CN107417680A - A kind of dye sensitizing agent and preparation method and application - Google Patents
A kind of dye sensitizing agent and preparation method and application Download PDFInfo
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- CN107417680A CN107417680A CN201710823920.7A CN201710823920A CN107417680A CN 107417680 A CN107417680 A CN 107417680A CN 201710823920 A CN201710823920 A CN 201710823920A CN 107417680 A CN107417680 A CN 107417680A
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- 230000001235 sensitizing effect Effects 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 52
- 150000001875 compounds Chemical class 0.000 claims description 43
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims description 18
- 238000006482 condensation reaction Methods 0.000 claims description 12
- JGRMXPSUZIYDRR-UHFFFAOYSA-N 2-(4-oxo-2-sulfanylidene-1,3-thiazolidin-3-yl)acetic acid Chemical compound OC(=O)CN1C(=O)CSC1=S JGRMXPSUZIYDRR-UHFFFAOYSA-N 0.000 claims description 10
- 239000003495 polar organic solvent Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 150000003053 piperidines Chemical group 0.000 claims description 7
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000005695 Ammonium acetate Substances 0.000 claims description 6
- 229940043376 ammonium acetate Drugs 0.000 claims description 6
- 235000019257 ammonium acetate Nutrition 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229920006397 acrylic thermoplastic Polymers 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 40
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 abstract description 5
- 230000005611 electricity Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 46
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 16
- 239000003480 eluent Substances 0.000 description 16
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 16
- 238000010898 silica gel chromatography Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000012074 organic phase Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 238000006170 formylation reaction Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 229910019213 POCl3 Inorganic materials 0.000 description 8
- 230000005693 optoelectronics Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000002114 high-resolution electrospray ionisation mass spectrometry Methods 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- -1 carbazole radical Chemical class 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241001464837 Viridiplantae Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B21/00—Thiazine dyes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2022—Light-sensitive devices characterized by he counter electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention provides a kind of dye sensitizing agent, has the structure shown in formula I, includes two kinds of D A structures in the structure, the D A structures respectively using phenthazine as the D A structures of electron donor and using carbazole as electron donor, constitute new (D A)2Type dye sensitizer, new working substance is provided for the screening of dye sensitizing agent.Dye sensitizing agent provided by the present invention has excellent photoelectric conversion performance, and electricity conversion is up to 4.79%.Present invention also offers the preparation method of above-mentioned dye sensitizing agent, preparation method provided by the present invention is simple, easily operated, is adapted to industrialized production.
Description
Technical field
The present invention relates to DSSC technical field, more particularly to a kind of dye sensitizing agent and its preparation side
Method and application.
Background technology
Solar battery technology can convert the solar into electric energy, it is considered to be the maximally effective side using solar energy
Formula.Solar cell is broadly divided into three kinds：Crystal silicon solar energy battery, multicomponent compound film solar cell and dye sensitization
Solar cell.DSSC (dye-sensitized solar cells, DSSCs) is due to raw material
It is abundant, cost is low, technique is simple, color tunable, the advantages such as flexibility can be made and by more and more extensive concern.
The operation principle of DSSC is by the big pi-conjugated knot with intramolecular charge transport (ICT)
Structure organic dyestuff is bonded on semiconductor surface, and by means of strong absorption of the dyestuff to visible ray, semiconductor spectral response is widened
To visible region even infrared region, photoelectric current is produced, luminous energy is converted into electric energy by natural imitation circle green plants photosynthesis.Make
For the core of solar cell, dye sensitizing agent, which plays, absorbs sunshine, generation and the important function for transmitting electronics, directly
Connecing influences DSSCs performance.Dye sensitizing agent is divided into metal complex sensitizer and pure organic dye sensitizer, pure organic dye
Sensitizer is due to cost is low, environmental pollution is small, structure is easy to adjust, be readily synthesized and high molar extinction coefficient etc. is excellent
Gesture, receive extensive concern.
The species of pure organic dye sensitizer mainly have D- π-A, D-D- π-A, D- π-A-A, D-A- π-A, A- π-D- π-A,
(D-A)2、(D-π-A)2, wherein, (D-A)2Type dye sensitizer is same due to two single D-A type dye sensitizing agents being attached to
In individual molecule, expand absorption spectrum response range and significantly improve molar absorption coefficient, add the light capture rate of dyestuff,
Be advantageous to improve the photoelectric transformation efficiency of DSSC.But (D-A)2The slower development of type dye sensitizer,
The problem of photoelectric transformation efficiency is low be present, as prior art " novel carbazole radical dye sensitization solar cell performance study " is prepared for
1,6- double-[3- (2- alpha-cyanoacrylates)-carbazole]-hexane 4, its electricity conversion is only 1.12%.
The content of the invention
It is provided by the invention new it is an object of the invention to provide a kind of dye sensitizing agent and preparation method and application
Dye sensitizing agent has excellent photoelectric conversion performance.
The invention provides a kind of dye sensitizing agent, has the structure shown in formula I：
The R is 2- cyano group -2- acrylics or 2- (rhodanine -3- acetic acid) vinyl；
The n is 4 or 8.
Present invention also offers the preparation method of above-mentioned dye sensitizing agent, comprise the following steps：
Cyanoacetic acid or rhodanine -3- acetic acid are mixed with the compound shown in formula II, alkaline condensing agent, polar organic solvent
After conjunction, condensation reaction is carried out, obtains dye sensitizing agent；
The n is 4 or 8.
Preferably, the alkaline condensing agent is piperidines and/or ammonium acetate.
Preferably, the mol ratio of the alkaline condensing agent and the compound shown in formula II is 2~4:1.
Preferably, the mol ratio of cyanoacetic acid or rhodanine-the 3- acetic acid and the compound shown in formula II is 3~5:1.
Preferably, the polar organic solvent is the one or more in acetonitrile, chloroform and acetic acid.
Preferably, the amount of the material of the compound shown in the formula II and the volume ratio of the polar organic solvent are
1mmol:15~20mL.
Preferably, the temperature of the condensation reaction is 60~120 DEG C.
Preferably, the reaction time of the condensation reaction is 6~8h.
Present invention also offers application of the above-mentioned dye sensitizing agent in DSSC.
The invention provides a kind of dye sensitizing agent, has the structure shown in formula I, two kinds of D-A structures are included in the structure,
Respectively using D-A structure of the phenthazine as the D-A structure of electron donor and using carbazole as electron donor, constitute new (D-A)2
Type dye sensitizer, new working substance is provided for the screening of dye sensitizing agent.It is test result indicates that provided by the present invention
Dye sensitizing agent has excellent photoelectric conversion performance, and electricity conversion is up to 4.79%.
Present invention also offers the preparation method of above-mentioned dye sensitizing agent, preparation method provided by the present invention is simple, easily
In operation, it is adapted to industrialized production.
Brief description of the drawings
Fig. 1 is photovoltage-current characteristic curve of the gained DSSC of embodiment 5~8.
Embodiment
The invention provides a kind of dye sensitizing agent, has the structure shown in formula I：
The R is 2- cyano group -2- acrylics or 2- (rhodanine -3- acetic acid) vinyl；
The n is 4 or 8.
In the present invention, the dye sensitizing agent is preferably the compound shown in a of formula I, I b, I c or I d：
Present invention also offers the preparation method of above-mentioned dye sensitizing agent, comprise the following steps：
Cyanoacetic acid or rhodanine -3- acetic acid are mixed with the compound shown in formula II, alkaline condensing agent, polar organic solvent
After conjunction, condensation reaction is carried out, obtains dye sensitizing agent；
The n is 4 or 8.
In the present invention, the alkaline condensing agent is preferably piperidines and/or ammonium acetate；When the condensing agent is piperidines and vinegar
During sour ammonium, the present invention is not particularly limited to the mol ratio of the piperidines and ammonium acetate.
The present invention does not have particular/special requirement to the source of compound shown in the formula II, using commercially available or those skilled in the art
It is prepared by known preparation method；In embodiments of the present invention, compound shown in the formula II is preferably made with the following method
It is standby to obtain, comprise the following steps：
(1) compound shown in formula III is mixed with DMF, obtains compound solution shown in formula III；
(2) it is -5~5 DEG C in the temperature of compound solution shown in the formula III, and under conditions of inert gas shielding, will
The solution of compound mixes with POCl3 shown in the formula III, carries out formylation reaction, obtains compound shown in formula II；
The n is 4 or 8.
The present invention preferably mixes compound shown in formula III with DMF, and it is molten to obtain compound shown in formula III
Liquid.In the present invention, compound and the mol ratio of DMF are preferably 1 shown in the formula III:250~270, more
Preferably 1:260~265.Order by merging of the present invention to compound and N,N-dimethylformamide shown in the formula III is without spy
It is different to limit.
After obtaining compound solution shown in formula III, compound solution shown in the formula III is preferably cooled to -5 by the present invention~
5 DEG C, POCl3 is then added under conditions of inert gas shielding, carries out formylation reaction.
The present invention is not particularly limited to the speed of the cooling, can use any cooldown rate.
In the present invention, the inert gas is preferably nitrogen or argon gas；In embodiments of the present invention, the inert gas
Preferably nitrogen；The inert gas is preferably before compound solution shown in the formula III is begun to cool down or before addition POCl3
It is passed through.In the present invention, the inert gas shielding is played a part of preventing raw material from aoxidizing.
In the present invention, compound and the mol ratio of POCl3 are preferably 1 shown in the formula III:3~5, more preferably
1:4~4.3.
The present invention preferably adds POCl3 into compound solution shown in the formula III；The present invention is to the trichlorine oxygen
The feed postition of phosphorus is not particularly limited；In embodiments of the present invention, preferably POCl3 is disposably added to the formula III
In the solution of shown compound.
In the present invention, the formylation reaction is preferably first to carry out initial reaction at -5~5 DEG C, then at 85~95 DEG C
Carry out deep reaction.
In the present invention, the reaction temperature of the initial reaction is more preferably -2~2 DEG C；During the reaction of the initial reaction
Between be preferably 20~40min, more preferably 25~35min.
The heating rate that the present invention is warming up to deep reaction to the initial reaction is not particularly limited.
In the present invention, the reaction temperature of the deep reaction is more preferably 88~92 DEG C；The reaction of the deep reaction
Time is preferably 3.5~4.5h；The reaction time of the deep reaction is preferably warming up to deep reaction from the temperature of reaction system
Required chronotherm rises.
After the completion of formylation reaction, the present invention is preferably post-processed the product of the formylation reaction, obtains formula II
Shown compound.
In the present invention, the post processing preferably includes pH value regulation, extraction and column chromatography successively.
In the present invention, the pH value regulation preferably includes following steps：The product of the formylation reaction is mixed with water
Close, regulation pH value obtains neutral mixed solution to neutrality.
In the present invention, the volume ratio of mixed solution and water obtained by the formylation reaction is preferably 1:20~30, it is more excellent
Elect 1 as:24~25.The temperature that the present invention mixes to mixed solution obtained by the formylation reaction with water is not particularly limited；
In the embodiment of the present invention, the mixed solution is preferably down to room temperature, then mix with water.The present invention is to the formylation reaction institute
The hybrid mode for obtaining mixed solution and water is not particularly limited, and can be well mixed the mixed solution with water.
In the present invention, the pH value is preferably adjusted using the aqueous solution of inorganic strong alkali.In the present invention, the nothing
Machine highly basic is preferably potassium hydroxide and/or sodium hydroxide；In embodiments of the present invention, the aqueous solution of the inorganic strong alkali is preferably
The aqueous solution of sodium hydroxide.The present invention is not particularly limited to the concentration of the aqueous solution of the inorganic strong alkali, can adjust system
Save to neutrality.
After obtaining neutral mixed solution, neutral mixed solution is extracted described in preferred pair of the present invention.In the present invention, institute
It is preferably dichloromethane to state the extractant that extraction uses；The number of the extraction is preferably 3~5 times；The extraction used is extracted every time
It is preferably 0.5~0.7 to take the ratio between the volume of agent and the volume of liquid to be extracted:1.
After the completion of extraction, the present invention will preferably extract gained organic phase every time and merge, and the organic phase of merging is washed.
In the present invention, the washing lotion used in the washing is preferably saturated aqueous common salt；The number of the washing is preferably 3~5 times；Every time
Wash the ratio between the volume of washing lotion used and the volume of organic phase merged preferably 0.4~0.6:1.
After the completion of washing, preferred pair washing gained organic phase of the present invention is dried.In the present invention, the drying is preferred
For desiccant dryness；The drier is preferably anhydrous sodium sulfate；The present invention is not special to the dosage of the anhydrous sodium sulfate
Limit, can be by the moisture removal in organic phase.
The dried organic phase is preferably evaporated under reduced pressure by the present invention, obtains the residue of organic phase.The present invention
The condition of the vacuum distillation is not particularly limited, organic solvent can be removed.
After obtaining the residue of organic phase, the residue of the organic phase is preferably carried out column chromatography by the present invention, is contained
The eluent of compound shown in formula II.In the present invention, the column chromatography preferably uses silicagel column；Washing used in the column chromatography
De- liquid is preferably the mixture of dichloromethane and petroleum ether, and the volume ratio of the dichloromethane and petroleum ether is preferably 1:1.8~
2.2, more preferably 1:2.The present invention is not particularly limited to the dosage of the eluent, can be by compound shown in the formula II
It is eluted out.
After the completion of column chromatography, preferably the eluent containing compound shown in formula II is dried by the present invention, obtains
To compound shown in formula II.The present invention is not special to the drying mode containing the eluent of compound shown in formula II obtained by column chromatography
Limit, solvent can be removed.In the present invention, the alkaline condensing agent and the mol ratio of the compound shown in formula II are excellent
Elect 2~4 as:1；More preferably 3~3.5:1.
In the present invention, cyanoacetic acid or rhodanine-the 3- acetic acid and the mol ratio of the compound shown in formula II are preferred
For 3~5:1；More preferably 4~4.5:1.
In the present invention, the polar organic solvent is preferably the one or more in acetonitrile, chloroform and acetic acid；When described
When polar organic solvent is the mixture of many kinds of substance, the present invention is not particularly limited to the ratio of each material.
In the present invention, the amount of the material of the compound shown in the formula II and the volume ratio of the polar organic solvent are excellent
Elect 1mmol as:15~20mL；More preferably 1mmol:17~18mL.
The present invention is to the cyanoacetic acid or rhodanine -3- acetic acid and the compound shown in formula II, alkaline condensing agent, polarity
The order of organic solvent mixing is not particularly limited, and random order can be used to mix.
In the present invention, the temperature of the condensation reaction is preferably 60~120 DEG C, more preferably 80~100 DEG C；The contracting
The reaction time for closing reaction is preferably 6~8h, more preferably 6.5~7.5h.In the present invention, it is described in condensation reaction
Methylene on methylene or rhodanine -3- acetic acid on cyanoacetic acid on five-ring heterocycles and the compound shown in formula II
Condensation reaction occurs for aldehyde radical, generates dye sensitizing agent.
After the completion of condensation reaction, the present invention preferably removes mixed solution obtained by the condensation reaction through solvent successively, post
Chromatograph and dry, obtain dye sensitizing agent.
In the present invention, the solvent is removed preferably using vacuum distillation；The present invention to the pressure of the vacuum distillation and
Temperature is not particularly limited, and can all remove solvent.
In the present invention, silicagel column is preferably used to the column chromatography that gained residue is removed through solvent；The column chromatography is adopted
Eluent preferably uses the mixed solution of dichloromethane, methanol and acetic acid；The volume of the dichloromethane, methanol and acetic acid
Than being preferably 95~105:3~7:1, more preferably 98~102:4~6:1, most preferably 100:5:1；The present invention washes to described
The dosage of de- liquid is not particularly limited, and can be eluted out the dye sensitizing agent.
The present invention is not particularly limited to the drying mode of the eluent containing dye sensitizing agent obtained by column chromatography, can will be molten
Agent removes.Present invention also offers application of the above-mentioned dye sensitizing agent in DSSC.The present invention is right
Application process of the dye sensitizing agent in DSSC is not particularly limited, using those skilled in the art
The conventional method for preparing DSSC uses the dye sensitizing agent, is such as supported on dye sensitizing agent
On optoelectronic pole matrix, with the DSSC to electrode assembling for sandwich structure.
Below in conjunction with the embodiment in the present invention, the technical scheme in the present invention is clearly and completely described.It is aobvious
So, described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Based on the reality in the present invention
Example is applied, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, is all belonged to
In the scope of protection of the invention.
Embodiment 1
(1) compound (n=4) shown in 4.2g (i.e. 10mmol) formula III is dissolved in the anhydrous N,N-dimethylformamides of 20mL
In, at 0 DEG C, and 6.1g (i.e. 40mmol) POCl3 is added under conditions of nitrogen protection, carry out formylation reaction, the formyl
It is in 0 DEG C of isothermal reaction 30 minutes to change reaction, then is warming up to 90 DEG C and reacts 4 hours；It is after the completion of reaction, reaction gained mixing is molten
Liquid is poured into 500mL water, is adjusted to neutrality with sodium hydroxide solution, is extracted using dichloromethane, and extraction every time uses
300mL dichloromethane, extract 3 times, after completing extraction, merge organic phase；Using organic phase obtained by saturated common salt water washing, every time
Washing uses 300mL saturated aqueous common salts, washs 3 times；Then gained organic phase will be washed successively through anhydrous sodium sulfate drying, decompression
Concentration, silica gel column chromatography purification, dry, obtain 2.4g bright yellow solids, the eluent used in the silica gel column chromatography is dichloro
Methane and petroleum ether are using volume as 1:The mixed liquor that 2 ratio is prepared, is computed, yield 50%.
After testing, the fusing point of the bright yellow solid is 165-166 DEG C.
Magnetic resonance detection is carried out to gained yellow solid, it is as a result as follows：
1H-NMR(500MHz,CDCl3)δ:10.10 (s, 1H), 9.78 (s, 1H), 8.55 (s, 1H), 8.10 (d, J=
7.7Hz, 1H), 7.96 (d, J=8.5Hz, 1H), 7.51 (dd, J=9.3Hz, 2H), 7.48 (d, J=6.5Hz, 1H), 7.35
(t, J=8.5Hz, 2H), 7.31 (t, J=7.3Hz, 1H), 7.10 (t, J=6.5Hz, 2H), 6.97 (t, J=7.9Hz, 1H),
6.76 (d, J=7.9Hz, 1H), 6.71 (d, J=8.3Hz, 1H), 4.33 (t, J=6.9Hz, 2H), 3.90 (t, J=6.3Hz,
2H),2.11-2.05(m,2H),1.89-1.84(m,2H)；
HRESIMS m/z 477.1638[M+H]+,cacld C30H25N2O2S for:477.1631；
Infer that the structure of products therefrom is as follows according to data above, it is seen that be structure shown in formula II：
(2) by 1.5g (i.e. 3mmol) step (1) products therefrom, 1g (i.e. 12mmol) cyanoacetic acids and 0.5g (i.e. 6mmol)
Piperidines is dissolved in 50mL acetonitriles, is heated to 61 DEG C, reacts 6h；After reaction terminates, reaction gained mixed solution is subjected to decompression steaming
Evaporate, by gained residue silica gel column chromatography, eluent used in the silica gel column chromatography is dichloromethane, methanol and acetic acid with body
Product is than being 100:5:1 ratio is mixed to get, and through silica gel column chromatography, is collected eluent, is dried to obtain 1.3g dark red powders, counts
It is 72% to calculate yield.
After testing, the fusing point of the dark red powder is 206-207 DEG C.
Magnetic resonance detection is carried out to gained dark red powder, it is as a result as follows：
1H-NMR(500MHz,DMSO-d6)δ(ppm):8.65 (s, 1H), 8.35 (s, 1H), 8.12 (d, J=7.2Hz,
1H), 8.02 (d, J=7.7Hz, 1H), 7.99 (s, 1H), 7.65 (d, J=8.6Hz, 1H), 7.60 (s, 1H), 7.51 (d, J=
8.8Hz, 1H), 7.47 (d, J=8.2Hz, 1H), 7.42 (t, J=7.5Hz, 1H), 7.23 (t, J=7.3Hz, 1H), 7.08 (t,
J=7.6Hz, 1H), 7.02 (d, J=7.3Hz, 1H), 6.91 (t, J=7.5Hz, 1H), 6.87 (d, J=8.2Hz, 1H), 6.84
(d, J=8.7Hz, 1H), 4.35 (t, J=6.6Hz, 2H), 3.87 (t, J=5.9Hz, 2H), 1.97-1.88 (m, 2H), 1.81-
1.73(m,2H)；
13C-NMR(125MHz,DMSO-d6)δ(ppm):164.20,163.69,154.81,152.01,148.32,
142.73,142.56,140.49,131.01,128.87,127.87,127.64,127.00,126.55,125.55,124.79,
124.03,123.45,122.82,122.55,122.31,121.95,120.31,120.23,117.06,116.46,116.17,
115.38,109.69,109.66,99.92,98.49,46.22,42.15,25.00,23.32；
HRESIMS m/z 610.1765[M]+,cacld C36H26N4O4S for:610.1675。
Infer that the structure of products therefrom is as follows according to data above, it is seen that be structure shown in formula I：
Embodiment 2
(1) compound (n=8) shown in 4.8g (i.e. 10mmol) formula III is dissolved in the anhydrous N,N-dimethylformamides of 20mL
In, at 0 DEG C, and 6.1g (i.e. 40mmol) POCl3 is added under conditions of nitrogen protection, carry out formylation reaction, the formyl
It is in 0 DEG C of isothermal reaction 30 minutes to change reaction, then is warming up to 90 DEG C and reacts 4 hours；It is after the completion of reaction, reaction gained mixing is molten
Liquid is poured into 500mL water, is adjusted to neutrality with sodium hydroxide solution, is extracted using dichloromethane, and extraction every time uses
300mL dichloromethane, extract 3 times, after completing extraction, merge organic phase；Using organic phase obtained by saturated common salt water washing, every time
Washing uses 300mL saturated aqueous common salts, washs 3 times；Then gained organic phase will be washed successively through anhydrous sodium sulfate drying, decompression
Concentration, silica gel column chromatography purification, dry, obtain 2.5g glassy yellow liquid, the eluent used in the silica gel column chromatography is dichloro
Methane and petroleum ether are using volume as 1:The mixed liquor that 2 ratio is prepared, is computed, yield 47%.
Magnetic resonance detection is carried out to gained glassy yellow liquid, it is as a result as follows：
1H-NMR(500MHz,CDCl3)δ:10.08 (s, 1H), 9.75 (s, 1H), 8.57 (s, 1H), 8.13 (d, J=
7.7Hz, 1H), 7.99 (d, J=8.5Hz, 1H), 7.61-7.57 (m, 1H), 7.56-7.50 (m, 2H), 7.42 (d, J=
8.6Hz, 2H), 7.32 (t, J=7.5Hz, 1H), 7.14 (t, J=7.0Hz, 1H), 7.09 (dd, J=7.6,1.5Hz, 1H),
6.97-6.93 (m, 1H), 6.83 (t, J=8.0Hz, 2H), 4.26 (t, J=7.2Hz, 2H), 3.82 (t, J=7.0Hz, 2H),
1.86-1.80(m,2H),1.77-1.71(m,2H),1.42-1.32(m,8H)；
HRESIMS m/z 533.2258[M+H]+,cacld C34H33N2O2S for:533.2263。
Infer that the structure of products therefrom is as follows according to data above, it is seen that be structure shown in formula II：
(2) by 1.6g (i.e. 3mmol) step (1) products therefrom, 1g (i.e. 12mmol) cyanoacetic acids and 0.5g (i.e. 6mmol)
Piperidines is dissolved in 50mL chloroforms, is heated to 60 DEG C, reacts 6h；After reaction terminates, reaction gained mixed solution is subjected to decompression steaming
Evaporate, by gained residue silica gel column chromatography, eluent used in the silica gel column chromatography is dichloromethane, methanol and acetic acid with body
Product is than being 100:5:1 ratio is mixed to get, and through silica gel column chromatography, is collected eluent, is dried to obtain 1.5g dark red powders, counts
It is 73% to calculate yield.
After testing, the fusing point of the dark red powder is 152~153 DEG C.
Magnetic resonance detection is carried out to gained dark red powder, it is as a result as follows：
1H-NMR(500MHz,DMSO-d6)δ:8.68 (s, 1H), 8.33 (s, 1H), 8.13 (d, J=8.5Hz, 1H), 8.04
(d, J=7.4Hz, 1H), 7.97 (s, 1H), 7.71 (d, J=8.0Hz, 1H), 7.63 (s, 1H), 7.50 (d, J=8.6Hz,
1H), 7.45 (s, 1H), 7.22 (s, 1H), 7.09 (t, J=7.4Hz, 1H), 7.00 (d, J=6.6Hz, 1H), 6.92-6.79
(m, 4H), 4.26 (t, J=6.9Hz, 2H), 3.76 (t, J=7.9Hz, 2H), 1.76-1.74 (m, 2H), 1.67-1.58 (m,
2H),1.35-1.27(m,8H)；
13C-NMR(125MHz,DMSO-d6)δ(ppm):155.02,152.23,148.73(2C),142.53(2C),
140.54,131.37,128.58,128.11,127.45(2C),126.93(2C),126.55,123.67,123.23(2C),
122.60,122.43,122.25,121.97,120.24,120.11,117.06,116.46,115.86(2C),114.94
(2C),109.49,109.45,54.04,46.97,28.52,28.26,26.23,25.86,28.84,25.77；
HRESIMS m/z 667.2370[M+H]+,cacld C40H35N4O4S for:667.2379。
Infer that the structure of products therefrom is as follows according to data above, it is seen that be structure shown in formula I：
Embodiment 3
(1) according to compound (n=4) shown in the method formula II described in the step of embodiment 1 (1)；
(2) by 1.5g (i.e. 3mmol) step (1) products therefrom, 1.7g (i.e. 9mmol) rhodanine -3- acetic acid and 0.69g
(i.e. 9mmol) ammonium acetate is dissolved in 45mL acetic acid, is heated to 100 DEG C, reacts 7h；It is after reaction terminates, reaction gained mixing is molten
Liquid is evaporated under reduced pressure, and by gained residue silica gel column chromatography, eluent used in the silica gel column chromatography is dichloromethane, first
Alcohol and acetic acid are using volume ratio as 100:5:1 ratio is mixed to get, and through silica gel column chromatography, is collected eluent, is dried to obtain 1.2g
Black powder, calculated yield 47%.
After testing, the fusing point of the black powder is 231~232 DEG C.
Magnetic resonance detection is carried out to gained black powder, it is as a result as follows：
1H-NMR(500MHz,DMSO-d6)δ(ppm):8.38 (s, 1H), 8.23 (d, J=7.7Hz, 1H), 8.03 (s,
1H), 7.70 (d, J=7.1Hz, 2H), 7.67 (d, J=9.0Hz, 1H), 7.62 (d, J=8.3Hz, 1H), 7.50 (t, J=
7.7Hz, 1H), 7.29 (t, J=7.3Hz, 1H), 7.25 (d, J=8.5Hz, 2H), 7.16 (t, J=7.8Hz, 1H), 7.13 (d,
J=7.6Hz, 1H), 7.01 (d, J=8.0Hz, 1H), 6.98 (d, J=7.4Hz, 1H), 6.95 (d, J=8.6Hz, 1H), 4.74
(s, 2H), 4.71 (s, 2H), 4.47 (t, J=6.9Hz, 2H), 3.93 (t, J=6.6Hz, 2H), 2.01-1.92 (m, 2H),
1.80-1.74(m,2H)；
13C-NMR(125MHz,DMSO-d6)δ:193.09,192.58,171.98,167.27,166.44,166.29,
146.66,143.09,141.33,140.66,135.75,132.99,130.45,129.30,128.58,127.85,127.17,
126.83,126.74,124.35,124.19,123.55,123.44,123.01,122.60,121.84,120.75,118.54,
117.15,116.40,116.16,113.92,110.42,109.99,46.22,45.09,42.10,40.03,25.11,
23.37；
HRESIMS m/z 821.0710[M-H]-,cacld C40H30N4O6S5for:821.0691。
Infer that the structure of products therefrom is as follows according to data above, it is seen that be structure shown in formula I：
Embodiment 4
(1) according to compound (n=8) shown in the method formula II described in the step of embodiment 2 (1)；
(2) by 1.6g (i.e. 3mmol) step (1) products therefrom, 2.9g (i.e. 15mmol) rhodanine -3- acetic acid and 0.97g
(i.e. 12mmol) ammonium acetate is dissolved in 60mL acetic acid, is heated to 120 DEG C, reacts 8h；It is after reaction terminates, reaction gained mixing is molten
Liquid is evaporated under reduced pressure, and by gained residue silica gel column chromatography, eluent used in the silica gel column chromatography is dichloromethane, first
Alcohol and acetic acid are using volume ratio as 100:5:1 ratio is mixed to get, and through silica gel column chromatography, is collected eluent, is dried to obtain 1.1g
Black powder, calculated yield 40%.
After testing, the fusing point of the black powder is 165~166 DEG C.
Magnetic resonance detection is carried out to gained black powder, it is as a result as follows：
1H-NMR(500MHz,DMSO-d6)δ(ppm):8.48 (s, 1H), 8.28 (d, J=7.7Hz, 1H), 8.06 (s,
1H), 7.79-7.74 (m, 2H), 7.73-7.71 (m, 1H), 7.65 (d, J=8.4Hz, 1H), 7.52 (d, J=7.6Hz, 1H),
7.42 (dd, J=9.0,1.5Hz, 1H), 7.35 (d, J=2.1Hz, 1H), 7.30 (t, J=7.2Hz, 1H), 7.19 (t, J=
7.8Hz, 1H), 7.13 (t, J=7.5Hz, 1H), 7.08 (d, J=8.8Hz, 1H), 7.05-6.95 (m, 2H), 4.78 (s, 2H),
4.74 (s, 2H), 4.43 (t, J=6.5Hz, 2H), 3.87 (t, J=6.6Hz, 2H), 1.81-1.74 (m, 2H), 1.68-1.61
(m,2H),1.48-1.30(m,8H).
13C-NMR(125MHz,DMSO-d6)δ(ppm):195.90,195.38,174.83,170.18,169.25,
169.07,149.79,145.64,144.24,143.48,138.53,135.74,133.56,132.08,131.34,130.69,
129.99,129.61,127.20,126.61,126.36,126.23,125.81,124.96,124.68,123.62,122.84,
121.31,119.99,119.05,118.99,118.65,113.18,112.72,58.88,49.57,47.88,45.25,
31.16,28.77,28.65,28.48,23.85,21.35；
HRESIMS m/z 877.1362[M-H]-,cacld C44H38N4O6S5for:877.1317。
Infer that the structure of products therefrom is as follows according to data above, it is seen that be structure shown in formula I：
Embodiment 5
The gained dye sensitizing agent of embodiment 1 is supported on optoelectronic pole matrix, with being sandwich structure to electrode assembling
DSSC, specific method are as follows：
(1) preparation of optoelectronic pole
Silk screen print method is used to print TiO 2 particles layer of the one layer of particle diameter for 20nm on electro-conductive glass FTO, described two
The thickness of Titanium particles layer is 12 μm, and the electro-conductive glass that gained is printed on to titanium dioxide nano-particle layer is placed in Muffle furnace,
30min is calcined at 450 DEG C；Will calcine gained be printed with titanium dioxide nano particle film electro-conductive glass be cooled to room temperature after immerse
Concentration is in 0.04mol/L titanium trichloride aqueous solution, pre-processes 30min at 70 DEG C, then uses water and alcohol flushing successively, dries
Muffle furnace is placed in after dry, secondary clacining 30min is carried out at 450 DEG C；Titanium dioxide nano-particle will be printed with obtained by secondary clacining
The electro-conductive glass of film immerses concentration after being cooled to 80 DEG C be 3 × 10-4The dye sensitization agent solution that mol/L embodiment 1 is provided
In, the solvent of the dye sensitization agent solution is by chloroform and methanol using volume ratio as 10:1 ratio is formulated, and soaks 24h
Afterwards, through being dried to obtain optoelectronic pole.
(2) to the preparation of electrode：
Using method for printing screen, platinum electrode slurry is printed on electro-conductive glass FTO, gained is printed with platinum electrode slurry
The electro-conductive glass of material is placed in Muffle furnace, calcines 20min at 400 DEG C, obtains to electrode；
(3) preparation of DSSC
By optoelectronic pole obtained by step (1) and the battery to electrode assembling into sandwich structure prepared by step (2), in electricity
Pool side edge instills electrolyte, and (I- containing 0.07mmol/L, the electrolyte come from difficult to understand of Yingkou limited public affairs of the special new energy science and technology of dimension
Department), inside battery is introduced using capillary percolation principle, obtains DSSC.
Embodiment 6
Using the method described in embodiment 5, the gained dye sensitizing agent of embodiment 2 is supported on optoelectronic pole matrix, it is and right
Electrode assembling is the DSSC of sandwich structure.
Embodiment 7
Using the method described in embodiment 5, the gained dye sensitizing agent of embodiment 3 is supported on optoelectronic pole matrix, it is and right
Electrode assembling is the DSSC of sandwich structure.
Embodiment 8
Using the method described in embodiment 5, the gained dye sensitizing agent of embodiment 4 is supported on optoelectronic pole matrix, it is and right
Electrode assembling is the DSSC of sandwich structure.
In 100mV/cm2Under light intensity, photovoltage-electric current of the gained DSSC of testing example 5~8 is special
Linearity curve, its result is as shown in figure 1, table 1 is as DSSC (DSSC) performance parameter obtained by Fig. 1：
The DSSC performance parameters of the gained DSSC of 1 embodiment of table 5~8
Dye sensitizing agent provided by the present invention is respectively provided with photoelectric conversion ability, Ke Yizuo it can be seen from Fig. 1 and table 1
For the dye sensitizing agent of DSSC, and its electricity conversion has excellent up to being 1.25~4.79%
Photoelectric conversion performance.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of dye sensitizing agent, there is the structure shown in formula I：
The R is 2- cyano group -2- acrylics or 2- (rhodanine -3- acetic acid) vinyl；
The n is 4 or 8.
2. a kind of preparation method of the dye sensitizing agent described in claim 1, comprises the following steps：
Cyanoacetic acid or rhodanine -3- acetic acid are mixed with the compound shown in formula II, alkaline condensing agent, polar organic solvent
Afterwards, condensation reaction is carried out, obtains dye sensitizing agent；
The n is 4 or 8.
3. preparation method according to claim 2, it is characterised in that the alkaline condensing agent is piperidines and/or ammonium acetate.
4. the preparation method according to Claims 2 or 3, it is characterised in that the alkaline condensing agent and the change shown in formula II
The mol ratio of compound is 2~4:1.
5. the preparation method according to Claims 2 or 3, it is characterised in that cyanoacetic acid or rhodanine-the 3- acetic acid with
The mol ratio of compound shown in formula II is 3~5:1.
6. preparation method according to claim 2, it is characterised in that the polar organic solvent is acetonitrile, chloroform and second
One or more in acid.
7. the preparation method according to claim 2 or 6, it is characterised in that the material of the compound shown in the formula II
Amount and the volume ratio of the polar organic solvent are 1mmol:15~20mL.
8. preparation method according to claim 2, it is characterised in that the temperature of the condensation reaction is 60~120 DEG C.
9. the preparation method according to claim 2 or 8, it is characterised in that the reaction time of the condensation reaction be 6~
8h。
10. application of the dye sensitizing agent described in claim 1 in DSSC.
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