WO2020232973A1 - 一种双D-π-A型柱[5]芳烃染料及其合成方法与应用 - Google Patents
一种双D-π-A型柱[5]芳烃染料及其合成方法与应用 Download PDFInfo
- Publication number
- WO2020232973A1 WO2020232973A1 PCT/CN2019/113790 CN2019113790W WO2020232973A1 WO 2020232973 A1 WO2020232973 A1 WO 2020232973A1 CN 2019113790 W CN2019113790 W CN 2019113790W WO 2020232973 A1 WO2020232973 A1 WO 2020232973A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dye
- arene
- double
- column
- application according
- Prior art date
Links
- 238000001308 synthesis method Methods 0.000 title abstract description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 28
- 239000000975 dye Substances 0.000 claims description 83
- 239000000243 solution Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 239000011521 glass Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- ISHFYECQSXFODS-UHFFFAOYSA-M 1,2-dimethyl-3-propylimidazol-1-ium;iodide Chemical compound [I-].CCCN1C=C[N+](C)=C1C ISHFYECQSXFODS-UHFFFAOYSA-M 0.000 claims description 3
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 claims description 3
- JCWIWBWXCVGEAN-UHFFFAOYSA-L cyclopentyl(diphenyl)phosphane;dichloropalladium;iron Chemical compound [Fe].Cl[Pd]Cl.[CH]1[CH][CH][CH][C]1P(C=1C=CC=CC=1)C1=CC=CC=C1.[CH]1[CH][CH][CH][C]1P(C=1C=CC=CC=1)C1=CC=CC=C1 JCWIWBWXCVGEAN-UHFFFAOYSA-L 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 claims 7
- 150000002941 palladium compounds Chemical class 0.000 claims 3
- LKHZWDIUNGOHBN-UHFFFAOYSA-N 2,3-dimethylbutane-2,3-diol;phenylboronic acid Chemical compound CC(C)(O)C(C)(C)O.OB(O)C1=CC=CC=C1 LKHZWDIUNGOHBN-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 238000003306 harvesting Methods 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000004220 aggregation Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 230000021615 conjugation Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 125000003118 aryl group Chemical group 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002146 bilateral effect Effects 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- VBXDEEVJTYBRJJ-UHFFFAOYSA-N diboronic acid Chemical compound OBOBO VBXDEEVJTYBRJJ-UHFFFAOYSA-N 0.000 description 2
- -1 dry Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 1
- WDBQJSCPCGTAFG-QHCPKHFHSA-N 4,4-difluoro-N-[(1S)-3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-pyridin-3-ylpropyl]cyclohexane-1-carboxamide Chemical compound FC1(CCC(CC1)C(=O)N[C@@H](CCN1CCC(CC1)N1C(=NN=C1C)C(C)C)C=1C=NC=CC=1)F WDBQJSCPCGTAFG-QHCPKHFHSA-N 0.000 description 1
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
- C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
- C09B23/0058—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof the substituent being CN
-
- 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
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/10—The polymethine chain containing an even number of >CH- groups
- C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Definitions
- the invention relates to the application field of photoelectric conversion materials in fine chemical industry and the technical field of dye-sensitized solar cells, in particular to a double D- ⁇ -A column [5] arene dye and its synthesis method and application.
- Dye-sensitized solar cells are a new type of flexible device that converts solar energy into electrical energy. Because of its simple and convenient preparation, this type of battery can obtain higher energy conversion efficiency under outdoor light and indoor low light, making it possible to be applied in commercial fields such as interior decoration and building curtain walls, which has attracted market attention.
- the advantage is that a small amount of dye can be used to prepare a large number of devices through the dye bath, the cost is low, and the preparation process is simple and repeatable.
- the structure of the sensitizing dye is very important, which plays a decisive role in the photoelectric conversion efficiency of the cell.
- dyes with the highest photoelectric conversion efficiency based on iodine-based electrolytes are polypyridine ruthenium and metalloporphyrin complex dyes. These two types of high-efficiency dyes are metal complexes.
- the preparation process is relatively long and separation and purification are relatively more difficult.
- the advantages of simple synthesis of pure organic dyes, easy design and modification of molecular structure, and high molar extinction coefficient have been widely developed and applied.
- the D- ⁇ -A structure can effectively capture solar photons through intramolecular photoelectron transfer, which has been proven to be a structure required for efficient dye molecules.
- Double (D- ⁇ -A) type dyes have two independent D- ⁇ -A structural units in a dye molecule, which is equivalent to a molecule with twice the light-harvesting unit, and the light-harvesting ability is significantly enhanced .
- the column [5] aromatic hydrocarbon has an excellent three-dimensional structure, which can effectively branch the ⁇ - ⁇ stacking caused by the conjugated surface of the dye molecule, and the conjugate bridge structure provided by its benzene ring can inhibit the intermolecular ⁇ - ⁇ gathers.
- the invention designs and synthesizes a kind of pure organic dyes with column [5] aromatic hydrocarbon as conjugated bridge structure and double (D- ⁇ -A) structure.
- the dye has the advantages of simple structure, easy synthesis, and good photoelectric conversion performance.
- the purpose of the present invention is to provide a method and application for the synthesis of double D- ⁇ -A column [5] arene dye.
- the purpose of the present invention is to provide a double D- ⁇ -A column [5] arene dye that inhibits the aggregation and enhances the light-harvesting ability in view of the serious aggregation of the dyes currently used for DSSCs.
- This type of dye is a bilateral pure organic dye with alkoxy column [5] aromatic hydrocarbon as the bridge structure, phenothiazine as the electron donor, thiophene/furan as the ⁇ bridge, and cyanoacetic acid as the electron acceptor and anchor group.
- Such dyes have good application performance in dye-sensitized solar cells.
- the double D- ⁇ -A column [5] aromatic dye provided by the invention has simple preparation method and high efficiency, can effectively carry out large-scale production, and has universality.
- the present invention also provides the application of a kind of double D- ⁇ -A type pillar [5] arene dyes in DSSCs, specifically as a sensitizer applied to the photoanode of DSSCs devices, which can effectively inhibit electronic recombination, Increase the open circuit voltage, the double D- ⁇ -A structure enhances the light-harvesting ability of the dye, and effectively increases the short-circuit current, thereby effectively improving the photoelectric performance of the dye-sensitized sun.
- a kind of double D- ⁇ -A type pillar [5] arene dyes in DSSCs specifically as a sensitizer applied to the photoanode of DSSCs devices, which can effectively inhibit electronic recombination, Increase the open circuit voltage, the double D- ⁇ -A structure enhances the light-harvesting ability of the dye, and effectively increases the short-circuit current, thereby effectively improving the photoelectric performance of the dye-sensitized sun.
- the present invention provides a double D- ⁇ -A column [5] arene dye, the general structural formula is as follows:
- n is 0-3;
- R 1 is a branched chain with 1-20 carbon atoms or a straight-chain alkyl group with 1-20 carbon atoms;
- R 2 is a straight chain with 1-4 carbon atoms Alkyl;
- X is O atom or S atom.
- the present invention provides a method for synthesizing the above-mentioned double D- ⁇ -A column [5] arene dyes, when the value of n is 0-3, R 1 is a branched alkyl group with 1-20 carbon atoms or The straight-chain alkyl group with 1-20 carbon atoms, R 2 is the straight-chain alkyl group with 1-4 carbon atoms, and X is an O atom or S atom, including the following steps:
- Intermediate 1 is efficiently prepared by bromination reaction with N-bromosuccinimide at room temperature to obtain Intermediate 2;
- Intermediate 2 is converted into phenylboronic acid pinnacle of intermediate 3 under the catalysis of divalent palladium Alcohol ester structure;
- further intermediate 3 and intermediate 4 are catalyzed by zero-valent palladium to efficiently synthesize key intermediate 5 under normal pressure; at room temperature, key intermediate 5 is hydrolyzed in trifluoroacetic acid,
- the double D- ⁇ -A column [5] aromatic dye can be obtained.
- the double D- ⁇ -A type column [5] arene dyes provided by the invention can be applied to prepare dye-sensitized solar cells.
- the method includes the following steps:
- the organic solvent in step (1) is a mixed solvent of chloroform and ethanol, wherein the volume ratio of chloroform to ethanol is 1-5:1.
- the concentration of the dye solution in step (1) is 1-5 ⁇ 10 -4 M.
- the glass with a transparent conductive layer has a width of 1.2 cm and a length of 1.7 cm;
- step (2) is performed in a dark environment, and the dye bath treatment time is 6-24 hours.
- the electrolyte solution in step (3) contains 1,2-dimethyl-3-propylimidazolium iodide with a concentration of 0.3-0.6M, LiI with a concentration of 0.1M, and I with a concentration of 0.05M. 2 And the concentration of 0.5M 4-tert-butylpyridine in acetonitrile solution.
- the synthesis method of the bis(D- ⁇ -A) dye containing column [5] aromatic hydrocarbon of the present invention is simple, and the raw materials are cheap and easy to obtain.
- the synthesis is carried out according to the following reaction formula:
- the dye material sensitized solar cell prepared by the synthesized double D- ⁇ -A type column [5] arene dye in the present invention is tested for battery performance, and the measured photoelectric conversion efficiency is 7.1-8.3%.
- the performance test includes the following steps: lead wires from the photoanode and photocathode of the dye-sensitized solar cell, and connect them to the battery performance test device (Keithley 2400), and use the solar simulator model (Newport-94043A, 450W).
- Xenon lamp, AM1.5G filter adjust the light intensity to 100mW/cm 2 , the working area of the battery is 0.12cm 2 , test the JV curve based on the dye-sensitized battery, the measured photoelectric conversion efficiency is 7.1-8.3% .
- the present invention has the following advantages and beneficial effects:
- the double D- ⁇ -A column [5] arene dye provided by the present invention, in order to inhibit the aggregation of dye molecules, a double D- ⁇ -A is synthesized by introducing two D- ⁇ -A structures into a dye molecule Type column [5] arene dyes; the double D- ⁇ -A type column [5] arene dyes can be used to prepare dye-sensitized solar cells, where the open-circuit voltage can be increased; The light absorption capacity increases the short-circuit current. Therefore, dye-sensitized solar cells based on this type of dye can obtain a large photovoltage and photocurrent, thereby achieving a higher photoelectric conversion efficiency.
- Figure 1 is an ultraviolet/visible absorption spectrum of the dye synthesized in Example 1 in a chloroform solution.
- Fig. 2 is the measured current-voltage curve of the dye-assembled battery synthesized in Example 1.
- n 1
- R 1 is a branched alkyl group with 8 carbon atoms
- R 2 is an alkyl group with 1 carbon atom
- X is an S atom.
- the method for synthesizing double D- ⁇ -A column [5] aromatic dye includes the following steps:
- the double D- ⁇ -A column [5] aromatic dye prepared in Example 1 shows two main absorption peaks, one is the absorption peak of the ⁇ - ⁇ * transition The other is the absorption peak of intramolecular charge transfer (I CT).
- the molar extinction coefficient of the dye is relatively high and the absorption range is wide. It exceeds 30000M -1 ⁇ cm -1 in the range of 400-550nm, which indicates that the dye has Good light trapping ability.
- the mixture After adding ethanol, acetic acid, terpineol and ethyl cellulose to the prepared TiO 2 nanocrystalline particles, the mixture is ground to obtain a slurry-like substance.
- the desired white viscous TiO 2 nanocrystalline slurry is obtained by ultrasound.
- Sensitization of the photoanode soak the photoanode prepared in step (3) in the dye solution prepared in step (4) and dye bath in a dark and dark environment for 12 hours, then take it out and rinse the surface with ethanol to remove residual or physical Dyes adsorbed on the surface of the film should be dried and stored in a dry and dark environment to be packaged for later use;
- Battery assembly Insulating epoxy resin film is coated around the sensitized photoanode TiO 2 film, with the TiO 2 layer in the middle. Add 1-2 drops of electrolyte to the surface of the TiO 2 film (prepared in step (5)), and cover the prepared platinum counter electrode on the photoanode (perforate first, remove bubbles and seal with epoxy resin), with clamps on both sides After fixing, the open sensitized dye solar cell to be tested is formed, and the dye sensitized solar cell is obtained.
- the lead wires from the photoanode and photocathode of the dye-sensitized solar cell prepared in Example 3 were connected to the battery performance test device (Keithley 2400), and the solar simulator model (Newport-94043A, 450W xenon lamp, AM1.5G) was used. filter) the light intensity was adjusted to 100mW / cm 2, the battery operating area of 0.12cm 2, the test based on the JV curve of the dye-sensitized cells.
- Table 1 is a data table of the performance of the dye-sensitized solar cell prepared in Example 3 and the performance of the solar cell prepared with existing dyes).
- the performance parameters of the solar cell prepared with dye a as the reference in Example 1 are from Org Electron, 14 (2013), 2662-2672.
- the solar cell prepared by using the dye obtained in Example 1 exhibits a higher photoelectric conversion efficiency, and has a higher short-circuit current and open-circuit voltage.
- the main reason is that the double (D- ⁇ -A) column [5] arene dye has good light trapping ability, the electron is injected into titanium dioxide with high efficiency, and the columnarene inhibits electronic recombination; from the data in Table 1, the present invention provides The performance of the solar cell prepared by the dye is better than the solar cell prepared by the existing dye a.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
Abstract
Description
Claims (10)
- 根据权利要求2所述的制备方法,其特征在于,所述二价钯化合物包括Pd(dPPf) 2Cl 2;所述零价钯化合物包括Pd(PPh 3) 4。
- 权利要求1所述双D-π-A型柱[5]芳烃染料在制备染料敏化太阳电池中的应用。
- 根据权利要求4所述的应用,其特征在于,包括如下步骤:(1)将所述双D-π-A型柱[5]芳烃染料加入有机溶剂中,混合均匀得到染料的溶液;(2)将吸附有纳米TiO 2薄膜的透明导电玻璃浸泡在步骤(1)所述染料的溶液中进行染浴处理,得到光阳极;(3)在另一块透明导电玻璃中间沉积Pt催化剂层,作为光阴极;将附有所述光阳极的纳米TiO 2薄膜层与光阴极催化剂层面对面排布,周边密封成密闭腔体,腔体内填充有电解质,得到所述染料敏化太阳电池。
- 根据权利要求5所述的应用,其特征在于,步骤(1)所述有机溶剂为氯仿和乙醇的混合溶剂,其中,氯仿与乙醇的体积比为1-5∶1。
- 根据权利要求5所述的应用,其特征在于,步骤(1)所述染料的溶液浓度为1-5×10 -4M。
- 根据权利要求5所述的应用,其特征在于,步骤(2)所述透明导电玻璃为具有掺F的SnO 2涂层的玻璃;所述纳米TiO 2薄膜的厚度为5-17μm。
- 根据权利要求5所述的应用,其特征在于,步骤(2)所述染浴处理是在避光环境下进行的,所述染浴处理的时间为6-24小时。
- 根据权利要求5所述的应用,其特征在于,步骤(3)所述电解质溶液为含有浓度为0.3-0.6M的1,2-二甲基-3-丙基碘化咪唑嗡、浓度为0.1M的LiI、浓度为0.05M的I 2及浓度为0.5M 4-叔丁基吡啶的乙腈溶液。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910426051.3A CN110183437B (zh) | 2019-05-21 | 2019-05-21 | 一种双D-π-A型柱[5]芳烃染料及其合成方法及其应用 |
CN201910426051.3 | 2019-05-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020232973A1 true WO2020232973A1 (zh) | 2020-11-26 |
Family
ID=67717115
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2019/113790 WO2020232973A1 (zh) | 2019-05-21 | 2019-10-28 | 一种双D-π-A型柱[5]芳烃染料及其合成方法与应用 |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN110183437B (zh) |
WO (1) | WO2020232973A1 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110437822A (zh) * | 2019-08-23 | 2019-11-12 | 西北民族大学 | 一种基于柱[5]芳烃的超分子白光材料及其制备方法 |
CN115672295A (zh) * | 2022-11-05 | 2023-02-03 | 中国科学院兰州化学物理研究所 | 一种亚胺型柱[5]芳烃修饰硅胶色谱填料的制备和应用 |
CN115739054A (zh) * | 2022-11-09 | 2023-03-07 | 兰州城市学院 | 一种羧酸柱[5]芳烃改性凹凸棒石的制备和应用 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110183437B (zh) * | 2019-05-21 | 2021-10-26 | 华南理工大学 | 一种双D-π-A型柱[5]芳烃染料及其合成方法及其应用 |
CN111423365B (zh) * | 2020-04-03 | 2020-11-20 | 华东师范大学 | 一种双官能团柱芳烃衍生物配体及金属有机笼和制备方法 |
CN112011034B (zh) * | 2020-08-19 | 2021-09-28 | 盐城海关综合技术服务中心 | 二甲氧基柱[n]芳烃打结共轭聚合物及其制备方法和应用 |
CN113200941B (zh) * | 2021-04-21 | 2022-08-26 | 华东理工大学 | 一类含吩噻嗪的柱芳烃荧光吸附材料及其制备方法 |
CN113980009B (zh) * | 2021-10-08 | 2023-08-22 | 华南理工大学 | 一种用于二胺检测的aie柱芳烃荧光探针及其制法与应用 |
CN114479838B (zh) * | 2022-01-20 | 2023-10-31 | 常州大学 | 一种基于柱芳烃的光捕获体系及其制备方法和应用 |
CN115286620B (zh) * | 2022-06-28 | 2024-04-05 | 中山大学 | 杯芳烃化合物、复合材料及其制备方法与应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103497532A (zh) * | 2013-07-02 | 2014-01-08 | 华南理工大学 | 一类三向延长共轭链吩噻嗪染料及其在染料敏化太阳电池中的应用 |
CN108148055A (zh) * | 2018-02-06 | 2018-06-12 | 陕西师范大学 | 一种基于萘的D-π-A型有机荧光材料及制备方法 |
CN108276795A (zh) * | 2018-02-27 | 2018-07-13 | 华南理工大学 | 桥环二噻吩-吩噻嗪染料及其在染料敏化太阳电池中的应用 |
CN110183437A (zh) * | 2019-05-21 | 2019-08-30 | 华南理工大学 | 一种双D-π-A型柱[5]芳烃染料及其合成方法及其应用 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102618066B (zh) * | 2012-02-28 | 2013-12-11 | 中山大学 | 含杯芳烃衍生物的有机染料、制备方法及其应用 |
CN103788679B (zh) * | 2014-01-24 | 2015-09-16 | 华南理工大学 | 在π桥中引入苯并三氮唑的双链吩噻嗪染料及其在制备染料敏化太阳电池中的应用 |
-
2019
- 2019-05-21 CN CN201910426051.3A patent/CN110183437B/zh active Active
- 2019-10-28 WO PCT/CN2019/113790 patent/WO2020232973A1/zh active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103497532A (zh) * | 2013-07-02 | 2014-01-08 | 华南理工大学 | 一类三向延长共轭链吩噻嗪染料及其在染料敏化太阳电池中的应用 |
CN108148055A (zh) * | 2018-02-06 | 2018-06-12 | 陕西师范大学 | 一种基于萘的D-π-A型有机荧光材料及制备方法 |
CN108276795A (zh) * | 2018-02-27 | 2018-07-13 | 华南理工大学 | 桥环二噻吩-吩噻嗪染料及其在染料敏化太阳电池中的应用 |
CN110183437A (zh) * | 2019-05-21 | 2019-08-30 | 华南理工大学 | 一种双D-π-A型柱[5]芳烃染料及其合成方法及其应用 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110437822A (zh) * | 2019-08-23 | 2019-11-12 | 西北民族大学 | 一种基于柱[5]芳烃的超分子白光材料及其制备方法 |
CN115672295A (zh) * | 2022-11-05 | 2023-02-03 | 中国科学院兰州化学物理研究所 | 一种亚胺型柱[5]芳烃修饰硅胶色谱填料的制备和应用 |
CN115672295B (zh) * | 2022-11-05 | 2023-12-15 | 中国科学院兰州化学物理研究所 | 一种亚胺型柱[5]芳烃修饰硅胶色谱填料的制备和应用 |
CN115739054A (zh) * | 2022-11-09 | 2023-03-07 | 兰州城市学院 | 一种羧酸柱[5]芳烃改性凹凸棒石的制备和应用 |
Also Published As
Publication number | Publication date |
---|---|
CN110183437B (zh) | 2021-10-26 |
CN110183437A (zh) | 2019-08-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2020232973A1 (zh) | 一种双D-π-A型柱[5]芳烃染料及其合成方法与应用 | |
JP4576494B2 (ja) | 光増感色素 | |
Tang et al. | New starburst sensitizer with carbazole antennas for efficient and stable dye-sensitized solar cells | |
Pasunooti et al. | Synthesis, characterization and application of trans-D–B–A-porphyrin based dyes in dye-sensitized solar cells | |
WO2017016177A1 (zh) | 异吡咯并吡咯二酮染料及其应用 | |
JP2004095450A (ja) | 有機色素を光増感剤とする半導体薄膜電極、光電変換素子及び光電気化学太陽電池 | |
Babu et al. | From Molecular Design to Co-sensitization; High performance indole based photosensitizers for dye-sensitized solar cells | |
Iqbal et al. | Impact of hydroxy and octyloxy substituents of phenothiazine based dyes on the photovoltaic performance | |
Iqbal et al. | Influence of spatial arrangements of π-spacer and acceptor of phenothiazine based dyes on the performance of dye-sensitized solar cells | |
Dai et al. | Synthesis and photovoltaic performance of asymmetric di-anchoring organic dyes | |
CN101899223B (zh) | 三聚茚基三芳胺有机染料及制备和用途 | |
WO2006120939A1 (ja) | 新規アミノ基含有複素環誘導体および該複素環誘導体を含有する光電変換用増感色素 | |
CN108164546B (zh) | 吲哚啉-二噻吩并喹喔啉-二苯并[a,c]吩嗪染料及其在染料敏化太阳电池中的应用 | |
Wu et al. | Novel 4, 4′-bis (alkylphenyl/alkyloxyphenyl)-2, 2′-bithiophene bridged cyclic thiourea functionalized triphenylamine sensitizers for efficient dye-sensitized solar cells | |
Liang et al. | New organic photosensitizers incorporating carbazole and dimethylarylamine moieties for dye-sensitized solar cells | |
Shivashimpi et al. | Effect of nature of anchoring groups on photosensitization behavior in unsymmetrical squaraine dyes | |
WO2008102962A1 (en) | Noble ruthenium-type sensitizer and method of preparing the same | |
Karjule et al. | Heterotriangulene-based unsymmetrical squaraine dyes: synergistic effects of donor moieties and out-of-plane branched alkyl chains on dye cell performance | |
CN102618066B (zh) | 含杯芳烃衍生物的有机染料、制备方法及其应用 | |
Manfredi et al. | Performance enhancement of a dye-sensitized solar cell by peripheral aromatic and heteroaromatic functionalization in di-branched organic sensitizers | |
CN103788679B (zh) | 在π桥中引入苯并三氮唑的双链吩噻嗪染料及其在制备染料敏化太阳电池中的应用 | |
JP5280853B2 (ja) | 新規アミノ基含有芳香族化合物および該芳香族化合物を含有する光電変換用増感色素 | |
CN104403351A (zh) | 基于对称的吡咯并吡咯二酮为共轭桥的有机光敏染料 | |
Houarner-Rassin et al. | Improved efficiency of a thiophene linked ruthenium polypyridine complex for dry dye-sensitized solar cells | |
JP2013164970A (ja) | 光増感色素ならびに該色素を含む金属酸化物半導体電極および色素増感太陽電池 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19930150 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 19930150 Country of ref document: EP Kind code of ref document: A1 |
|
32PN | Ep: public notification in the ep bulletin as address of the adressee cannot be established |
Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 19/05/2022) |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 19930150 Country of ref document: EP Kind code of ref document: A1 |