CN105175455A - Water-soluble dipyridine-ruthenium photosensitizers with imidazolium as cation, and application thereof in dye-sensitized solar cell - Google Patents
Water-soluble dipyridine-ruthenium photosensitizers with imidazolium as cation, and application thereof in dye-sensitized solar cell Download PDFInfo
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- CN105175455A CN105175455A CN201510557794.6A CN201510557794A CN105175455A CN 105175455 A CN105175455 A CN 105175455A CN 201510557794 A CN201510557794 A CN 201510557794A CN 105175455 A CN105175455 A CN 105175455A
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- 239000003504 photosensitizing agent Substances 0.000 title claims abstract description 42
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 title abstract 3
- 150000001768 cations Chemical class 0.000 title abstract 2
- CQPRXCARUJOTNF-UHFFFAOYSA-N pyridine;ruthenium Chemical compound [Ru].C1=CC=NC=C1.C1=CC=NC=C1 CQPRXCARUJOTNF-UHFFFAOYSA-N 0.000 title abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- 125000003545 alkoxy group Chemical group 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 125000004414 alkyl thio group Chemical group 0.000 claims description 24
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 24
- 125000001033 ether group Chemical group 0.000 claims description 24
- 125000001072 heteroaryl group Chemical group 0.000 claims description 24
- 125000003107 substituted aryl group Chemical group 0.000 claims description 24
- 125000000101 thioether group Chemical group 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 125000002091 cationic group Chemical group 0.000 claims description 19
- 150000002460 imidazoles Chemical class 0.000 claims description 18
- 206010070834 Sensitisation Diseases 0.000 claims description 16
- 230000008313 sensitization Effects 0.000 claims description 16
- 230000009466 transformation Effects 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 125000000304 alkynyl group Chemical group 0.000 claims description 12
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 12
- 125000004185 ester group Chemical group 0.000 claims description 12
- -1 aldehyde radical Chemical class 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- QLWOUBCORTYSPP-UHFFFAOYSA-N 1h-imidazol-1-ium;hydroxide Chemical class O.C1=CNC=N1 QLWOUBCORTYSPP-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 claims description 4
- AXHRGVJWDJDYPO-UHFFFAOYSA-N 2-bromo-1h-imidazole Chemical class BrC1=NC=CN1 AXHRGVJWDJDYPO-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 9
- 150000001875 compounds Chemical class 0.000 claims 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 239000004408 titanium dioxide Substances 0.000 abstract description 11
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000004040 coloring Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 16
- 150000002431 hydrogen Chemical class 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- KJYQVRBDBPBZTD-UHFFFAOYSA-N methanol;nitric acid Chemical compound OC.O[N+]([O-])=O KJYQVRBDBPBZTD-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- 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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
-
- 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
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2013—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte the electrolyte comprising ionic liquids, e.g. alkyl imidazolium iodide
-
- 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
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- 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
- 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
- Y02E10/549—Organic PV cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to molecular structures and water solubility of water-soluble photosensitizers with imidazolium as a cation, and an application of the photosensitizers in a dye-sensitized solar cell. The imidazolium cation is introduced to solve the water solubility problem of dipyridine-ruthenium photosensitizers. Water is used in preparation of photosensitizer solutions to substitute common organic solvents in order to colorize titanium dioxide, the adsorption quantity is large, the adsorption time is short, and the problem of unable coloring or water meeting decolorizing of aqueous solutions of other photosensitizers is solved. Mass use of the organic solvent is avoided in the cell production process, so the cost is reduced, and the environment and organism compatibility is improved; decolorizing of nanometer titanium dioxide by water is very difficult, so the service life of the cell is prolonged; the photoelectric conversion efficiency of the produced dye-sensitized solar cell exceeds 10%, so the problem of great reduction of the water meeting performance of other dye-sensitized solar cells in the production process is solved; and the difficulty of a production process is reduced, so the photosensitizers have huge values in practical application and industrial production.
Description
Technical field
The present invention relates to a class with imidazoles is the molecular structure of cationic water-soluble dipyridyl-ruthenium class photosensitizers, water-soluble and application in dye sensitization solar battery.
Background technology
Sun power is considered to effectively substituting of traditional fossil energy as a kind of clean energy.Dye-sensitized cell has the advantages such as manufacture craft is relatively simple, effciency of energy transfer is higher, cost is lower, has very strong application prospect.[see: Hagfeldt, A., Boschloo, G.; Sun, L., Kloo.L., Pettersson, H.,
chem.Rev. 2010,
110, 6595].1993, Gr professor tzel etc. of Switzerland reported famous photosensitizers
n3the dye sensitization solar battery photoelectric transformation efficiency made reaches 10.3%.[see: Nazeeruddin, M.K.; Kay, A., Rodicio, L.; Humphry-Baker, R.; MRller, E.; Liska, P.; Vlachopoulos, N.; Grtzel, M.
j.Am.Chem.Soc. 1993,
115, 6382.].Next, this seminar is also by inciting somebody to action
n3two hydrogen positive ions in photosensitizers replace with the amino positive ion of the tetrabutyl and obtain another famous photosensitizers
n719,photoelectric transformation efficiency reaches 11%, becomes the photosensitizers that field of dye-sensitized solar cells is the most frequently used.[see: (a) Nazeeruddin, M.K.; Zakeeruddin, S.M.; Humphry-Baker, R.; Jirousek, M.; Liska, P.; Vlachopoulos, N.; Shklover, V.; FischerChristian-H., Gr tzel, M.
inorg.Chem. 1999,
38, 6298; (b) Nazeeruddin, M.K.; Angelis, F.D.; Fantacci, S.; Selloni, A.; Viscardi, G.; Liska, P.; Ito, S.; Takeru, B.; Grtzel, M.
j.Am.Chem.Soc. 2005,
127, 16835.].
But with
n3with
n719for the dipyridyl-ruthenium class photosensitizers of representative is insoluble in water, be mainly prepared into after solution pigmented with titanium dioxide with organic solvent.A large amount of uses of organic solvent can not look down upon to environment and the biological potential threat caused.In addition, painted titanium dioxide also easily meets water decolorization, and this makes finished product solar cell properties inevitable rapid decay in the physical environment that drenches with rain of exposing to the weather.Certainly, solve photosensitizers water solubility problems, and pigmented with titanium dioxide process is carried out in aqueous, not only can reduce costs, and more friendly with biology for environment, will huge value be produced in practical application and industrial production.
Summary of the invention
The object of the invention is to exploitation imidazole is cationic water-soluble dipyridyl-ruthenium class photosensitizers, solve photosensitizers water solubility problems, solve a titanium dioxide difficult problem painted in the aqueous solution of photosensitizers simultaneously, and apply it in high efficiency dye sensitization solar battery, obtain the photoelectric transformation efficiency more than 10%.
The present invention solves the technical scheme of this problem: by introducing glyoxaline cation, strengthen cis-bis-(isothiocyano) two (2,2'-bipyridyl-4,4'-dicarboxyl) ruthenium (II) class photosensitizers is water-soluble, the tinting material of solution as titanium dioxide photo anode of conventional organic solvent configuration photosensitizers is replaced using water, adsorptive capacity is larger, and adsorption time is faster, and the aqueous solution of the photosensitizers of solving over can not painted or serious problem of decolouring.
Such imidazoles is the general structure of cationic water-soluble photosensitizers:
Wherein R
1for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl; R
2for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl, aldehyde radical, alkynyl, carbonyl, ester group, cyano group, nitro; R
3for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl; Carbochain wherein in alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl, alkynyl, carbonyl, ester group to be carbon number be 0 ~ 40 straight chain, one or more in side chain or naphthenic hydrocarbon.
The raw material adopted and syntheti c route (as accompanying drawing 1):
(1) bromo imidazoles be dissolved in methyl alcohol and react with the methanol solution of potassium hydroxide, after being filtered by insolubles, obtaining the methanol solution of hydroxide imidazoles;
(2) by cis-bis-(isothiocyano) two (2,2'-bipyridyl-4,4'-dicarboxyl) ruthenium (II) is dissolved in methyl alcohol, add the methanol solution of the hydroxide imidazoles of 4 times of equivalents, drip nitre aqueous acid again to suitable pH value, add ether after methyl alcohol is concentrated, product is separated out, and it is cationic dipyridyl-ruthenium class photosensitizers that vacuum-drying obtains imidazoles.Wherein, the general structure of hydroxide imidazoles is:
Wherein R
1for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl; R
2for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl, aldehyde radical, alkynyl, carbonyl, ester group, cyano group, nitro; R
3for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl; Carbochain wherein in alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl, alkynyl, carbonyl, ester group to be carbon number be 0 ~ 40 straight chain, one or more in side chain or naphthenic hydrocarbon.
With proton nmr spectra (
1hNMR) and high resolution mass spectrum confirm that imidazoles is the structure of cationic dipyridyl-ruthenium class dyestuff.Detection instrument is: BrukerAVII-400MHz type nuclear magnetic resonance analyser, and wherein TMS is interior mark, and deuterated DMSO is solvent; Waters-Q-TOF-Premier (ESI) type high-resolution mass spectrometer.
It is good water-soluble that imidazoles is that cationic dipyridyl-ruthenium class photosensitizers has.
Nano titanium oxide light anode imidazoles be have in the aqueous solution of cationic dipyridyl-ruthenium class photosensitizers that adsorption rate is fast, adsorptive capacity is large, adsorb stable feature.The adsorption time reaching optimum efficiency is only 1 hour-3 hours.
Imidazoles is that the incidence monochromatic photon-electron transformation efficiency curve of cationic dipyridyl-ruthenium class photosensitizers covers 300nm-750nm, reaches as high as 80%-90%.
Imidazoles is that the photoelectric transformation efficiency of cationic dipyridyl-ruthenium class photosensitizers can reach 10%-11%, and open circuit voltage can reach 0.74-0.78V, and short-circuit current can reach 19-22mA/cm
2, packing factor can reach 68-75%.
In the embodiment of the present invention, titanium dioxide photo anode, platinum electrode and 30
μthe Kapton Tape of m thickness is all outsourcings.Titanium dioxide photo anode specification is: on conductive glass, cover a layer thickness is 13 ~ 15
μm, area is 0.4 × 0.4cm
2titanium oxide nanoparticles.
The photoelectric property of dye-sensitized cell characterizes instrument and is: monochromatic photon-electron transformation efficiency is at QTestStation1000AD (Crowntech, Inc.) upper test, photoelectric transformation efficiency Oriel94023A, NewportCorp. solar simulator provides power to be 100mWcm
-2condition under, record density of photocurrent-voltage curve with KeithleySeries2000 type current potential table.
Compared with the various dipyridyls-ruthenium class photosensitizers preparing dye sensitization solar battery, be that cationic water-soluble dipyridyl-ruthenium class photosensitizers performance is more excellent with imidazoles in the present invention, be embodied as:
1. imidazoles is that cationic water-soluble dipyridyl-ruthenium class photosensitizers is water-soluble greatly increases;
2. imidazoles is that cationic water-soluble dipyridyl-ruthenium class photosensitizers in aqueous to nano titanium oxide light anodic coloration, can be avoided in a large number with an organic solvent, reduce cost, improve environment and biocompatibility in cell manufacturing process;
3. be that the painted nano titanium oxide light anode of cationic water-soluble dipyridyl-ruthenium class photosensitizers is not easy by water decolorization with imidazoles, improve the work-ing life of battery;
4. with imidazoles be dye sensitization solar battery photoelectric transformation efficiency that cationic water-soluble dipyridyl-prepared by ruthenium class photosensitizers more than 10%, with
n3with
n719be in same level etc. outstanding photosensitizers, solve other dye sensitization solar battery performances preparing in cell process the problem of meeting water and greatly reducing, reducing preparation technology's difficulty.
four, accompanying drawing explanation
The synthetic route of Fig. 1 to be imidazoles be cationic dipyridyl-ruthenium class photosensitizers.Wherein R
1for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl; R
2for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl, aldehyde radical, alkynyl, carbonyl, ester group, cyano group, nitro; R
3for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl; Carbochain wherein in alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl, alkynyl, carbonyl, ester group to be carbon number be 0 ~ 40 straight chain, one or more in side chain or naphthenic hydrocarbon;
Fig. 2 is synthesized by the embodiment of the present invention 1
m2C6molecular structure and hydrogen nuclear magnetic resonance spectrogram;
Fig. 3 is synthesized by the embodiment of the present invention 1
m2C6monochromatic photon-electron transformation efficiency figure;
Fig. 4 is synthesized by the embodiment of the present invention 1
m2C6density of photocurrent-voltage pattern.
five, embodiment
Below in conjunction with concrete case study on implementation, the invention will be further described, will contribute to the understanding of the present invention.But interest field of the present invention can not be limited with this, and interest field of the present invention should being as the criterion with claims elaboration.
the synthesis of embodiment 1:M2C6
(1) by bromo 3-n-hexyl-1,2-methylimidazole (522.4mg, 2mmol, one times of equivalent) be dissolved in methyl alcohol (1mL), separately by potassium hydroxide (117.8mg, 2.1mmol, 1.05 times of equivalents) be dissolved in methyl alcohol, the methanol solution of potassium hydroxide is dripped the methanol solution into bromo 3-n-hexyl-1,2 dimethylimidazole, stirred at ambient temperature 12 hours.Obtain settled solution after suction filtration, the solution with methanol after suction filtration is diluted to 8mL, and being mixed with containing hydroxide 3-n-hexyl-1,2 dimethylimidazole concentration is the methanol solution of 0.25mmol/mL.
(2) by cis-bis-(isothiocyano) two (2, 2'-bipyridyl-4, 4'-dicarboxyl) ruthenium (II) (211.7mg, 0.3mmol, 1.0 times of equivalents) be dissolved in methyl alcohol (5mL), add the hydroxide 3-n-hexyl-1 obtained in step (1), methanol solution (the 4.8mL of 2-methylimidazole 0.25mmol/mL, 1.2mmol, 4.0 times of equivalents), stirring at normal temperature adds ether (20mL) and separates out solid after 1 hour, solid 310mg is obtained with after Büchner funnel suction filtration, solid is dissolved in methyl alcohol (10mL), add the nitric acid methanol solution that 4.3mL concentration is 0.1mol/L, be concentrated into 2mL, add ether (10mL), solid is separated out, suction filtration vacuum-drying, obtain black solid
m2C6(153.6mg, productive rate: 48.0%).
1hNMR (400MHz, CDCl
3):
δ=0.84 (t,
j=6.2Hz, 6H), 1.20-1.30 (m, 12H), 1.67 (t,
j=6.8Hz, 4H), 2.57 (m, 6H), 3.74 (s, 6H), 4.09 (t,
j=7.4Hz, 4H), 7.41-7.45 (m, 4H), 7.63 (2.0Hz, 2H), 7.66 (d,
j=2.0Hz, 2H), 8.08 (dd,
j=5.6Hz, 1.2Hz, 2H), 8.53 (s, 2H), 8.70 (s, 2H), 9.17 (d,
j=5.6Hz, 2H) ppm.(accompanying drawing 2)
embodiment 2: the solubility test of photosensitizers in water
In 10.0mL water synthesized by maximum solubilized 83.1mg embodiment 1
m2C6, obtain dark red solution, calculate thus
m2C6solubleness in water is 8.3mg/mL.
embodiment 3: the assembling of dye sensitization solar battery
By synthesized by embodiment 1
m2C6(8.00mg) be dissolved in distilled water (14.5mL), regulate with the aqueous nitric acid of 0.010M under the monitoring of pH meter
m2C6the pH of the aqueous solution to 3.8, now the concentration of photosensitizers is 0.50mmol/L, is immersed by nano titanium oxide light anode, and normal temperature is placed after 2 hours and taken out, and with distilled water flushing, dries under 80 DEG C of conditions.Again with Kapton Tape by painted titanium dioxide photo anode and platinum electrode bonding, inject electrolyte solution, prepare dye sensitization solar battery.
embodiment 4: dye sensitization solar battery photoelectric property characterizes
Room temperature condition, the monochromatic photon-electron transformation efficiency of dye sensitization solar battery obtained in testing example 3.The monochromatic photon-electron transformation efficiency peak value recording dye sensitization solar battery is that 90%(is as accompanying drawing 3); Room temperature condition, at 100mWcm
-2under the solar simulator irradiation of power and 1.5G irradiation, the dye sensitization solar battery parameter of gained in testing example 3.Record the photoelectric transformation efficiency 10.6% of dye sensitization solar battery, wherein open circuit voltage 0.74V, short-circuit current density 21.2mA/cm
-2, packing factor 0.67(is as accompanying drawing 4).
embodiment 5: photosensitizers detects titanium dioxide photo anode retention of color
By synthesized by embodiment 1
m2C6(8.00mg) be dissolved in distilled water (14.5mL), regulate with the aqueous nitric acid of 0.010M under the monitoring of pH meter
m2C6the pH of the aqueous solution to 3.8, now the concentration of photosensitizers is 0.50mmol/L, nano titanium oxide light anode is immersed, normal temperature is placed after 2 hours and is taken out, with distilled water flushing, after drying under 80 DEG C of conditions, then use a large amount of distilled water flushing, without obviously decolouring, be assembled into the dye sensitization solar battery of battery behind efficiency compared with gained in embodiment 3 without obvious reduction.
Claims (6)
1. be cationic water-soluble dipyridyl-ruthenium class photosensitizers with imidazoles, its general structure is as follows:
Wherein R
1for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl; R
2for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl, aldehyde radical, alkynyl, carbonyl, ester group, cyano group, nitro; R
3for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl; Carbochain wherein in alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl, alkynyl, carbonyl, ester group to be carbon number be 0 ~ 40 straight chain, one or more in side chain or naphthenic hydrocarbon.
2. be the preparation method of cationic water-soluble dipyridyl-ruthenium class photosensitizers with imidazoles, it is characterized in that preparation process is as follows:
(1) bromo imidazoles is dissolved in methyl alcohol, and reacts with the methanol solution of potassium hydroxide, after being filtered by insolubles, obtain the methanol solution of hydroxide imidazoles;
(2) by cis-bis-(isothiocyano) two (2,2'-bipyridyl-4,4'-dicarboxyl) ruthenium (II) is dissolved in methyl alcohol, add the methanol solution of the hydroxide imidazoles of 4 times of equivalents, the methanol solution dripping nitric acid again, to suitable pH value, adds ether after methyl alcohol is concentrated, separates out product, vacuum-drying, obtaining imidazoles is cationic water-soluble dipyridyl-ruthenium class photosensitizers.
3. preparation method according to claim 2, the general structure of bromo imidazoles is as follows:
Wherein R
1for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl; R
2for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl, aldehyde radical, alkynyl, carbonyl, ester group, cyano group, nitro; R
3for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl; Carbochain wherein in alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl, alkynyl, carbonyl, ester group to be carbon number be 0 ~ 40 straight chain, one or more in side chain or naphthenic hydrocarbon.
4. preparation method according to claim 2, the general structure of hydroxide imidazoles is as follows:
Wherein R
1for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl; R
2for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl, aldehyde radical, alkynyl, carbonyl, ester group, cyano group, nitro; R
3for hydrogen, alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl; Carbochain wherein in alkyl, alkoxyl group, benzyl, ether chain, alkylthio, thioether chain, substituted aryl, substituted heteroaryl, alkynyl, carbonyl, ester group to be carbon number be 0 ~ 40 straight chain, one or more in side chain or naphthenic hydrocarbon.
5. the purposes of compound described in claim 1, is characterized in that: can be water-soluble, and the aqueous solution of compound described in available claim 1 is to nano titanium oxide light anodic coloration.
6. the purposes of compound described in claim 1, is characterized in that: the dye sensitization solar battery prepared with compound described in claim 1, and monochromatic photon-electron transformation efficiency can reach 80% ~ 90%, and photoelectric transformation efficiency reaches 10.0 ~ 11.0%.
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| CN1359901A (en) * | 2000-12-21 | 2002-07-24 | 中国科学院感光化学研究所 | Ru-polypyridine complex and its synthesizing process and use |
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| CN1359901A (en) * | 2000-12-21 | 2002-07-24 | 中国科学院感光化学研究所 | Ru-polypyridine complex and its synthesizing process and use |
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| CN109923104A (en) * | 2016-07-29 | 2019-06-21 | 西蒙弗雷泽大学 | Stable poly- (imidazoles) hydroxide |
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