
As the important component of battery, photosensitizer dye can effectively absorb sunlight, and thus generate excitation
Electronics is then injected into the conduction band of the semiconductors such as titanium dioxide, therefore the photoelectric properties of dyestuff are to dye sensitization of solar electricity
The photoelectric conversion efficiency in pond has vital influence.Currently, the light of the dye-sensitized solar cells based on ruthenium complex
Photoelectric transformation efficiency limits its practical application up to 11%, but since its is at high price, pollutes the shortcomings that larger etc..
Summary of the invention
The purpose of the present invention is to provide a kind of small molecule organic dyestuff, and the dyestuff is compared to previous metal ligand compound
Object dyestuff has higher molar extinction coefficient and photoelectric conversion efficiency, can significantly increase the efficiency of solar battery.
Small molecule organic dyestuff of the present invention, shown in general formula of the chemical structure such as following formula (1):
Double bond or three keys are represented in formula, in [], Ar is such as flowering structure,
Wherein, R1Represent hydrogen atom, alkyl or alkoxy.
As a general technical idea, the present invention provides a kind of synthetic method for being used to prepare above-mentioned target compound,
Include the following steps:
Step 1: under nitrogen protection, compound A and compound B are occurred in the presence of potassium carbonate Suzuki or
Sonogashira reacts the step of prepare compound C,
Wherein, R2Represent double bond or three keys；
Step 2: under nitrogen protection, by compound C and cyanoacetic acid in catalyst CH3COONH4In the presence of occur
The step of Knoevenagel condensation reaction prepares target product,
Further, in step 1, the molar ratio of compound A and potassium carbonate is 1:8~8.1；Compound A's and compound B
Molar ratio is 5:12~12.5.
Further, in step 1, as the R of compound B2When for double bond, the reaction is in catalyst Pd (PPh3)4In the presence of
Suzuki reaction, compound A and Pd (PPh occurs3)4Molar ratio be 10:1~1.2, reaction temperature be 90~100 DEG C.
Further, in step 1, as the R of compound B2When for three keys, the reaction is in catalyst Pd (PPh3)2Cl2With
Sonogashira reaction, compound A and Pd (PPh occur in the presence of CuI3)2Cl2Molar ratio be 10~10.1:1, compound A
Molar ratio with CuI is 28~28.5:1, and reaction temperature is room temperature.
Further, in step 1, the reaction system is with Isosorbide-5-Nitrae-dioxane and H2The mixed liquor of O is as reaction dissolvent.
Further, in step 2, compound C and CH3COONH4Molar ratio 1:2.4~3, compound C and cyanoacetic acid
Molar ratio be 10:19~19.2, acetic acid is as solvent.
Compared with prior art, the invention has the following advantages that
Three kinds of dye molecules that the present invention synthesizes have long conjugation D- π-A structure, while containing cyano and carboxylic in molecule
Base, electron-withdrawing group is cyanoacetic acid, and can be combined in the form of chemical bond with semiconductor nano in the dyestuff containing carboxyl,
Facilitate the fixing of dye in the battery, while also helping the transmission of electronics, along with the increase of conjugate length becomes too
The ideal material of positive energy battery sensitizer.More importantly these compound synthesis routes are simple, reaction condition temperature
Simple and convenient and yield is higher with post-processing.Therefore such dyestuff has wide in field of dye-sensitized solar cells
Development and application prospect.
Detailed description of the invention
Fig. 1 is density of photocurrent-voltage curve of the organic dye sensitized solar battery based on compound FWD1~3.
Specific embodiment
The synthesis of dyestuff:
Unless otherwise indicated, all reactions carry out in a nitrogen atmosphere.
Embodiment 1
The preparation of compound FWD2
Compound FWD2 is obtained according to following route:
The synthesis of intermediate product 2
It is added into round-bottomed flask(1470mg, 2.80mmol), Pd (PPh3)4(325mg,
0.28mmol), K2CO3(3100mg, 22.4mmol) and styrene (821mg, 6.72mmol), Isosorbide-5-Nitrae-dioxane ((32mL) and
H2Mixture is stirred overnight by O (8mL) at 90 DEG C.After cooling, reaction mixture is extracted with dichloromethane.Organic phase is used
Anhydrous Na2SO4It is dry.After filtering, solvent is removed by rotary evaporation.Gained crude product is by means of using petroleum ether/methylene chloride
The mixture of (1:1, v/v) is purified as the flashchromatography on silica gel of eluant, eluent, obtains the 1 (yield of intermediate product of 1220mg
It 91.2%), is yellow solid.
The intermediate product 2 by means of1H NMR(300MHz,CDCl3) characterization, following spectrum: δ: 7.08 (s, 2H) is obtained,
7.09 (s, 2H), 7.12 (d, J=8.5Hz, 2H), 7.16 (d, J=8.5Hz, 4H), 7.28 (d, J=8.5Hz, 2H), 7.37
(t, J=7.5Hz, 4H), 7.48-7.52 (m, 8H), 7.72 (d, J=8.5Hz, 2H), 9.84 (s, 1H).
The synthesis of compound FWD2
Intermediate product 2 (860mg, 1.80mmol) is added into round-bottomed flask, ammonium acetate (333mg, 4.32mmol), cyanogen
Guanidine-acetic acid (291mg, 3.42mmol) and acetic acid (40mL), are heated to reflux 5 hours.After cooling, 200mL water is poured the mixture into
In.After filtering, residue recrystallize with dichloromethane obtains 411mg red solid FWD2 (yield 42.0%).
The compound FWD2 by means of1H NMR(300MHz,CDCl3) characterization, obtain following spectrum: δ: 7.01 (d, J
=8.7Hz, 2H), 7.18-7.31 (m, 10H), 7.38 (t, J=7.5Hz, 4H), 7.59-7.67 (m, 8H), 7.96 (d, J=
9.0Hz,2H),8.17(s,1H)13.62(br,1H).13C NMR(125MHz,DMSO)δ:98.57, 117.07,119.70,
123.85,126.04,126.54,127.63,128.06,128.39,128.78,132.93,134.18, 137.09,
144.53,151.22,153.26,164.18.HRMS(ESI-)m/z:calcd for(M-H)-C38H27N2O2 -: 543.2078,
found:543.2084.
Embodiment 2
The preparation of compound FWD3
Compound FWD3 is obtained according to following route:
Change the synthesis of intermediate product 3
It is added into round-bottomed flask(1470mg, 2.80mmol), Pd (PPh3)2Cl2(325mg,
0.28mmol), K2CO3(3100mg, 22.4mmol), CuI (53mg, 0.10mmol) and phenylacetylene (600mg,
6.16mmol), toluene (40mL) and diisopropylamine (5mL), and mixture is stirred at room temperature overnight.Then reaction is mixed
Object is closed to be extracted with dichloromethane.Organic phase anhydrous Na2SO4It is dry.After filtering, solvent is removed by rotary evaporation.Gained slightly produces
Object is obtained by means of using the mixture of petroleum ether/methylene chloride (1:1, v/v) to purify as the flashchromatography on silica gel of eluant, eluent
The intermediate product 3 (yield 84.8%) of 1250mg is obtained, is yellow solid.
The intermediate product 3 by means of1H NMR(300MHz,CDCl3) characterization, obtain following spectrum: δ: 7.11-7.15
(m, 6H), 7.34-7.36 (m, 6H), 7.48-7.54 (m, 8H), 7.74 (d, J=9.0Hz, 2H), 9.86 (s, 1H)
The synthesis of compound FWD3
Compound 3 (1040mg, 2.20mmol) is added into round-bottomed flask, ammonium acetate (407mg, 5.28mmol), cyano
Acetic acid (356mg, 4.18mmol) and acetic acid (48mL), are heated to reflux 5 hours.After cooling, pour the mixture into 200mL water.
After filtering, residue is in gained crude product by means of using the mixture conduct of methylene chloride/methanol (30:1 to 1:1, v/v)
The flashchromatography on silica gel of eluant, eluent purifies, and obtains 610mg red solid FWD3 (yield 51.3%).
The compound FWD3 by means of1H NMR(300MHz,CDCl3) characterization, obtain following spectrum: δ: 7.10-7.14
(m, 6H), 7.42-7.43 (m, 6H), 7.54-7.55 (m, 8H), 7.89 (d, J=8.5Hz, 2H), 7.98 (s, 1H)13C NMR
(125MHz,DMSO)δ:89.13,89.43,118.12,122.22,122.40,125.04,126.50,128.78, 131.33,
132.00,133.05,145.83,149.38,150.04,164.00.HRMS(ESI-)m/z:calcd for (M-H)-
C38H23N2O2 -:539.1765,found:539.1772.
Embodiment 3
The measurement of the photovoltaic performance of compound FWD1~3 (FW1 is compound of having registered, and structure is as follows)
Under standard AM1.5 simulated solar irradiation, in light intensity 100mW/cm2Simulated solar irradiation under, measure based on compound
Density of photocurrent-voltage curve of the organic dye sensitized solar battery of FWD1~3 is illustrated in fig. 1 shown below.
Its corresponding optoelectronic pole chemical property: short-circuit current density (Jsc), open-circuit voltage (Voc), fill factor (FF)
It is listed in Table 1 below with power conversion efficiency (η) data
Table 1
Compared by the analysis of above-mentioned data, it is known that: by introducing additional phenyl ring in donor set, especially with double
Key is a kind of effective way for obtaining high efficiency dye as bridge.
The optics of DSSC by systematic research based on the small molecule organic dyestuff, electrochemistry and Photovoltaic Properties,
We can be found that: a series of small molecule organic dyestuff of the invention are shown more preferable compared to traditional metallized dye
Molar extinction coefficient, circuit photocurrent density and photoelectric conversion efficiency, to greatly enhance the efficiency of solar battery.
In addition, especially with double bond as bridge, being the one kind for obtaining high efficiency dye by introducing additional phenyl ring in donor set
Effective way.These all show the bright prospects of manufacture high efficiency dye sensitization solar battery.
Claims (7)
1. small molecule organic dyestuff, which is characterized in that shown in its general formula of the chemical structure such as following formula (1):
In formula (1), double bond or three keys are represented in [], Ar is such as flowering structure,
Wherein, R1Represent hydrogen atom, alkyl or alkoxy.
2. a kind of synthetic method of small molecule organic dyestuff as described in claim 1, which comprises the steps of:
Step 1: under nitrogen protection, compound A and compound B are occurred in the presence of potassium carbonate Suzuki or
Sonogashira reacts the step of prepare compound C,
Wherein, R2Represent vinyl or acetenyl；
Step 2: under nitrogen protection, by compound C and cyanoacetic acid in catalyst CH3COONH4In the presence of occur
The step of Knoevenagel condensation reaction prepares target product,
3. the synthetic method of small molecule organic dyestuff as claimed in claim 2, which is characterized in that in step 1, compound A with
The molar ratio of potassium carbonate is 1:8~8.1；The molar ratio of compound A and compound B is 5:12~12.5.
4. the synthetic method of small molecule organic dyestuff as claimed in claim 2, which is characterized in that in step 1, as compound B
R2When for vinyl, the reaction is in catalyst Pd (PPh3)4In the presence of Suzuki reaction, compound A and Pd (PPh occurs3)4
Molar ratio be 10:1~1.2, reaction temperature be 90~100 DEG C.
5. the synthetic method of small molecule organic dyestuff as claimed in claim 2, which is characterized in that in step 1, as compound B
R2When for acetenyl, the reaction is in catalyst Pd (PPh3)2Cl2It is reacted with Sonogashira occurs in the presence of CuI, chemical combination
Object A and Pd (PPh3)2Cl2Molar ratio be 10~10.1:1, the molar ratio of compound A and CuI is 28~28.5:1, reaction temperature
Degree is room temperature.
6. the synthetic method of small molecule organic dyestuff as claimed in claim 2, which is characterized in that in step 1, reaction system with
1,4- dioxane and H2The mixed liquor of O is as reaction dissolvent.
7. the synthetic method of small molecule organic dyestuff as claimed in claim 2, which is characterized in that in step 2, compound C with
CH3COONH4Molar ratio 1:2.4~3, the molar ratio of compound C and cyanoacetic acid is 10:19~19.2, and acetic acid is as solvent.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627868A (en) * | 2012-03-13 | 2012-08-08 | 长沙矿冶研究院有限责任公司 | Organic aryne dye, its preparation method and use, dye-sensitized solar cell and preparation method of the dye-sensitized solar cell |
| CN105038294A (en) * | 2015-07-30 | 2015-11-11 | 江苏师范大学 | Indole-triphenylamine-arylmethylidenemalononitrile solar energy co-sensitization dye, synthetic method and application thereof |
| CN106366691A (en) * | 2016-08-05 | 2017-02-01 | 南京理工大学 | D-pi-A-structured organic dye embedded with diacetylenyl unit and synthetic method thereof |
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2017
- 2017-08-04 CN CN201710665504.9A patent/CN107446373B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627868A (en) * | 2012-03-13 | 2012-08-08 | 长沙矿冶研究院有限责任公司 | Organic aryne dye, its preparation method and use, dye-sensitized solar cell and preparation method of the dye-sensitized solar cell |
| CN105038294A (en) * | 2015-07-30 | 2015-11-11 | 江苏师范大学 | Indole-triphenylamine-arylmethylidenemalononitrile solar energy co-sensitization dye, synthetic method and application thereof |
| CN106366691A (en) * | 2016-08-05 | 2017-02-01 | 南京理工大学 | D-pi-A-structured organic dye embedded with diacetylenyl unit and synthetic method thereof |
Non-Patent Citations (3)
| Title |
|---|
| "Molecular Rotors as Fluorescent Viscosity Sensors: Molecular Design, Polarity Sensitivity, Dipole Moments Changes, Screening Solvents, and Deactivation Channel of the Excited States;Fuke Zhou等;《Eur. J. Org. Chem.》;20110715;第2011卷(第25期);4773–4787 |
| V-shaped organic dyes with triphenylamine core for dye-sensitized solar cells: Simple synthesis with enhanced open-circuit voltage;Tainan Duan等;《Synthetic Metals》;20151203;第211卷;19–24 |
| Y-shaped dyes based on triphenylamine for efficient dye-sensitized solar cells;Jia, Junhui等;《Tetrahedron 》;20120313;第68卷(第18期);3626-3632 |
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