CN102417511A - Acylhydrazone zinc protoporphyrin, and synthesis and application of complex thereof - Google Patents
Acylhydrazone zinc protoporphyrin, and synthesis and application of complex thereof Download PDFInfo
- Publication number
- CN102417511A CN102417511A CN2011102836283A CN201110283628A CN102417511A CN 102417511 A CN102417511 A CN 102417511A CN 2011102836283 A CN2011102836283 A CN 2011102836283A CN 201110283628 A CN201110283628 A CN 201110283628A CN 102417511 A CN102417511 A CN 102417511A
- Authority
- CN
- China
- Prior art keywords
- zinc protoporphyrin
- acylhydrazone
- zinc
- methoxycarbonyl
- protoporphyrin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 72
- 238000003786 synthesis reaction Methods 0.000 title abstract 2
- 230000015572 biosynthetic process Effects 0.000 title 1
- 239000011701 zinc Substances 0.000 claims abstract description 53
- 238000002360 preparation method Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 16
- 206010070834 Sensitisation Diseases 0.000 claims description 51
- 230000008313 sensitization Effects 0.000 claims description 51
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- -1 zinc protoporphyrin compound Chemical class 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 25
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000002086 nanomaterial Substances 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 229960001701 chloroform Drugs 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- 229950003776 protoporphyrin Drugs 0.000 claims description 18
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- IARNVKSBRPYBMQ-UHFFFAOYSA-N COC(=O)C1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 Chemical compound COC(=O)C1=CC=C(C=C1)C1=C2NC(=C1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N=1)=C2 IARNVKSBRPYBMQ-UHFFFAOYSA-N 0.000 claims description 12
- JHAMVIKVDJETQA-UHFFFAOYSA-N COC(=O)C1=CC=C([Zn])C=C1 Chemical compound COC(=O)C1=CC=C([Zn])C=C1 JHAMVIKVDJETQA-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 10
- 150000003233 pyrroles Chemical class 0.000 claims description 10
- 230000001235 sensitizing effect Effects 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 8
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical group O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical group OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- QPJVMBTYPHYUOC-UHFFFAOYSA-N Methyl benzoate Natural products COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 4
- 229940095102 methyl benzoate Drugs 0.000 claims description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 121
- 150000004700 cobalt complex Chemical class 0.000 abstract description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 15
- 150000004032 porphyrins Chemical group 0.000 abstract description 14
- 239000000446 fuel Substances 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 abstract description 4
- 230000027756 respiratory electron transport chain Effects 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 13
- 239000003086 colorant Substances 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 238000000862 absorption spectrum Methods 0.000 description 8
- 238000002211 ultraviolet spectrum Methods 0.000 description 7
- GQDCUDAXOMFYFV-UHFFFAOYSA-N [Zn]C1=CC=CC=C1 Chemical compound [Zn]C1=CC=CC=C1 GQDCUDAXOMFYFV-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 125000001824 selenocyanato group Chemical group *[Se]C#N 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- QCWPXJXDPFRUGF-UHFFFAOYSA-N N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 Chemical compound N1C=2C=C(N=3)C=CC=3C=C(N3)C=CC3=CC(=N3)C=CC3=CC1=CC=2C1=CC=CC=C1 QCWPXJXDPFRUGF-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- MVDKKZZVTWHVMC-UHFFFAOYSA-N 2-hexadecylpropanedioic acid Chemical compound CCCCCCCCCCCCCCCCC(C(O)=O)C(O)=O MVDKKZZVTWHVMC-UHFFFAOYSA-N 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000005518 carboxamido group Chemical group 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Images
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
- C09B47/00—Porphines; Azaporphines
-
- 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
- C09B55/00—Azomethine dyes
- C09B55/005—Disazomethine dyes
- C09B55/006—Disazomethine dyes containing at least one heteroring
-
- 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
-
- 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
- H10K85/381—Metal complexes comprising a group IIB metal element, e.g. comprising cadmium, mercury or zinc
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses an acylhydrazone zinc protoporphyrin and a zinc and cobalt complex thereof, belonging to the field of chemical synthesis. In the acylhydrazone zinc protoporphyrin, an acylhydrazone structure and a porphyrin structure form a large conjugated system which can absorb a wider range of sunlight as compared with most of porphyrin dyes; and in the zinc and cobalt complex of the acylhydrazone zinc protoporphyrin, acylhydrazone zinc protoporphyrin molecules are connected to form a chain structure or high-dimensional structure, thereby improving the electron transfer efficiency and consequently improving the photoelectric conversion efficiency. Thus, the zinc and cobalt complex can be used as a dye sensitizer for the preparation of fuel-sensitive solar cells. Photoelectric property test results show that the fuel-sensitive solar cells prepared by the invention are capable of outputting a certain current to an external load and have different degrees of photoelectric conversion efficiency under the irradiation of standard light; and for the photocell using the zinc complex of the zinc protoporphyrin acylhydrazone as the dye, the maximum IPCE (Incident Photon to Current Efficiency) value is 13.4%.
Description
Technical field
The invention belongs to chemosynthesis technical field, relate to the compound method of a kind of porphyrins and metal complexes thereof, relate in particular to the compound method of a kind of acylhydrazone zinc protoporphyrin and zinc thereof, chromic compound; The invention still further relates to this acylhydrazone zinc protoporphyrin and zinc thereof, chromic compound as the application of dye sensitizing agent in the preparation dye sensitization solar battery.
Background technology
Energy dilemma is the pressing problem that human survival and development are faced.Traditional energy coal, oil and timber can only be kept 50 to 100 years by present spending rate.In addition, the environmental pollution that is brought is thus also threatening the human earth of depending on for existence.Sun power is as a kind of inexhaustible, distribute extensive, convenient utilization, eco-friendly renewable energy source, and is increasingly high to the cry of its development and use.Utilization and conversion solar are important channels that solves worldwide energy dilemma and environmental problem.
Porphyrin is the conjugation macrocylc compound with 18 electron systems that is linked to each other and form through methylene radical by four pyrrole rings.Its molecule ligancy is outstanding, and atoms metal nearly all on the periodictable can both form the metalloporphyrin title complex with the nitrogen-atoms coordination at center.Around the porphyrin molecule, two types of the position of substitution are arranged, different substituting groups can be introduced through chemical process in position (meso) and β position between being respectively.Porphyrin compound has good light, heat and chemicalstability, at visible region very strong characteristic electronic absorption spectroscopy is arranged.Therefore, utilize porphyrin and title complex thereof unique electronic structure and photoelectric properties, the synthetic solar cell light-sensitive coloring agent of design has become in the world very active research field.The transformation efficiency of the porphyrin light-sensitive coloring agent that great majority have been reported is also only between 5%～7%; People such as professor Ye Zhenyu up to Taiwan in 2010 have synthesized a kind of D-A porphyrin; Its transformation efficiency reaches 11% rare (Angew.Chem.Int.Ed.2010; 49,6646-6649), this also is the non-ruthenium organic dye with so high transformation efficiency of the first example report.
Summary of the invention
The objective of the invention is the low defective of transformation efficiency, a kind of acylhydrazone zinc protoporphyrin and title complex thereof are provided to prior art NSC 19665 light-sensitive coloring agent.
Another object of the present invention provides the compound method of a kind of acylhydrazone zinc protoporphyrin and title complex thereof.
A further object of the invention just provides this acylhydrazone zinc protoporphyrin and title complex thereof as the application of dye sensitizing agent in the preparation dye sensitization solar battery.
(1) structure of acylhydrazone zinc protoporphyrin and title complex thereof
The chemical structure of general formula of acylhydrazone zinc protoporphyrin is:
Wherein, R is 2-pyridylaldehyde, salicylic aldehyde, 2-acetyl benzoglyoxaline.
In the acylhydrazone zinc protoporphyrin, acylhydrazone structure and porphyrin structure form big conjugated system, can make the natural raising of its electricity conversion so that its absorption to sunshine is wideer.Meso position on the acylhydrazone zinc protoporphyrin meets the N on the group; Elements such as O all can form coordination with different metallic; The coordination metal can couple together acylhydrazone zinc protoporphyrin molecule and form chain-like structure or higher-dimension structure, has improved the efficient of electron transport, and then improves electricity conversion.
(2) acylhydrazone zinc protoporphyrin and title complex thereof is synthetic
1, the compound method of acylhydrazone zinc protoporphyrin comprises following process step:
(1) 5,10,15,20-four (4-methoxycarbonyl) phenyl porphyrin synthetic
Pyrroles and the 4-acyl radical methyl benzoate mol ratio with 1:1 ~ 1:1.2 is dissolved in the methylene dichloride, and the methanesulfonic that adds 0.6 ~ 0.7 times of pyrroles's molar weight is as catalyzer, room temperature reaction 25 ~ 30 minutes; The dichloro dicyan para benzoquinone (oxygenant) that adds 0.8 ~ 0.9 times of pyrroles's molar weight evenly stirs, and adds in the triethylamine then and methanesulfonic, makes pH=6.8 ~ 7.2 of system; The reaction solution that obtains contracts through revolving inspissation, the methylene dichloride wash-out, and drying promptly gets purple powdery product 5,10,15,20-four (4-methoxycarbonyl) phenyl porphyrin.
(2) 5,10,15,20-four (4-methoxycarbonyl) phenyl zinc protoporphyrin synthetic
With 5,10,15,20-four (4-methoxycarbonyl) phenyl porphyrin is dissolved in the trichloromethane, adds Zn (OAc)
22H
2The methanol solution of O, back flow reaction 3 ~ 5 hours; Solvent evaporated is collected the red-purple solid, and with ethanol, water washing, drying gets product 5,10,15,20-four (4-methoxycarbonyl) phenyl zinc protoporphyrin; Said Zn (OAc)
22H
2The concentration of the methanol solution of O is 0.1 ~ 0.15mol/L, Zn (OAc)
22H
2The consumption of O is 5,10,15,4 ~ 5 times of 20-four (4-methoxycarbonyl) phenyl porphyrin molar weight.
(3) 5,10,15, the basic zinc protoporphyrin of 20-four (4-benzoyl hydrazine) synthetic
With 5,10,15,20-four (4-methoxycarbonyl) phenyl zinc protoporphyrin stirring and dissolving is dissolved in Hydrazine Hydrate 80 in the ethanol in trichloromethane, stir and to mix these two kinds of solution down, and with this mixed solution 70 ~ 80 ℃ of refluxed 20 ~ 24 hours; Revolve inspissation after reaction finishes and contract, separate out green precipitate with zero(ppm) water, suction filtration, filter cake water, trichloromethane wash respectively; 70 ~ 80 ℃ of freeze-day with constant temperature are collected blackish green product 5,10,15, the basic zinc protoporphyrin of 20-four (4-benzoyl hydrazine).
Said 5,10,15, the molar weight of 20-four (4-methoxycarbonyl) phenyl zinc protoporphyrin and Hydrazine Hydrate 80 is than being 1:4 ~ 1:5;
(4) acylhydrazone zinc protoporphyrin compound is synthetic
With 5,10,15, the basic zinc protoporphyrin stirring and dissolving of 20-four (4-benzoyl hydrazine) is in DMF; With 5,10,15, nitrogen heterocyclic aldehyde or azepine cyclic ketones that the basic zinc protoporphyrin molar weight of 20-four (4-benzoyl hydrazine) is 4 ~ 5 times are dissolved in the ethanol; Stir and to mix above-mentioned two kinds of solution down, 70 ~ 80 ℃ of refluxed 7 ~ 8 hours; Remove after reaction is accomplished and desolvate, separate out deposition with ether, suction filtration, recrystallization, the collecting precipitation powder obtains acylhydrazone zinc protoporphyrin compound;
Said nitrogen heterocyclic aldehyde is 2-pyridylaldehyde or salicylic aldehyde, and said azepine cyclic ketones is a 2-acetyl benzoglyoxaline.
Its synthetic route is following:
2, acylhydrazone zinc protoporphyrin title complex is synthetic
In 60 ~ 70 ℃ ethanol, add the acylhydrazone zinc protoporphyrin, stirring and refluxing is fully dissolved it; Add Zn (NO then
3)
26H
2O or Co (NO
3)
26H
2The ethanolic soln of O refluxed 0.75 ~ 1 hour; Reaction finishes the back except that desolvating, and with-10 ~ 0 ℃ ethanol supersound washing, with the ether flushing, drying obtains pressed powder to pressed powder, is acylhydrazone zinc protoporphyrin title complex more earlier.
Zn (NO
3)
26H
2O or Co (NO
3)
26H
2The concentration of the ethanolic soln of O is 1 ~ 1.5 mmol/L, Zn (NO
3)
26H
2O or Co (NO
3)
26H
2The consumption of O is 4 ~ 5 times of acylhydrazone zinc protoporphyrin molar weight.
Aforesaid method synthetic acylhydrazone zinc protoporphyrin and title complex thereof detect through ultraviolet, nuclear-magnetism, and be consistent with the structure of the compound that designs, and shows and synthesize successfully.
(3) the photoelectric properties analysis of acylhydrazone zinc protoporphyrin and zinc thereof, cobalt complex
Fig. 1,2,3 is respectively dyestuff I of the present invention, II, the uv-visible absorption spectra of III in DMF.As can be seen from the figure, porphyrin ring structure has the very absorption of characteristic on UV spectrum, and near the strong absorption peak the 420nm is called Soret band (being the B band), is absorbed as the Q band a little less than several of 500～750nm scope.When not forming metalloporphyrin, the Q of porphyrin has four absorption peaks; After forming metalloporphyrin, because the symmetry of molecular structure increases, Q band absorption peak number reduces one or two usually.Significantly demonstrate the characteristic absorbance of porphyrin ring on the UV spectrum of three kinds of acylhydrazone zinc protoporphyrins, Soret with on strong absorption all appear at the 430nm place; Owing to formed zinc protoporphyrin, the absorption peak number of Q band becomes two, but all appears at 561nm and 601nm place.The absorption peak medium on the weak side at the 310nm that occurs respectively on three's UV spectrum in addition,, 326nm, 327nm place is owing to the conjugation group carboxamido-group in the acylhydrazone structure (CO-NH-).
Fig. 4 is dyestuff I of the present invention and the uv-visible absorption spectra comparison diagram of Zn complex in DMF thereof.The UV spectrum of dyestuff I and its Zn complex relatively, the Soret band of finding Zn complex absorb with respect to the Soret band absorption of dyestuff I slightly to be widened and small red shift has all taken place; The influence that the position of two weak absorption peaks of Q band receives is little.Can confirm basically also that thus we have obtained the Zn complex of dyestuff I.
Fig. 5 is dyestuff I of the present invention and the uv-visible absorption spectra comparison diagram of cobalt complex in DMF thereof.The UV spectrum of dyestuff I and its cobalt complex relatively, we find that the Soret band of cobalt complex absorbs with respect to the Soret band absorption of dyestuff I and slightly widen and small red shift taken place; The influence that the position of two weak absorption peaks of Q band receives is little.Can confirm basically also that thus we have obtained the cobalt complex of dyestuff I.
In sum, acylhydrazone zinc protoporphyrin of the present invention and zinc, cobalt complex have good photoelectric properties, compare with traditional ruthenium dye, and raw material is simple and easy to, and need not to use the expensive metal raw material, and environmental pollution is low.Because the big conjugated system of its acylhydrazone and porphyrin makes that its absorption to sunshine is wideer, surpass most of porphyrin dye.Therefore, it can be used as dye sensitizing agent and is used to prepare the fuel sensitization solar battery.
(4) with acylhydrazone zinc protoporphyrin and title complex thereof be the fuel sensitization solar battery of dye sensitizing agent preparation
Method 1: dyestuff axial coordination method: earlier with TiO
2Nanostructure duplicature electrode is at the holdfast molecule of 0.3 ~ 2mmol---soak 1 ~ 24h in the benzoic aqueous solution of 4-[(pyridyl-4-methyl) amino]; Washing after drying, is soaked 1 ~ 24h again in the DMF solution of the zinc of the chloroform soln of the acylhydrazone zinc protoporphyrin of concentration 1.5 ~ 2.5mmol or acylhydrazone zinc protoporphyrin, cobalt complex; At this moment, holdfast molecule and dye molecule are adsorbed on the electrode with the mode of axial coordination, and can guarantee 90% above fraction of coverage; Washing is after drying, with the same TiO of the glass electrode of nanometer platinum
2Nanostructure duplicature heated by electrodes is melting sealed, at last electrolyte is injected in the slit of two electrodes, promptly constitutes dye sensitization solar battery.
Method 2: dyestuff side-on coordination method: with TiO
2Nanostructure duplicature electrode is at the holdfast molecule of 0.3 ~ 2mmol---soak 1 ~ 24h in the benzoic aqueous solution of 4-[(pyridyl-4-methyl) amino]; Washing is after drying, again at the metal-salt (Zn (NO of concentration 1.5 ~ 2.5 mmol
3)
26H
2O or Co (NO
3)
26H
2O etc.) soak 1 ~ 24h in the aqueous solution, washing is dried the back and in the DMF solution of the zinc of the chloroform soln of the acylhydrazone zinc protoporphyrin of concentration 1.5 ~ 2.5 mmol or acylhydrazone zinc protoporphyrin, cobalt complex, is soaked 1 ~ 24h; At this moment, anchoring molecule and metal, dye molecule just are adsorbed on the electrode with the mode of side-on coordination, and can guarantee 90% above fraction of coverage, then with the same TiO of the glass electrode of nanometer platinum
2Nanostructure duplicature heated by electrodes is melting sealed; At last electrolyte is injected in the slit of two electrodes, has promptly constituted dye sensitization solar battery.
(5) performance test of fuel sensitization solar battery
Fig. 7 is that dyestuff I of the present invention, II, III are according to the current density of the dye sensitization solar battery of method 1 preparation and the graphic representation of voltage relationship.As can be seen from the figure, the dyestuff I has current density bigger under the same voltage conditions, and this also is that various structure causes the difference that electron transport efficient is different and cause.
Fig. 8 is dyestuff I of the present invention, II, the III IPCE figure according to the dye sensitization solar battery of method 1 preparation.As can be seen from the figure, the dyestuff I has IPCE value higher under the same illumination condition.This is owing to structure influence character causes.
Fig. 9 is that dyestuff I of the present invention, II, III are according to the current density of the dye sensitization solar battery of method 2 preparations and the graphic representation of voltage relationship.As can be seen from the figure, the dyestuff I has current density bigger under the same voltage conditions, and this also is that various structure causes the difference that electron transport efficient is different and cause.
Figure 10 is dyestuff I of the present invention, II, the III IPCE figure according to the dye sensitization solar battery of method 2 preparations.As can be seen from the figure, the dyestuff III has IPCE value higher under the same illumination condition at this moment.This possibly be to cause its IPCE value to reduce owing to polymerization has to a certain degree taken place for dye sensitization solar battery structure I, II according to method 2 preparations.
Figure 11 be dyestuff I of the present invention and zinc thereof, cobalt complex as dyestuff according to the current density of the dye sensitization solar battery of method 2 preparations and the graphic representation of voltage relationship.As can be seen from the figure, the Zn complex of dyestuff I has current density bigger under the same voltage conditions, and this is because the d10 track of Zn helps electron transport, so the current density ratio cobalt complex of its Zn complex or dyestuff itself are all good.
Figure 12 is that dyestuff I of the present invention and zinc thereof, cobalt complex are as the IPCE figure of dyestuff according to the dye sensitization solar battery of method 2 preparations.As can be seen from the figure, the Zn complex of dyestuff I has IPCE value higher under the same illumination condition, and this also is because the d10 track of Zn helps electron transport, so the IPCE value of its Zn complex is all higher than cobalt complex or dyestuff itself, reaches 13.4%.
In sum; The dye sensitization solar battery of preparation of the present invention; Under the standard light irradiation, these sensitive cells have ability from certain electric current to extraneous load that export, have electricity conversion in various degree; Wherein, be that the photronic maximum IPCE value of dyestuff is 13.4% with the Zn complex of zinc protoporphyrin acylhydrazone.
Description of drawings
Fig. 1 is the uv-visible absorption spectra of dyestuff I provided by the invention in DMF.
Fig. 2 is the uv-visible absorption spectra of dyestuff II provided by the invention in DMF.
Fig. 3 is the uv-visible absorption spectra of dyestuff III provided by the invention in DMF.
Fig. 4 is the Zn complex and the uv-visible absorption spectra comparison diagram of I in DMF of dyestuff I provided by the invention.
Fig. 5 is the cobalt complex and the uv-visible absorption spectra comparison diagram of I in DMF of dyestuff I provided by the invention.
Fig. 6 is that dyestuff I provided by the invention, II, III are according to the current density of the dye sensitization solar battery of method 1 preparation and the graphic representation of voltage relationship.
Fig. 7 is dyestuff I provided by the invention, II, the III IPCE figure according to the dye sensitization solar battery of method 1 preparation.
Fig. 8 is that dyestuff I provided by the invention, II, III are according to the current density of the dye sensitization solar battery of method 2 preparations and the graphic representation of voltage relationship.
Fig. 9 is dyestuff I provided by the invention, II, the III IPCE figure according to the dye sensitization solar battery of method 2 preparations.
Figure 10 be I provided by the invention and zinc thereof, cobalt complex as dyestuff according to the current density of the dye sensitization solar battery of method 2 preparations and the graphic representation of voltage relationship.
Figure 11 is that I provided by the invention and zinc thereof, cobalt complex are as the IPCE figure of dyestuff according to the dye sensitization solar battery of method 2 preparations.
Embodiment
(1) will newly distill the pyrroles (15mmol, 1.04mL) with the 4-acyl radical methyl benzoate (15mmol, 2.4624g) stirring and dissolving is in the 1500mL methylene dichloride; (10.4mmol 0.68mL), reacted 30 minutes to be added dropwise to methanesulfonic; (13.2mmol 3g), stirred 1 minute to add dichloro dicyan para benzoquinone; Add in the 3mL triethylamine then and methanesulfonic (MSA), make the pH=7.0 of system, reaction is accomplished.Reaction solution is revolved inspissation contract, be loaded on silicagel column (diameter 5cm * long 15cm) upper end, be eluted to solution with the methylene dichloride that contains 1% methyl alcohol and be light brown, collect whole wash-out compositions, revolve inspissation and contract; Again this liquid concentrator is loaded on alkali alumina post (diameter 5cm * long 12cm) upper end, uses the methylene dichloride wash-out, collect the purplish red chromatograph of the second layer; Revolve evaporate to dryness and promptly get purple powdery product a---5,10,15; 20-four (4-methyl-formiate base) phenyl porphyrin, productive rate: 25%.
(2) with 5,10,15, (0.4mmol, 0.3388g) stirring and dissolving adds Zn (OAc) to 20-four (4-methyl-formiate base) phenyl porphyrin in the 670mL trichloromethane
22H
2(1.6mmol's O refluxed 4 hours behind 15mL methanol solution 0.7024g).Reaction finishes solvent is revolved evaporate to dryness, collects the red-purple solid, and with ethanol, water washing for several times, drying gets product b---and 5,10,15,20-four (4-methyl-formiate base) phenyl zinc protoporphyrin, productive rate: 97%.
(3) with 5; 10,15,20-four (4-methyl-formiate base) phenyl zinc protoporphyrin (0.5mmol; 0.4560g) stirring and dissolving is in the 40mL trichloromethane; 80% Hydrazine Hydrate 80 25mL is dissolved in the 100mL ethanol with massfraction, stir and to mix these two kinds of solution down, and with this mixed solution 75 ℃ of refluxed 24 hours; Revolve inspissation after reaction finishes and contract, add an amount of zero(ppm) water, separate out a large amount of green precipitates, suction filtration, water and a small amount of trichloromethane flush cake several; 80 ℃ of freeze-day with constant temperature, collect blackish green product---5,10,15,20-four (4-hydrazide group) phenyl zinc protoporphyrin c, productive rate 98%.
(4) with 5,10,15; 20-four (4-hydrazide group) phenyl zinc protoporphyrin (0.5mmol, 0.4551g) stirring and dissolving is in 40mL DMF (N, dinethylformamide); With 2-pyridylaldehyde (4mmol; 0.3424g) be dissolved in the 30mL ethanol, stir and to mix these two kinds of solution down, and with this mixed solution 85 ℃ of refluxed.Follow the tracks of with TLC, reaction lasts 8 hours.Reaction will add an amount of ether except that desolvating after accomplishing, and leave standstill, and separate out a large amount of red-purple depositions; Suction filtration, with alcohol-water (volume ratio 1:1) recrystallization, the title product I of collecting precipitation purple powder---5; 10,15,20-four [(4-(2-pyridylaldehyde-benzoyl hydrazone)] basic zinc protoporphyrin.Productive rate 83%.
Adopt Varian type NMR (400M) testing product, the nuclear magnetic data of dyestuff I:
1H NMR (400MHz, DMSO-d
6) δ: 12.28 (s, 4H), 8.88 (d, 8H), 8.67 (d, 4H), 8.37 (s, 16H), 8.08～8.16 (m, 8H), 7.81～7.95 (m, 8H).
Its structure is following:
Step (1), (2), (3) are with embodiment 1.
(4) with 5,10,15, and 20-four (4-hydrazide group) phenyl zinc protoporphyrin (0.4mmol, 0.3640g) stirring and dissolving is in 35mL DMF; With 2-acetyl benzoglyoxaline (3.2mmol 0.5128g) is added dropwise to Glacial acetic acid min. 99.5 1.5ml (catalyzer) after being dissolved in the ethanol of 45mL60 ~ 70 ℃, stir and mix these two kinds of solution down, and with this mixed solution 105 ℃ of refluxed.Follow the tracks of with TLC, reaction lasts 16 hours.Remove after reaction is accomplished and desolvate, add an amount of ether, leave standstill; Separate out a large amount of red-purple depositions, suction filtration is with DMF-water (volume ratio 1:1) recrystallization; Collect green precipitate, 100 ℃ of freeze-day with constant temperature get product mulberry powder II---and 5; 10,15,20-four [(4-(2-acetyl benzoglyoxaline-benzoyl hydrazone)] basic zinc protoporphyrin.Productive rate 75%.
Wherein raw material (2) but the compound method reference of 2-acetyl benzoglyoxaline: Philps M. A.
J. Chem. Soc.,1982,2393-2399; Cheesman G. W. H.
J. Chem. Soc.,1964,4645-4646.
Its structure is following:
Adopt Varian type NMR (400M) testing product, the nuclear magnetic data of dyestuff II:
1H NMR (400MHz, DMSO-d
6) δ: 13.29 (s, 2H), 12.81 (s, 2H), 11.40 (s, 4H), 8.93 (d, 8H), 8.54 (s, 8H), 8.40 (s, 8H), 7.99 (d, 2H), 7.71 (t, 4H), 7.59 (d, 28H), 7.22～7.41 (m, 8H), 2.68 (d, 12H).
Step (1), (2), (3) are with embodiment 1.
(4) with 5,10,15, and 20-four (4-hydrazide group) phenyl zinc protoporphyrin (0.5mmol, 0.4550g) stirring and dissolving is in 40mL DMF; With salicylic aldehyde (4mmol 0.3908g) is dissolved in the 35mL ethanol, stir and to mix these two kinds of solution down, and with this mixed solution 100 ℃ of refluxed.Follow the tracks of with TLC, reaction lasts 6 hours.Remove after reaction is accomplished and desolvate, add an amount of ether, leave standstill, separate out a large amount of purple depositions, suction filtration, with acetone-ethanol (volume ratio 1:1) recrystallization, collecting precipitation purple powder III---5,10,15,20-four [(4-(salicylic aldehyde-benzoyl hydrazone)] basic zinc protoporphyrin.Productive rate 88%.
Its structure is following:
Adopt Varian type NMR (400M) testing product, the nuclear magnetic data of dyestuff III:
1H NMR (400MHz, DMSO-d
6) δ: 12.49 (s, 4H), 11.37 (s, 4H), 8.84 (s, 8H), 8.78 (s, 4H), 8.36 (s, 16H), 7.63 (d, 4H), 7.34 (t, 4H), 6.94～6.99 (m, 8H).
Synthesizing of embodiment 4, dyestuff I Zn complex
The acylhydrazone zinc protoporphyrin I of adding embodiment 1 preparation in 60 ~ 70 ℃ ethanol (0.1mmol, 0.1264g), stirring is fully dissolved it; Be added dropwise to Zn (NO then
3)
26H
2(0.4mmol, ethanolic soln 5mL 0.1190g) continue to reflux 1 hour O.Reaction finishes solvent is revolved evaporate to dryness, and the ethanol supersound washing that pressed powder usefulness is-10 ~ 0 ℃ is washed with ether several times again, and drying is collected the dark blackish green powder of product and promptly got productive rate 80%.
By confirming basically that with the visible UV spectrum contrast of dyestuff I dyestuff I Zn complex is synthesized in the accompanying drawing 4.
Synthesizing of embodiment 5, dyestuff I cobalt complex
The acylhydrazone zinc protoporphyrin I of adding embodiment 1 preparation in 60 ~ 70 ℃ ethanol (0.1mmol, 0.1264g), stirring is fully dissolved it; Be added dropwise to Co (NO then
3)
26H
2(0.4mmol, ethanolic soln 5mL 0.1190g) continue to reflux 1 hour O.Reaction finishes solvent is revolved evaporate to dryness, and the ethanol supersound washing that pressed powder usefulness is-10 ~ 0 ℃ is washed with ether several times again, and drying is collected the dark blackish green powder of product and promptly got productive rate 73%.
By confirming basically that with the visible UV spectrum contrast of dyestuff I dyestuff I Zn complex is synthesized in the accompanying drawing 5.
(1) TiO
2Nanocrystalline and TiO
2The preparation of nanostructure duplicature electrode: at FTO conductive glass (Nippon Sheet Glass; 4 mmol thick) 7.0 μ m transparent layers (20-nm-sized) and 5.0 μ m scattering layer (Dyesol in the silk screen printing; 400-nm-sized) process double-deck mesoporous titanium dioxide film as GND, the method for following reference is adopted in concrete preparation.(reference Wang P. et al., Enhance the performance of dye-Sensitized Solar cells by co-grafting amphiphilic sensitizer and hexadecylmalonic acid on TiO
2Nanocrystals, J. Phys. Chem. B., 2003,107,14336).
(2) dyestuff axial coordination: earlier with the TiO for preparing
2Nanostructure duplicature electrode is at the holdfast molecule of 0.3 ~ 2mmol---soak 1 ~ 24h in the benzoic aqueous solution of 4-[(pyridyl-4-methyl) amino]; Washing; After drying; In the chloroform soln of concentration 1.5 ~ 2.5mmol dyestuff I, soak 1 ~ 24h again, at this moment, holdfast molecule and dye molecule just are adsorbed on the electrode with the mode of axial coordination and can guarantee 90% above fraction of coverage; Washing after drying, is melted the same TiO of ring with the glass electrode of nanometer platinum through one the 35 thick heat of μ m
2Nanostructure duplicature heated by electrodes is melting sealed, at last electrolyte is injected in the slit of two electrodes, has promptly constituted dye sensitization solar battery.Detailed device preparation method reference (Wang P.et al., A Solvent-Free, SeCN
-/ (SeCN)
3-Based Ionic Liquid Electrolyte for High-Efficiency Dye-Sensitized Nanocrystalline Solar Cell, J. Am. Chem. Soc., 126,2004,7164).
The current density of dye sensitization solar battery and the graphic representation of voltage relationship are seen Fig. 6, and IPCE figure sees Fig. 7.
(1) TiO
2Nanocrystalline and TiO
2The preparation of nanostructure duplicature electrode: with embodiment 6.
(2) dyestuff side-on coordination: earlier with the TiO for preparing
2Nanocrystalline and TiO
2Nanostructure duplicature electrode is at the holdfast molecule of 0.3 ~ 2mmol---and soak 1 ~ 24h in 4-[(pyridyl-4-methyl) amino] benzoic acid solution, washing is after drying, again at the metal-salt Zn of 1.5 ~ 2.5mmol (NO
3)
26H
2O or Co (NO
3)
26H
2Soak 1-24h in the aqueous solution of O; Washing after drying, is soaked 1 ~ 24h in the chloroform soln of the dyestuff I of 1.5 ~ 2.5mmol, at this moment, and holdfast molecule and metal, and dye molecule just is adsorbed on the electrode with the mode of side-on coordination and also can guarantees 90% above fraction of coverage; Washing after drying, is melted the same TiO of ring with the glass electrode of nanometer platinum through one the 35 thick heat of μ m
2Nanostructure duplicature heated by electrodes is melting sealed, at last electrolyte is injected in the slit of two electrodes, has promptly constituted dye sensitization solar battery.Detailed device preparation method reference (Wang P.et al., A Solvent-Free, SeCN
-/ (SeCN)
3-Based Ionic Liquid Electrolyte for High-Efficiency Dye-Sensitized Nanocrystalline Solar Cell, J. Am. Chem. Soc., 126,2004,7164).
The current density of dye sensitization solar battery and the graphic representation of voltage relationship are seen Fig. 8, and IPCE figure sees Fig. 9.
Embodiment 8
,Dye sensitization solar battery with the preparation of dyestuff II
Replace the light-sensitive coloring agent I with the light-sensitive coloring agent II, other is with embodiment 6.
The current density of dye sensitization solar battery and the graphic representation of voltage relationship are seen Fig. 6, and IPCE figure sees Fig. 7.
Embodiment 9, with the dye sensitization solar battery of dyestuff II preparation
Replace the light-sensitive coloring agent I with the light-sensitive coloring agent II, other is with embodiment 7.
The current density of dye sensitization solar battery and the graphic representation of voltage relationship are seen Fig. 8, and IPCE figure sees Fig. 9.
Replace the light-sensitive coloring agent I with the light-sensitive coloring agent III, other is with embodiment 6.
The current density of dye sensitization solar battery and the graphic representation of voltage relationship are seen Fig. 6, and IPCE figure sees Fig. 7.
Embodiment 11, with the dye sensitization solar battery of dyestuff III preparation
Replace the light-sensitive coloring agent I with the light-sensitive coloring agent III, other is with embodiment 7.
The current density of dye sensitization solar battery and the graphic representation of voltage relationship are seen Fig. 8, and IPCE figure sees Fig. 9.
Embodiment 12, with the dye sensitization solar battery of the Zn complex of dyestuff I preparation
(1) TiO
2Nanocrystalline and TiO
2The preparation of nanostructure duplicature electrode: with embodiment 6.
(2) dyestuff axial coordination: earlier with the TiO for preparing
2Nanostructure duplicature electrode is at the holdfast molecule of 0.3 ~ 2mmol---soak 1 ~ 24h in the benzoic aqueous solution of 4-[(pyridyl-4-methyl) amino]; Washing; After drying; In the DMF solution of concentration 1.5 ~ 2.5mmol dyestuff I Zn complex, soak 1 ~ 24h again, at this moment, holdfast molecule and dye molecule just are adsorbed on the electrode with the mode of axial coordination and can guarantee 90% above fraction of coverage; Washing after drying, is melted the same TiO of ring with the glass electrode of nanometer platinum through one the 35 thick heat of μ m
2Nanostructure duplicature heated by electrodes is melting sealed, at last electrolyte is injected in the slit of two electrodes, has promptly constituted dye sensitization solar battery.
The current density of dye sensitization solar battery and the graphic representation of voltage relationship are seen Fig. 6, and IPCE figure sees Fig. 7.
Embodiment 13, with the dye sensitization solar battery of the cobalt complex of dyestuff I preparation
(1) TiO
2Nanocrystalline and TiO
2The preparation of nanostructure duplicature electrode: with embodiment 6.
(2) dyestuff side-on coordination: earlier with the TiO for preparing
2Nanocrystalline and TiO
2Nanostructure duplicature electrode is at the holdfast molecule of 0.3 ~ 2mmol---and soak 1 ~ 24h in 4-[(pyridyl-4-methyl) amino] benzoic acid solution, washing is after drying, again at the metal-salt Co of 1.5 ~ 2.5mmol (NO
3)
26H
2Soak 1-24h in the aqueous solution of O; Washing after drying, is soaked 1 ~ 24h in the DMF solution of the dyestuff I of 1.5 ~ 2.5mmol, at this moment, and holdfast molecule and metal, and dye molecule just is adsorbed on the electrode with the mode of side-on coordination and also can guarantees 90% above fraction of coverage; Washing after drying, is melted the same TiO of ring with the glass electrode of nanometer platinum through one the 35 thick heat of μ m
2Nanostructure duplicature heated by electrodes is melting sealed, at last electrolyte is injected in the slit of two electrodes, has promptly constituted dye sensitization solar battery.
The current density of dye sensitization solar battery and the graphic representation of voltage relationship are seen Figure 10, and IPCE figure sees Figure 11.
Claims (9)
1. acylhydrazone zinc protoporphyrin compound, its chemical structural formula is:
Wherein, R is 2-pyridylaldehyde, salicylic aldehyde, 2-acetyl benzoglyoxaline.
2. the compound method of acylhydrazone zinc protoporphyrin compound according to claim 1 comprises following process step:
(1) 5,10,15,20-four (4-methoxycarbonyl) phenyl porphyrin synthetic
Pyrroles and the 4-acyl radical methyl benzoate mol ratio with 1:1 ~ 1:1.2 is dissolved in the methylene dichloride, and the methanesulfonic that adds 0.6 ~ 0.7 times of pyrroles's molar weight is as catalyzer, room temperature reaction 25 ~ 30 minutes; The dichloro dicyan para benzoquinone that adds 0.8 ~ 0.9 times of pyrroles's molar weight more evenly stirs, and adds in the triethylamine then and methanesulfonic, makes pH=6.8 ~ 7.2 of system; Reaction solution contracts through revolving inspissation, the methylene dichloride wash-out, and drying gets purple powdery product 5,10,15,20-four (4-methoxycarbonyl) phenyl porphyrin;
(2) 5,10,15,20-four (4-methoxycarbonyl) phenyl zinc protoporphyrin synthetic
With 5,10,15,20-four (4-methoxycarbonyl) phenyl porphyrin is dissolved in the trichloromethane, adds Zn (OAc)
22H
2The methanol solution of O, back flow reaction 3 ~ 5 hours; Remove and desolvate, collect the red-purple solid, with ethanol, water washing, drying gets product 5,10,15,20-four (4-methoxycarbonyl) phenyl zinc protoporphyrin;
Said Zn (OAc)
22H
2Concentration 1 ~ 1.5 mmol/L of the methanol solution of O, Zn (OAc)
22H
2The consumption of O is 5,10,15,4 ~ 5 times of 20-four (4-methoxycarbonyl) phenyl porphyrin molar weight;
(3) 5,10,15, the basic zinc protoporphyrin of 20-four (4-benzoyl hydrazine) synthetic
With 5,10,15,20-four (4-methoxycarbonyl) phenyl zinc protoporphyrin stirring and dissolving is in trichloromethane; Hydrazine Hydrate 80 is dissolved in the ethanol, stir mix these two kinds of solution down after, 70 ~ 80 ℃ of refluxed 20 ~ 24 hours; Revolve inspissation and contract, separate out green precipitate with zero(ppm) water, suction filtration, filter cake water, trichloromethane wash respectively; In 70 ~ 80 ℃ of following freeze-day with constant temperature, collect blackish green product 5,10,15, the basic zinc protoporphyrin of 20-four (4-benzoyl hydrazine);
Said 5,10,15, the molar weight of 20-four (4-methoxycarbonyl) phenyl zinc protoporphyrin and Hydrazine Hydrate 80 is than being 1:4 ~ 1:5;
(4) acylhydrazone zinc protoporphyrin compound is synthetic
With 5,10,15, the basic zinc protoporphyrin stirring and dissolving of 20-four (4-benzoyl hydrazine) is in DMF; With 5,10,15, nitrogen heterocyclic aldehyde or azepine cyclic ketones that the basic zinc protoporphyrin molar weight of 20-four (4-benzoyl hydrazine) is 4 ~ 5 times are dissolved in the ethanol; Stir and to mix two kinds of solution down, 70 ~ 80 ℃ of refluxed 7 ~ 8 hours; Remove after reaction is accomplished and desolvate, separate out deposition with ether, suction filtration, recrystallization, the collecting precipitation powder obtains acylhydrazone zinc protoporphyrin compound;
Said nitrogen heterocyclic aldehyde is 2-pyridylaldehyde or salicylic aldehyde, and said azepine cyclic ketones is a 2-acetyl benzoglyoxaline.
According to claim 1 the acylhydrazone zinc protoporphyrin as dye sensitizing agent in the application of preparation in the dye sensitization solar battery.
Like the said acylhydrazone zinc protoporphyrin of claim 3 as dye sensitizing agent in the application of preparation in the dye sensitization solar battery, it is characterized in that: earlier with TiO
2Nanostructure duplicature electrode is at the holdfast molecule of 0.3 ~ 2mmol---and soak 1 ~ 24h in the benzoic aqueous solution of 4-[(pyridyl-4-methyl) amino], dry; In the acylhydrazone zinc protoporphyrin chloroform soln of 1.5 ~ 2.5mmol, soak 1 ~ 24h again; At this moment, holdfast molecule and acylhydrazone zinc protoporphyrin molecule are adsorbed on the electrode with the mode of axial coordination, and can guarantee 90% above fraction of coverage; Then with the same TiO of the glass electrode of nanometer platinum
2Nanostructure duplicature heated by electrodes is melting sealed, at last electrolyte is injected in the slit of two electrodes, promptly constitutes dye sensitization solar battery.
Like the said acylhydrazone zinc protoporphyrin of claim 3 as dye sensitizing agent in the application of preparation in the dye sensitization solar battery, it is characterized in that: with TiO
2Nanostructure duplicature electrode is at the holdfast molecule of 0.3 ~ 2mmol---and soak 1 ~ 24h in the benzoic aqueous solution of 4-[(pyridyl-4-methyl) amino], dry; Again at the (Zn (NO of 1.5 ~ 2.5mmol
3)
26H
2O or Co (NO
3)
26H
2Soak 1 ~ 24h in the aqueous solution of O, in the chloroform soln of the acylhydrazone zinc protoporphyrin of 1.5 ~ 2.5mmol, soak 1 ~ 24h then; At this moment, holdfast molecule and metal, acylhydrazone zinc protoporphyrin are adsorbed on the electrode with the mode of side-on coordination, and can guarantee 90% above fraction of coverage; At last with the same TiO of the glass electrode of nanometer platinum
2Nanostructure duplicature heated by electrodes is melting sealed, electrolyte is injected in the slit of two electrodes, has promptly constituted dye sensitization solar battery.
6. the compound method of an acylhydrazone zinc protoporphyrin title complex comprises following process step:
(1) 5,10,15,20-four (4-methoxycarbonyl) phenyl porphyrin synthetic
Pyrroles and the 4-acyl radical methyl benzoate mol ratio with 1:1 ~ 1:1.2 is dissolved in the methylene dichloride, and the methanesulfonic that adds 0.6 ~ 0.7 times of pyrroles's molar weight is as catalyzer, room temperature reaction 25 ~ 30 minutes; Add the dichloro dicyan para benzoquinone of 0.8 ~ 0.9 times of pyrroles's molar weight, evenly stirred 0.75 ~ 1.25 minute, add in the triethylamine then and methanesulfonic, make pH=6.8 ~ 7.2 of system; The reaction solution that obtains contracts through revolving inspissation, the methylene dichloride wash-out, and drying promptly gets purple powdery product 5,10,15,20-four (4-methoxycarbonyl) phenyl porphyrin;
(2) 5,10,15,20-four (4-methoxycarbonyl) phenyl zinc protoporphyrin synthetic
With 5,10,15,20-four (4-methoxycarbonyl) phenyl porphyrin is dissolved in the trichloromethane, adds Zn (OAc)
22H
2The methanol solution of O, back flow reaction 3 ~ 5 hours; Solvent evaporated is collected the red-purple solid, and with ethanol, water washing, drying gets product 5,10,15,20-four (4-methoxycarbonyl) phenyl zinc protoporphyrin; Said Zn (OAc)
22H
2The concentration of the methanol solution of O is 0.1 ~ 0.15mol/L, Zn (OAc)
22H
2The consumption of O is 5,10,15,4 ~ 5 times of 20-four (4-methoxycarbonyl) phenyl porphyrin molar weight;
(3) 5,10,15, the basic zinc protoporphyrin of 20-four (4-benzoyl hydrazine) synthetic
With 5,10,15,20-four (4-methoxycarbonyl) phenyl zinc protoporphyrin stirring and dissolving is dissolved in Hydrazine Hydrate 80 in the ethanol in trichloromethane, stir and to mix these two kinds of solution down, and with this mixed solution 70 ~ 80 ℃ of refluxed 20 ~ 24 hours; Revolve inspissation after reaction finishes and contract, separate out green precipitate with zero(ppm) water, suction filtration, filter cake water, trichloromethane wash respectively; 70 ~ 80 ℃ of freeze-day with constant temperature are collected blackish green product 5,10,15, the basic zinc protoporphyrin of 20-four (4-benzoyl hydrazine);
Said 5,10,15, the molar weight of 20-four (4-methoxycarbonyl) phenyl zinc protoporphyrin and Hydrazine Hydrate 80 is than being 1:4 ~ 1:5;
(4) acylhydrazone zinc protoporphyrin compound is synthetic
With 5,10,15, the basic zinc protoporphyrin stirring and dissolving of 20-four (4-benzoyl hydrazine) is in DMF; With 5,10,15, the nitrogen heterocyclic aldehyde or the azepine cyclic ketones of 4 ~ 5 times of amounts of the basic zinc protoporphyrin molar weight of 20-four (4-benzoyl hydrazine) are dissolved in the ethanol; Stir and to mix above-mentioned two kinds of solution down, 70 ~ 80 ℃ of refluxed 7 ~ 8 hours; Remove after reaction is accomplished and desolvate, separate out deposition with ether, suction filtration, recrystallization, the collecting precipitation powder obtains acylhydrazone zinc protoporphyrin compound;
Said nitrogen heterocyclic aldehyde is 2-pyridylaldehyde or salicylic aldehyde, and said azepine cyclic ketones is a 2-acetyl benzoglyoxaline;
(5) acylhydrazone zinc protoporphyrin title complex is synthetic
In 60 ~ 70 ℃ ethanol, add the acylhydrazone zinc protoporphyrin, stirring and refluxing is fully dissolved it; Add Zn (NO then
3)
26H
2O or Co (NO
3)
26H
2The ethanolic soln of O refluxed 0.75 ~ 1 hour; Reaction finishes the back except that desolvating, and with-10 ~ 0 ℃ ethanol supersound washing, with the ether flushing, drying obtains pressed powder to pressed powder, is acylhydrazone zinc protoporphyrin title complex more earlier;
Zn (NO
3)
26H
2O or Co (NO
3)
26H
2The concentration of the ethanolic soln of O is 1 ~ 1.5 mmol/L, Zn (NO
3)
26H
2O or Co (NO
3)
26H
2The consumption of O is 4 ~ 5 times of acylhydrazone zinc protoporphyrin molar weight.
Like the said acylhydrazone zinc protoporphyrin of claim 6 title complex as dye sensitizing agent in the application of preparation in the dye sensitization solar battery.
Like the said acylhydrazone zinc protoporphyrin of claim 7 title complex as dye sensitizing agent in the application of preparation in the dye sensitization solar battery, it is characterized in that: earlier with TiO
2Nanostructure duplicature electrode is at the holdfast molecule of 0.3 ~ 2mmol---soak 1 ~ 24h in the benzoic aqueous solution of 4-[(pyridyl-4-methyl) amino]; Washing after drying, is soaked 1 ~ 24h again in the acylhydrazone zinc protoporphyrin title complex DMF of 1.5 ~ 2.5mmol solution; At this moment, holdfast molecule and acylhydrazone zinc protoporphyrin title complex are adsorbed on the electrode with the mode of axial coordination, and can guarantee 90% above fraction of coverage; Then with the same TiO of the glass electrode of nanometer platinum
2Nanostructure duplicature heated by electrodes is melting sealed, at last electrolyte is injected in the slit of two electrodes, promptly constitutes dye sensitization solar battery.
Like the said acylhydrazone zinc protoporphyrin of claim 7 title complex as dye sensitizing agent in the application of preparation in the dye sensitization solar battery, it is characterized in that: with TiO
2Nanostructure duplicature electrode is at the holdfast molecule of 0.3 ~ 2mmol---soak 1 ~ 24h in the benzoic aqueous solution of 4-[(pyridyl-4-methyl) amino]; Washing is dried, again at the Zn of 1.5 ~ 2.5 mmol (NO
3)
26H
2O or Co (NO
3)
26H
2Soak 1 ~ 24h in the O aqueous solution, washing is dried the back and in the DMF solution of the acylhydrazone zinc protoporphyrin title complex of 1.5 ~ 2.5mmol, is soaked 1 ~ 24h; At this moment, holdfast molecule and metal, acylhydrazone zinc protoporphyrin just are adsorbed on the electrode with the mode of side-on coordination, and can guarantee 90% above fraction of coverage; Then with the same TiO of the glass electrode of nanometer platinum
2Nanostructure duplicature heated by electrodes is melting sealed; At last electrolyte is injected in the slit of two electrodes, has promptly constituted dye sensitization solar battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102836283A CN102417511B (en) | 2011-09-22 | 2011-09-22 | Acylhydrazone zinc protoporphyrin, and synthesis and application of complex thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102836283A CN102417511B (en) | 2011-09-22 | 2011-09-22 | Acylhydrazone zinc protoporphyrin, and synthesis and application of complex thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102417511A true CN102417511A (en) | 2012-04-18 |
| CN102417511B CN102417511B (en) | 2013-08-21 |
Family
ID=45942173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102836283A Expired - Fee Related CN102417511B (en) | 2011-09-22 | 2011-09-22 | Acylhydrazone zinc protoporphyrin, and synthesis and application of complex thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102417511B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827169A (en) * | 2012-09-04 | 2012-12-19 | 西安瑞联近代电子材料有限责任公司 | Novel porphyrin ligand and metal complex, preparation method and application for novel porphyrin ligand |
| CN103588677A (en) * | 2013-12-09 | 2014-02-19 | 南京信息工程大学 | 1, 2-2(benzophenone-hydrazone-yl)-acenaphthequinone-dihydrazone and preparation method thereof |
| CN105315699A (en) * | 2014-07-09 | 2016-02-10 | 财团法人工业技术研究院 | Zinc purple photosensitive dye and photoelectric conversion device thereof |
| CN105367589A (en) * | 2015-10-19 | 2016-03-02 | 桂林理工大学 | Isophthalic acid-5-silver sulfonate coordination polymer and preparation method |
| CN105399750A (en) * | 2015-12-11 | 2016-03-16 | 西北师范大学 | Tetrazole porphyrin metal complexes, synthesis thereof and applications of the metal complexes as dye sensitizing agents |
| CN105694525A (en) * | 2016-03-24 | 2016-06-22 | 西北师范大学 | Axial-coordination self-assembly metalloporphyrin dye sensitizer and preparation method thereof |
| CN107828236A (en) * | 2017-10-30 | 2018-03-23 | 江苏理工学院 | It is a kind of using hydrazides as zinc protoporphyrin dye sensitizing agent of anchoring group and preparation method thereof |
| CN108276796A (en) * | 2017-12-25 | 2018-07-13 | 阜阳师范学院 | Preparation method for the porphyrin sensitizer for building quasi- solid-state dye battery |
| CN111135871A (en) * | 2020-01-07 | 2020-05-12 | 西北大学 | Imidazole ionic liquid functionalized zinc porphyrin and application thereof |
| CN112827477A (en) * | 2020-12-31 | 2021-05-25 | 西南科技大学 | Preparation method and application of hydroxyquinone adsorbing material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235214A (en) * | 2008-02-27 | 2008-08-06 | 中国科学院长春应用化学研究所 | Organic ruthenium dye and dye sensitization solar battery |
| US20100125136A1 (en) * | 2008-11-17 | 2010-05-20 | Dc Solar Corp. A Taiwan Corporation | Porphyrin-based photosensitizer dyes for dye-sensitized solar cells |
| CN101805906A (en) * | 2010-04-15 | 2010-08-18 | 桂林理工大学 | Composite corrosion inhibitor for restraining corrosion of carbon steel in seawater and preparation method thereof |
-
2011
- 2011-09-22 CN CN2011102836283A patent/CN102417511B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101235214A (en) * | 2008-02-27 | 2008-08-06 | 中国科学院长春应用化学研究所 | Organic ruthenium dye and dye sensitization solar battery |
| US20100125136A1 (en) * | 2008-11-17 | 2010-05-20 | Dc Solar Corp. A Taiwan Corporation | Porphyrin-based photosensitizer dyes for dye-sensitized solar cells |
| CN101805906A (en) * | 2010-04-15 | 2010-08-18 | 桂林理工大学 | Composite corrosion inhibitor for restraining corrosion of carbon steel in seawater and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| HE C. 等: "Metal-Tunable Nanocages as Artificial Chemosensors", 《ANGEW. CHEM. INT. ED.》 * |
| 李蒙 等: "meso-四苯甲酰腙锌卟啉的合成及其光电性质的研究", 《2011年中西部地区无机化学化工学术研讨会论文集》 * |
| 赵鸿斌 等: "meso-四(4-酰肼基苯基) 卟啉及其金属配合物共价和非共价修饰多壁碳纳米管", 《高等学校化学学报》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827169A (en) * | 2012-09-04 | 2012-12-19 | 西安瑞联近代电子材料有限责任公司 | Novel porphyrin ligand and metal complex, preparation method and application for novel porphyrin ligand |
| CN102827169B (en) * | 2012-09-04 | 2014-11-05 | 西安瑞联近代电子材料有限责任公司 | Novel porphyrin ligand and metal complex, preparation method and application for novel porphyrin ligand |
| CN103588677A (en) * | 2013-12-09 | 2014-02-19 | 南京信息工程大学 | 1, 2-2(benzophenone-hydrazone-yl)-acenaphthequinone-dihydrazone and preparation method thereof |
| CN105315699B (en) * | 2014-07-09 | 2018-04-13 | 财团法人工业技术研究院 | Zinc purple photosensitive dye and photoelectric conversion device thereof |
| CN105315699A (en) * | 2014-07-09 | 2016-02-10 | 财团法人工业技术研究院 | Zinc purple photosensitive dye and photoelectric conversion device thereof |
| CN105367589A (en) * | 2015-10-19 | 2016-03-02 | 桂林理工大学 | Isophthalic acid-5-silver sulfonate coordination polymer and preparation method |
| CN105367589B (en) * | 2015-10-19 | 2017-05-17 | 桂林理工大学 | Isophthalic acid-5-silver sulfonate coordination polymer and preparation method |
| CN105399750A (en) * | 2015-12-11 | 2016-03-16 | 西北师范大学 | Tetrazole porphyrin metal complexes, synthesis thereof and applications of the metal complexes as dye sensitizing agents |
| CN105399750B (en) * | 2015-12-11 | 2018-07-17 | 西北师范大学 | Tetrazole porphyrin metal complex and its synthesis and application as dye sensitizing agent |
| CN105694525A (en) * | 2016-03-24 | 2016-06-22 | 西北师范大学 | Axial-coordination self-assembly metalloporphyrin dye sensitizer and preparation method thereof |
| CN107828236A (en) * | 2017-10-30 | 2018-03-23 | 江苏理工学院 | It is a kind of using hydrazides as zinc protoporphyrin dye sensitizing agent of anchoring group and preparation method thereof |
| CN107828236B (en) * | 2017-10-30 | 2019-12-10 | 江苏理工学院 | zinc porphyrin dye sensitizer with hydrazide as anchoring group and preparation method thereof |
| CN108276796A (en) * | 2017-12-25 | 2018-07-13 | 阜阳师范学院 | Preparation method for the porphyrin sensitizer for building quasi- solid-state dye battery |
| CN111135871A (en) * | 2020-01-07 | 2020-05-12 | 西北大学 | Imidazole ionic liquid functionalized zinc porphyrin and application thereof |
| CN112827477A (en) * | 2020-12-31 | 2021-05-25 | 西南科技大学 | Preparation method and application of hydroxyquinone adsorbing material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102417511B (en) | 2013-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102417511B (en) | Acylhydrazone zinc protoporphyrin, and synthesis and application of complex thereof | |
| Zhang et al. | Enhanced efficiency with CDCA co-adsorption for dye-sensitized solar cells based on metallosalophen complexes | |
| Kurotobi et al. | Highly Asymmetrical Porphyrins with Enhanced Push–Pull Character for Dye‐Sensitized Solar Cells | |
| Naik et al. | Investigation of new carbazole based metal-free dyes as active photo-sensitizers/co-sensitizers for DSSCs | |
| Naik et al. | New carbazole based dyes as effective co-sensitizers for DSSCs sensitized with ruthenium (II) complex (NCSU-10) | |
| Hagberg et al. | Symmetric and unsymmetric donor functionalization. comparing structural and spectral benefits of chromophores for dye-sensitized solar cells | |
| JP5501239B2 (en) | Squarylium dyes containing anchor groups | |
| She et al. | Novel ruthenium sensitizers with a phenothiazine conjugated bipyridyl ligand for high-efficiency dye-sensitized solar cells | |
| CN102391269B (en) | Zinc protoporphyrin containing heterocyclic ring as well as synthesis and applications of zinc protoporphyrin containing heterocyclic ring and metal complex of zinc protoporphyrin containing heterocyclic ring | |
| Hu et al. | β-Functionalized push–pull opp-dibenzoporphyrins as sensitizers for dye-sensitized solar cells: The role of the phenylethynyl bridge | |
| Kandavelu et al. | Novel iminocoumarin dyes as photosensitizers for dye-sensitized solar cell | |
| Tan et al. | Novel zinc porphyrin sensitizers for dye-sensitized solar cells: Synthesis and spectral, electrochemical, and photovoltaic properties | |
| Ishida et al. | β-(Ethynylbenzoic acid)-substituted push–pull porphyrins: DSSC dyes prepared by a direct palladium-catalyzed alkynylation reaction | |
| CN101855739B (en) | Preparation of high-quality sensitizer dye for dye-sensitized solar cells | |
| Takahashi et al. | Highly efficient polypyridyl-ruthenium (II) photosensitizers with chelating oxygen donor ligands: β-diketonato-bis (dicarboxybipyridine) ruthenium | |
| Huang et al. | Novel dyes based on naphthalimide moiety as electron acceptor for efficient dye-sensitized solar cells | |
| Ince et al. | Convergent Synthesis of Near‐Infrared Absorbing,“Push–Pull”, Bisthiophene‐Substituted, Zinc (II) Phthalocyanines and their Application in Dye‐Sensitized Solar Cells | |
| CN102417510A (en) | Conjugated Schiff base Zn (zinc) porphyrin as well as preparation and application thereof | |
| Hara et al. | New Ru (II) phenanthroline complex photosensitizers having different number of carboxyl groups for dye-sensitized solar cells | |
| Cogal et al. | Asymmetric phthalocyanine derivatives containing 4-carboxyphenyl substituents for dye-sensitized solar cells | |
| Lu et al. | Influence of the additional electron-withdrawing unit in β-functionalized porphyrin sensitizers on the photovoltaic performance of dye-sensitized solar cells | |
| Xiang et al. | Synthesis and characterization of trivalent metal porphyrin with NCS ligand for application in dye-sensitized solar cells | |
| Ooyama et al. | A new co-sensitization method employing D–π–A dye with pyridyl group and D–π–Cat dye with catechol unit for dye-sensitized solar cells | |
| Li et al. | A new carbazole-based phenanthrenyl ruthenium complex as sensitizer for a dye-sensitized solar cell | |
| Sreenivasu et al. | Synthesis and Characterization of Donor–π‐Acceptor‐Based Porphyrin Sensitizers: Potential Application of Dye‐Sensitized Solar Cells |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130821 Termination date: 20140922 |
|
| EXPY | Termination of patent right or utility model |