CN106046009B - Triphenylamine supplied for electronic group's zinc protoporphyrin and its synthesis and the application as dye sensitizing agent - Google Patents
Triphenylamine supplied for electronic group's zinc protoporphyrin and its synthesis and the application as dye sensitizing agent Download PDFInfo
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- CN106046009B CN106046009B CN201610376224.1A CN201610376224A CN106046009B CN 106046009 B CN106046009 B CN 106046009B CN 201610376224 A CN201610376224 A CN 201610376224A CN 106046009 B CN106046009 B CN 106046009B
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- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 title claims abstract description 43
- FUTVBRXUIKZACV-UHFFFAOYSA-J zinc;3-[18-(2-carboxylatoethyl)-8,13-bis(ethenyl)-3,7,12,17-tetramethylporphyrin-21,24-diid-2-yl]propanoate Chemical compound [Zn+2].[N-]1C2=C(C)C(CCC([O-])=O)=C1C=C([N-]1)C(CCC([O-])=O)=C(C)C1=CC(C(C)=C1C=C)=NC1=CC(C(C)=C1C=C)=NC1=C2 FUTVBRXUIKZACV-UHFFFAOYSA-J 0.000 title claims abstract description 41
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 10
- 230000001235 sensitizing effect Effects 0.000 title claims abstract description 10
- 150000004032 porphyrins Chemical class 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 206010070834 Sensitisation Diseases 0.000 claims abstract description 10
- 230000008313 sensitization Effects 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 57
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 23
- 239000012043 crude product Substances 0.000 claims description 22
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 20
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 17
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 10
- 150000004054 benzoquinones Chemical class 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 150000003233 pyrroles Chemical class 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- AKOIGRUAHVCABP-UHFFFAOYSA-N COC=1C=C(C=O)C=C(C1)OC.CCCC[O] Chemical class COC=1C=C(C=O)C=C(C1)OC.CCCC[O] AKOIGRUAHVCABP-UHFFFAOYSA-N 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- FZRCKLPSHGTOAU-UHFFFAOYSA-N 6-amino-1,4-dimethylcyclohexa-2,4-diene-1-carbaldehyde Chemical compound CC1=CC(N)C(C)(C=O)C=C1 FZRCKLPSHGTOAU-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 239000003012 bilayer membrane Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- -1 4- butyl Chemical group 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 190000032366 Miboplatin Chemical compound 0.000 claims 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims 1
- 239000012298 atmosphere Substances 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229950002777 miboplatin Drugs 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000001338 self-assembly Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 4
- 238000000862 absorption spectrum Methods 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000010970 precious metal Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229960001866 silicon dioxide Drugs 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 244000061458 Solanum melongena Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000005805 dimethoxy phenyl group Chemical group 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000029553 photosynthesis Effects 0.000 description 2
- 238000010672 photosynthesis Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000010351 charge transfer process Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 210000004276 hyalin Anatomy 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
A kind of application the invention discloses triphenylamine for the synthesis of group zinc protoporphyrin and with holdfast molecule axial direction Coordinate self-assembly as dye sensitizing agent in preparing dye-sensitized solar cells, belongs to chemosynthesis technical field and dye-sensitized solar cells technical field.The present invention is using triphenylamine as electron-donating group, since its structure is special, it can effectively inhibit the aggregation of dye molecule, be introduced into dye sensitization porphyrin dye, there is good light, thermally and chemically stability as stronger donor set, have very strong characteristic electron absorption spectrum in visible region.Therefore, can be as the excellent sensitizer of dye-sensitized solar cells, then carry out axial coordination self assembly with holdfast porphyrin and constitute sensitization solar battery, under the irradiation of standard light, these batteries have the ability for outwardly loading output current, further promote photoelectric conversion efficiency.Compared with traditional ruthenium dye, raw material is simple and easy to get, need not use precious metal material, and environmental pollution is small.
Description
Technical field
The present invention relates to a kind of triphenylamine supplied for electronic group zinc protoporphyrin synthetic methods, and the invention further relates to the supplied for electronic porphyrins
Application with holdfast molecule axial direction Coordinate self-assembly as dye sensitizing agent in preparing dye-sensitized solar cells, belonging to
Learn synthesis technical field and dye-sensitized solar cells technical field.
Background technology
Since modern society causes global warming, the natural calamities such as environmental pollution more next the excavation of fossil fuel
More people are absorbed in regenerative resource.Solar cell is a kind of clean energy resource, it can build supermolecule photosynthesis frame
Remove simulation photoinduction energy and charge transfer process.It is well known that Porphyrin Molecule can collect solar energy during photosynthesis,
Realize photoinduction transfer so that solar energy is converted into electric energy.Porphyrin is the Conjugate macrocycle compound with 18 electron systems.Due to
Its structural particularity is easy to modify, can be by being chemically incorporated into different substituent groups.
Porphyrin self-assembly system, such as energy, electronics and hole transfer, receive prodigious concern.Because porphyrin is from group
Dress system can effectively make separation of charge and separate charge carrier, and porphyrin self-assembly system utilizes the central metal of metalloporphyrin
Axial coordination is realized with ligand, can further be controlled the direction of dye units in this way, be realized long separation of charge, to a system
The success of row porphyrin assembly is orderly to be assembled in electrode surface.
Triphenylamine and its derivative have unique free radical property, and connected group is larger around nitrogen-atoms so that three
The tension at aniline free radical center is eliminated, and increases its stability, in addition, larger steric hindrance factor is also unfavorable for
Free radical reacts, and hyperconjugation electronic effect also further increases the stability of free radical.This unique free mafic
Matter makes triphenylamine and its derivative have higher hole mobility and good transmission performance, therefore is widely used in
Photoelectric material and hole mobile material.However trianilino group is used for the synthesis of porphyrin light-sensitive coloring agent not yet as electron-donating group
It appears in the newspapers.
Invention content
The object of the present invention is to provide a kind of triphenylamine supplied for electronic group zinc protoporphyrins；
It is a further object of the present invention to provide a kind of synthetic methods of triphenylamine supplied for electronic group zinc protoporphyrin；
There are one prior purposes by the present invention, are just to provide triphenylamine supplied for electronic group's zinc protoporphyrin and holdfast porphyrin
Application of the axial coordination self assembly as dye sensitizing agent in preparing dye-sensitized solar cells.
One, triphenylamine supplied for electronic group zinc protoporphyrin
The structure of triphenylamine supplied for electronic of the present invention group zinc protoporphyrin is as follows：
。
Two, the synthesis of triphenylamine supplied for electronic group zinc protoporphyrin
The synthesis of triphenylamine supplied for electronic of the present invention group zinc protoporphyrin, comprises the following steps that：
（1）The synthesis of 2,2 '-((- 3,5 Dimethoxyphenyl of 4- methoxyl groups) methylene) dipyrrylmethanes：In argon atmospher
Under enclosing, by pyrroles（Not only it had made solvent but also had served as reactant）With 4- butyl oxygen -3,5- dimethoxy benzaldehydes with 25:1~30:1 rubs
Simultaneously than mixing room temperature is protected from light 10 ~ 15min of stirring for you；Add catalyst trifluoroacetic acid, reacting at normal temperature without light 5 ~ 6 hours, reaction
After with triethylamine quench react, boil off solvent, after being evaporated obtain crude product；Crude product is dissolved with dichloromethane,
Column chromatography for separation, it is 2,2 '-((4- methoxyl groups -3,5 Dimethoxyphenyl) methylene) two pyrroles's first to obtain pale yellow powder
Alkane.
The molar ratio of 4- butyl oxygen -3,5- dimethoxy benzaldehydes and catalyst trifluoroacetic acid is 140:1~150:1.
（2）The synthesis of free alkali porphyrin：By 2,2 '-((- 3,5 Dimethoxyphenyl of 4- methoxyl groups) methylene) two pyrroles's first
Alkane is dissolved in 4- diphenylamines benzaldehyde or paradime thylaminobenzaldehyde in dichloromethane solution, and catalyst trifluoro second is added
Acid, 30 ~ 40min of stirring at normal temperature in argon atmosphere, adds oxidant 2, bis- chloro- 5,6- dicyanos-Isosorbide-5-Nitrae benzoquinones of 3-, room temperature stirs
It mixes reaction 1 ~ 2 hour, waits for after reaction, removing solvent, continuously adding equivalent oxidant 2, bis- chloro- 5,6- dicyanos-Isosorbide-5-Nitraes of 3-
The toluene solution of benzoquinones is heated to 90 ~ 100 DEG C, reacts 1 ~ 1.5h；Wait for that temperature is down to 70 ~ 80 DEG C, vacuum distillation removes toluene and obtains
Crude product；Crude product is dissolved with dichloromethane, column chromatography for separation, obtains purple free alkali porphyrin.
2,2 '-((- 3,5 Dimethoxyphenyl of 4- methoxyl groups) methylene) dipyrrylmethanes and 4- diphenylamines benzaldehyde or
The molar ratio of paradime thylaminobenzaldehyde is 1:1~1:1.5.
2,2 '-((- 3,5 Dimethoxyphenyl of 4- methoxyl groups) methylene) dipyrrylmethanes rub with catalyst trifluoroacetic acid
You are than being 1:1.5~1:2.
2,2 '-((- 3,5 Dimethoxyphenyl of 4- methoxyl groups) methylene) dipyrrylmethanes and oxidant 2,3- bis- chloro- 5,
The molar ratio of -1,4 benzoquinones of 6- dicyanos is 1:2.5~1:3.
（3）The synthesis of triphenylamine supplied for electronic group zinc protoporphyrin
Free alkali porphyrin is dissolved in chloroform soln, the methanol solution of zinc acetate, 65 ~ 75 DEG C of reflux 4 ~ 5 are added
Hour, cooling room temperature, solvent evaporated is washed with dichloromethane solution, and 5% sodium bicarbonate solution is used in combination to extract, collected organic layer,
Anhydrous sodium sulfate is dried, and crude product is obtained；Crude product uses column chromatography, and obtains target product --- triphenylamine supplied for electronic group
Zinc protoporphyrin.The molar ratio of free alkali porphyrin and zinc acetate is 1:4~1:5.
Three, structure and the optical property analysis of triphenylamine electron-donating group zinc protoporphyrin
Fig. 1 is that ultraviolet-visible of the triphenylamine electron-donating group zinc protoporphyrin of the invention synthesized in chloroform soln is inhaled
Receive spectrum.From figure 1 it appears that porphyrin ring structure has the absorption peak of very feature on ultraviolet spectra, the strong suction near 430nm
It receives peak and is known as Soret bands（That is B bands）, several weak absorbings of 500~700nm ranges are Q bands.The ultraviolet light of tetrazole zinc protoporphyrin
The characteristic absorption peak that porphyrin ring is significantly shown in spectrum has stronger Soret bands to absorb, 560nm and 600nm at 430nm
Nearby there are two weaker Q bands to absorb.Uv-visible absorption spectra explanation, the different supplied for electronic metals that the present invention synthesizes
Zinc protoporphyrin is consistent with the structure of the compound of design.
Four, triphenylamine electron-donating group porphyrin and holdfast porphyrin axial coordination self assembly prepare dye-sensitized solar cells
First by TiO2CHCl of the nanostructure bilayer membrane electrode in the holdfast porphyrin (ZnPA) of 0.3 ~ 2mmol3/EtOH (10/
90, v/v) it is impregnated 2 ~ 24 hours in solution；Washing, after drying, then in the triphenylamine electron-donating group porphyrin of 0.15 ~ 0.2mmol
CHCl3It is impregnated 1 ~ 2 hour in/DMF (85/15, v/v) solution, to ensure the 90% above coverage rate；Washing is taken out, is dried in the air
It is melting sealed with the glass electrode heating of Platinum Nanoparticles after dry, finally electrolyte is injected into the gap of two electrodes, i.e.,
It may make up dye-sensitized solar cells.
The structural formula of holdfast porphyrin (ZnPA) is：
Fig. 2 is triphenylamine supplied for electronic porphyrin axial coordination self assembling process schematic diagram.As seen from Figure 2, holdfast porphyrin
(ZnPA) molecule is bundled in TiO with carboxylic acid2Electrode surface, triphenylamine supplied for electronic porphyrin is with central metal zinc and holdfast porphyrin ligand
Axial coordination self assembly is formed by coordinate bond.This self assembly mode can further increase the efficiency of electron transmission, to
Further promote photoelectric conversion efficiency.Therefore, dye-sensitized solar cells can be used to prepare as photosensitizer.Triphenylamine
Supplied for electronic porphyrin is combined with holdfast porphyrin (ZnPA) by metal-ligand axial coordination self assembly, then with titanium deoxid film.
Fig. 3 is the curve graph of the current density and voltage relationship of the dye-sensitized solar cells of above-mentioned preparation.From Fig. 3
As can be seen that there is higher output current by the porphyrin assembly dyestuff of electron-donating group of triphenylamine, it is primarily due to three
Aniline has stronger electron supplying capacity, so having preferable current density.
Fig. 4 is the IPCE figures of the dye-sensitized solar cells of above-mentioned preparation.Figure 4, it is seen that triphenylamine is powered
Subbase group porphyrin dye has higher IPCE values under same illumination condition, this is because trianilino group can be effective after introducing
The aggregation for inhibiting dye molecule, so it is with preferable IPCE.
In conclusion the present invention can effectively be pressed down as electron-donating group since its structure is special using triphenylamine for group
The aggregation of system dye molecule is introduced into dye sensitization porphyrin dye, as stronger donor set have good light, heat and
Chemical stability has very strong characteristic electron absorption spectrum in visible region.It therefore, can be as dye sensitization of solar electricity
The excellent sensitizer in pond, then carry out axial coordination self assembly with holdfast porphyrin and constitute sensitization solar battery, it is irradiated in standard light
Under, these batteries have the ability for outwardly loading output current, further promote photoelectric conversion efficiency.With traditional ruthenium dye
It compares, raw material is simple and easy to get, need not use precious metal material, and environmental pollution is small.
Description of the drawings
Fig. 1 is that ultraviolet-visible of the triphenylamine supplied for electronic group zinc protoporphyrin of the invention synthesized in chloroform soln is inhaled
Receive spectrum.
Fig. 2 is the triphenylamine supplied for electronic group's zinc protoporphyrin and holdfast porphyrin axial coordination self assembling process that the present invention synthesizes
Schematic diagram.
Fig. 3 is the electric current of the solar cell prepared using triphenylamine supplied for electronic of the present invention group's zinc protoporphyrin as dye sensitizing agent
The curve graph of density and voltage relationship.
Fig. 4 is the IPCE of the solar cell prepared using triphenylamine supplied for electronic of the present invention group's zinc protoporphyrin as dye sensitizing agent
Figure.
Specific implementation mode
Below by specific embodiment to the synthesis of triphenylamine supplied for electronic of the present invention group zinc protoporphyrin, structure and as dyestuff
The application of sensitizer preparationization solar cell is described further.
Embodiment one
1, the synthesis of triphenylamine supplied for electronic group zinc protoporphyrin (ZnP1)
（1）The synthesis of 2,2 '-((- 3,5 Dimethoxyphenyl of 4- methoxyl groups) methylene) dipyrrylmethanes：It will newly distill
Pyrroles (360mmol, 25mL) and 4- butyl oxygen -3,5- dimethoxy benzaldehyde (4- butyl oxygen -3,5- dimethoxy benzaldehydes
Synthesized reference document：Helvetica Chimica Acta.2002, 85:3019-3025) (14.4mmol, 3.42g) is mixed
It closes, is protected from light stirring 10 minutes in argon atmosphere, room temperature, adds the trifluoroacetic acid of (0.1mmol, 0.12mL), it is anti-to be protected from light room temperature
It answers 6 hours, waits for after reaction, adding the quenching reaction of 2mL triethylamines, boiling off pyrroles（It is both solvent and reaction
Object）, crude product is obtained after being evaporated, crude product is dissolved with dichloromethane, and crude product is loaded on silicagel column (diameter 5cm × long 15cm)
First layer buffy layer is collected, pale yellow powder target product is obtained with dichloromethane eluent in end --- 2,2 '-((4- methoxyl groups-
3,5 Dimethoxyphenyls) methylene) dipyrrylmethanes, yield：65.3%.
Product, the nuclear magnetic data of dipyrrylmethanes (b) are detected using Varian types Nuclear Magnetic Resonance (600M)：1H NMR
(600 MHz, CDCl3) δ 6.69 (dd, 2H), 6.40 (s, 2H), 6.15 (d, 2H), 5.99-5.91 (m,
2H), 5.40 (s, 1H), 3.94 (t, 2H), 3.73 (s, 6H), 1.75-1.69 (m, 2H), 1.46 (dd,
2H), 0.94 (t, 3H)。
（2）The synthesis of free alkali porphyrin P1：By 2,2 '-((- 3,5 Dimethoxyphenyl of 4- methoxyl groups) methylene) two pyrroles
Methane (1mmol, 0.35g) is dissolved in 4- diphenylamines benzaldehyde (1mmol, 0.27g) in 100mL dichloromethane solutions, is added
Enter catalyst trifluoroacetic acid (1.5mmol, 0.12mL), 2,3-, bis- chloro- 5,6- bis- are added in stirring at normal temperature 30 minutes in argon atmosphere
Cyano-Isosorbide-5-Nitrae benzoquinones (DDQ) 0.57g reacts 1 hour in stirring at normal temperature, waits for after reaction, removing solvent, adding 0.57g
The toluene solution of DDQ（20~30mL）, it is heated to 90 ~ 100 DEG C of 1 ~ 1.5h of reaction；Wait for that temperature is down to 70 ~ 80 DEG C, vacuum distillation removes
Toluene is gone to obtain crude product, in methylene chloride, column chromatography for separation, silica gel crosses column to crude product for dissolving on a small quantity（Diameter 4cm × length
15cm）, with dichloromethane and petroleum ether 1:1 elution, collects second layer aubergine, obtains purple target porphyrin P1, yield：12%.
（3）The synthesis of metal zinc protoporphyrin ZnP1：Free alkali porphyrin P1 (0.2mmol, 0.255g) is dissolved in 60mL trichlorines
In dichloromethane, the 5mL methanol solutions of zinc acetate (0.8mmol, 0.175g) are added, flow back 5 hours at 70 DEG C or so, cooling chamber
Temperature, solvent evaporated are washed with dichloromethane solution, and 5% sodium bicarbonate solution is used in combination to extract, and collected organic layer uses anhydrous sodium sulfate
It is dry, obtain crude product；Crude product uses column chromatography, and obtains target product metal zinc protoporphyrin ZnP1, yield：73%.
Product, the nuclear magnetic data of zinc protoporphyrin dyestuff are detected using Varian types Nuclear Magnetic Resonance (400M)：1H NMR (400
MHz, CDCl3) δ 8.90 (d, 6H), 7.99 (s, 2H), 7.36 (d, 12H), 7.05 (s, 2H), 5.17
(s, 12H), 4.23 (s, 4H), 3.87 (s, 12H), 1.89 (s, 4H), 1.59 (d, 4H), 1.01 (t,
6H)。
The structure of ZnP1 is as follows：
2, the preparation of dye-sensitized solar cells
（1）TiO2Nanocrystalline and TiO2The preparation of nanostructure bilayer membrane electrode：In FTO electro-conductive glass (Nippon Sheet
Glass, 4 mmol thick) 7.0 μm of hyaline layers (20-nm-sized) and 5.0 μm of scattering layers in silk-screen printing (Dyesol,
The double-deck mesoporous titanium dioxide film 400-nm-sized) is made as battery cathode, specific prepare uses following bibliography
《J.Phys.Chem.B.,2003,107,14336》。
（2 Dye Adsorptions：First by TiO2Holdfast porphyrin (ZnPA) of the nanostructure bilayer membrane electrode in 0.3 ~ 2mmol
CHCl3It is impregnated 2 ~ 24 hours in/EtOH (10/90, v/v) solution；Washing, after drying, then 0.15 ~ 0.2mmol ZnP1's
CHCl3It is impregnated 1 ~ 2 hour in/DMF (85/15, v/v) solution；Washing is taken out, after drying, the above of guarantee 90% is covered in this way
Lid rate.
（3）The preparation of dye-sensitized solar cells：By the glass electrode of Platinum Nanoparticles with the TiO of absorption dyestuff2Nano junction
Structure duplicature heated by electrodes is melting sealed, is finally injected into electrolyte in the gap of two electrodes, you can constitutes dyestuff
Sensitization solar battery.Detailed device preparation method bibliography (JACS 2004,126,7164)。
（4）The performance of battery：The current density of dye-sensitized solar cells and the curve of voltage relationship are shown in Fig. 3.J is
4.65mA/cm2 , V 502mV, IPCE maximum values are 78%.
Embodiment two
1, the synthesis of supplied for electronic group of front three ammonia group zinc protoporphyrin (ZnP2)
（1）The synthesis of 2,2 '-((- 3,5 Dimethoxyphenyl of 4- methoxyl groups) methylene) dipyrrylmethanes：Same embodiment
One.
（2）The synthesis of free alkali porphyrin P2：By 2,2 '-((- 3,5 Dimethoxyphenyl of 4- methoxyl groups) methylene) two pyrroles
Methane (1mmol, 0.35g) is dissolved in paradime thylaminobenzaldehyde (1mmol, 0.15g) in 100mL dichloromethane solutions, is added
Enter catalyst trifluoroacetic acid (1.5mmol, 0.12mL), 2,3-, bis- chloro- 5,6- bis- are added in stirring at normal temperature 30 minutes in argon atmosphere
Cyano-Isosorbide-5-Nitrae benzoquinones (DDQ) 0.57g reacts 1 hour in stirring at normal temperature, waits for after reaction, removing solvent, adding 0.57g
DDQ and 20 ~ 30mL toluene solutions are heated to 90 ~ 100 DEG C of 1 ~ 1.5h of reaction；Wait for that temperature is down to 70 ~ 80 DEG C, vacuum distillation removes
Toluene obtains crude product；Crude product is dissolved in a small amount of dichloromethane, and column chromatography for separation, silica gel crosses column（Diameter 4cm × long 15cm）,
With dichloromethane and ethyl acetate 1:1 elution, collects second layer aubergine, obtains purple target porphyrin P2, yield：8%.
（3）The synthesis of metal zinc protoporphyrin ZnP2：Free alkali porphyrin P2 (0.2mmol, 0.211g) is dissolved in 60mL trichlorines
In methane, the 5mL methanol solutions of zinc acetate (0.8mmol, 0.175g) are added, flows back 4 hours at 70 DEG C or so, is cooled to room
Temperature, solvent evaporated are washed with dichloromethane solution, and 5% sodium bicarbonate solution is used in combination to extract, and collected organic layer uses anhydrous sodium sulfate
It is dry, obtain crude product；Crude product uses column chromatography, and obtains target product metal zinc protoporphyrin ZnP2, yield：70%.
Product, the nuclear magnetic data of zinc protoporphyrin dyestuff are detected using Varian types Nuclear Magnetic Resonance (400M)：1H NMR (400
MHz, CDCl3) δ 7.98-7.82 (m, 4H), 7.46 (s, 2H), 7.25 (d, 4H), 6.64 (dd, 4H),
6.38 (d, 4H), 5.40 (dd, 2H), 4.06 (m, 4H), 3.89 (dd, 12H), 3.06 (d, 12H),
1.75-1.69 (m, 4H), 1.46 (dd, 4H), 0.94 (t, 6H)。
The structure of ZnP2 is as follows：
。
2, the preparation of dye-sensitized solar cells
Preparation method is the same as embodiment one.
The performance of battery：The current density of dye-sensitized solar cells and the curve of voltage relationship are shown in Fig. 4.J is 4.323
mA/cm2 , V 502mV, IPCE maximum values are 70%.
Claims (10)
1. a kind of triphenylamine supplied for electronic group zinc protoporphyrin, structure are as follows：
。
2. the synthesis of triphenylamine supplied for electronic as described in claim 1 group zinc protoporphyrin, comprises the following steps that：
（1）The synthesis of 2,2 '-((- 3,5 Dimethoxyphenyl of 4- methoxyl groups) methylene) dipyrrylmethanes：Under argon atmosphere,
By pyrroles and 4- butyl oxygen -3,5- dimethoxy benzaldehydes with 25:1~30:1 molar ratio mixing and room temperature be protected from light stirring 10 ~
15min；Catalyst trifluoroacetic acid is added, reacting at normal temperature without light 5 ~ 6 hours is quenched with triethylamine react after reaction, subtracted
Pressure boils off solvent, and crude product is obtained after being evaporated；Crude product is dissolved with dichloromethane, and column chromatography for separation obtains pale yellow powder
As 2,2 '-((- 3,5 Dimethoxyphenyl of 4- methoxyl groups) methylene) dipyrrylmethanes；
（2）The synthesis of free alkali porphyrin：By 2,2 '-((- 3,5 Dimethoxyphenyl of 4- methoxyl groups) methylene) dipyrrylmethanes with
4- diphenylamines benzaldehyde or paradime thylaminobenzaldehyde are dissolved in dichloromethane solution, and catalyst trifluoroacetic acid, argon is added
Atmosphere encloses 30 ~ 40 min of interior stirring at normal temperature, adds oxidant 2, bis- chloro- 5,6- dicyanos-Isosorbide-5-Nitrae benzoquinones of 3-, and stirring at normal temperature is anti-
It answers 1 ~ 2 hour, waits for after reaction, removing solvent, continuously adding equivalent oxidant 2, bis- chloro- 5,6- dicyanos-Isosorbide-5-Nitrae benzoquinones of 3-
Toluene solution, be heated to 90 ~ 100 DEG C, react 1 ~ 1.5h；Wait for that temperature is down to 70 ~ 80 DEG C, vacuum distillation removing toluene, which obtains, slightly to be produced
Object；Crude product is dissolved with dichloromethane, column chromatography for separation, obtains purple free alkali porphyrin；
（3）The synthesis of triphenylamine supplied for electronic group zinc protoporphyrin：Free alkali porphyrin is dissolved in chloroform soln, acetic acid is added
The methanol solution of zinc, 65 ~ 75 DEG C are flowed back 4 ~ 5 hours, and cooling room temperature, solvent evaporated is washed with dichloromethane solution, and 5% carbon is used in combination
Sour hydrogen sodium solution extraction, collected organic layer, anhydrous sodium sulfate drying obtain crude product；Crude product uses column chromatography, and obtains mesh
Mark product --- triphenylamine supplied for electronic group zinc protoporphyrin.
3. the synthesis of triphenylamine supplied for electronic as claimed in claim 2 group zinc protoporphyrin, it is characterised in that：Step（1）In, 4- butyl
The molar ratio of oxygen -3,5- dimethoxy benzaldehydes and catalyst trifluoroacetic acid is 140:1~150:1.
4. the synthesis of triphenylamine supplied for electronic group as claimed in claim 2 zinc protoporphyrin, it is characterised in that：Step（2）In, 2,2 '-
((- 3,5 Dimethoxyphenyl of 4- methoxyl groups) methylene) dipyrrylmethanes are with 4- diphenylamines benzaldehyde or to Dimethylaminobenzene
The molar ratio of formaldehyde is 1:1~1:1.5.
5. the synthesis of triphenylamine supplied for electronic as claimed in claim 2 group zinc protoporphyrin, it is characterised in that：Step（2）In, 2,2 '-
The molar ratio of ((- 3,5 Dimethoxyphenyl of 4- methoxyl groups) methylene) dipyrrylmethanes and catalyst trifluoroacetic acid is 1:1.5~
1:2。
6. the synthesis of triphenylamine supplied for electronic as claimed in claim 2 group zinc protoporphyrin, it is characterised in that：Step（2）In, 2,2 '-
((- 3,5 Dimethoxyphenyl of 4- methoxyl groups) methylene) dipyrrylmethanes and bis- chloro- -1,4 benzene of 5,6- dicyanos of oxidant 2,3-
The molar ratio of quinone is 1:2.5~1:3.
7. the synthesis of triphenylamine supplied for electronic as claimed in claim 2 group zinc protoporphyrin, it is characterised in that：Step（3）In, free alkali
The molar ratio of porphyrin and zinc acetate is 1:4~1:5.
8. triphenylamine supplied for electronic as described in claim 1 group's zinc protoporphyrin is preparing dye sensitization of solar as dye sensitizing agent
Application in battery.
9. triphenylamine supplied for electronic as claimed in claim 8 group's zinc protoporphyrin is preparing dye sensitization of solar as dye sensitizing agent
Application in battery, it is characterised in that：First by TiO2Holdfast porphyrin of the nanostructure bilayer membrane electrode in 0.3 ~ 2mmol
CHCl3It is impregnated 2 ~ 24 hours in/EtOH solution；Washing, after drying, then in the triphenylamine electron-donating group of 0.15 ~ 0.2mmol
The CHCl of porphyrin3It is impregnated 1 ~ 2 hour in/DMF solution, to ensure the 90% above coverage rate；Take out washing, dry after with receive
The glass electrode heating of Miboplatin is melting sealed, is finally injected into electrolyte in the gap of two electrodes, you can constitute dye
Expect sensitization solar battery.
10. triphenylamine supplied for electronic as claimed in claim 9 group's zinc protoporphyrin is preparing the dye sensitization sun as dye sensitizing agent
Application in energy battery, it is characterised in that：The structural formula of holdfast porphyrin is：
。
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| A new family of A2B2 type porphyrin derivatives: synthesis, physicochemical characterization and their application in dye-sensitized solar cells;Manas K. Panda等;《J.Mater.Chem.》;20120315;第8092-8102页，Scheme 1，Fig.1-Fig.9, Table 1 -Table 5 * |
| A Systematic Study of Electrochemical and Spectral Properties for the Electronic Interactions in Porphyrin–Triphenylamine Conjugates;Chih-Yen Huang等;《Eur.J.Inorg.Chem.》;20120130;第1038-1047页，Fig.1-7 ,Table 1-Table 3. * |
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