CN110577754B - Dye photosensitizer and preparation method and application thereof - Google Patents
Dye photosensitizer and preparation method and application thereof Download PDFInfo
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- CN110577754B CN110577754B CN201910851084.2A CN201910851084A CN110577754B CN 110577754 B CN110577754 B CN 110577754B CN 201910851084 A CN201910851084 A CN 201910851084A CN 110577754 B CN110577754 B CN 110577754B
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- 239000003504 photosensitizing agent Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 230000001699 photocatalysis Effects 0.000 claims abstract description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 8
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010865 sewage Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- 238000007146 photocatalysis Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- 238000010992 reflux Methods 0.000 abstract description 7
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- QTUUBOZSGQFLRZ-UHFFFAOYSA-N 2-(3,5,5-trimethylcyclohex-2-en-1-ylidene)propanedinitrile Chemical compound CC1=CC(=C(C#N)C#N)CC(C)(C)C1 QTUUBOZSGQFLRZ-UHFFFAOYSA-N 0.000 abstract description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract description 4
- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 abstract description 3
- YDXLVFKTOSKBKT-UHFFFAOYSA-N 3-bromo-n,n-diphenylaniline Chemical compound BrC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 YDXLVFKTOSKBKT-UHFFFAOYSA-N 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract description 3
- 239000000975 dye Substances 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 5
- 208000017983 photosensitivity disease Diseases 0.000 description 5
- 231100000434 photosensitization Toxicity 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 2
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 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
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229940099898 chlorophyllin Drugs 0.000 description 1
- 235000019805 chlorophyllin Nutrition 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229930187593 rose bengal Natural products 0.000 description 1
- 229940081623 rose bengal Drugs 0.000 description 1
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0248—Nitriles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- C09B23/14—Styryl dyes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention provides a dye photosensitizer and a preparation method and application thereof. The chemical name of the dye photosensitizer is (E) -2- (3- (2- (4'- (diphenylamine) - [1,1' -biphenyl)]-4-yl) vinyl) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile having the formula C37H31N3. The preparation method comprises the following steps: adding 3-bromo-N, N-diphenylaniline and 4-formylphenylboronic acid into a reactor, and adding Pd (dppf) Cl2And K2CO3Introducing nitrogen for protection, and heating and refluxing in a DMF solution to obtain a compound B; then dissolving the compound B and the (3,5, 5-trimethylcyclohex-2-enylidene) malononitrile in ethanol, adding a small amount of piperidine, and heating and refluxing to obtain a red target product. The dye photosensitizer has strong absorption in the range of 450-750nm, generates active oxygen under the irradiation of visible light, and can be used for photocatalytic sewage treatment.
Description
Technical Field
The invention relates to a photosensitization material, in particular to a dye photosensitizer and a preparation method and application thereof.
Background
The photocatalytic oxidation is a new advanced oxidation technology, which means that semiconductor catalyst and H are utilized under the irradiation of various light sources2O、O2And organic matters are mutually interacted to realize the oxidative degradation of the organic matters. The photocatalysis technology is widely applied to degradation of heavy metal ions, dyes and toxic and harmful organic pollutants in water, and has wide application prospect in the aspects of air purification and sterilization.
The semiconductor photocatalysis technology has the characteristics of low energy consumption, mild reaction conditions, high reaction efficiency and the like, particularly organic pollutants can be rapidly decomposed under the action of ultraviolet photocatalysis, and the semiconductor photocatalysis technology has obvious degradation effect on organic pollutants which are difficult to biodegrade and have high toxicity. In order to increase its absorption capacity for visible light, semiconductor photosensitization techniques have been developed in which a photoactive substance having a chromophoric group is adsorbed onto a wide bandgap semiconductor surface (e.g., TiO) by a physical or chemical adsorption process2) When the sensitizer is excited under the illumination of energy lower than the band gap of the semiconductor, photo-generated electrons of the sensitizer can migrate to the semiconductor, and the recombination of the electrons and holes is prevented. Therefore, the semiconductor photosensitization technology can extend the response range of the excitation wavelength of the wide band gap semiconductor, so that inexhaustible sunlight can be fully utilized, and the light excitation efficiency is improved. The commonly used photosensitizing materials are bipyridine ruthenium,Organic dyes such as chlorophyllin, phthalocyanine, rose bengal, eosin and the like are taken as main materials, and electrons are easily excited under the action of visible light. However, these organic dyes have good water solubility and poor adhesion to carriers, and are difficult to be practically used in sewage treatment, and development of new dye photosensitizers is urgently needed.
Disclosure of Invention
The invention aims to provide a novel dye photosensitizer and a preparation method thereof, the photosensitizer generates active oxygen free radicals under the irradiation of visible light, has good lipid solubility and strong adhesive force to a carrier, has strong absorption in a range of 450-750nm, and can be applied to the photocatalytic treatment of sewage.
The chemical name of the dye photosensitizer provided by the invention is (E) -2- (3- (2- (4'- (diphenylamine) - [1,1' -biphenyl)]-4-yl) vinyl) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile having the formula C37H31N3The structural formula is as follows:
the invention provides a preparation method of a dye photosensitizer, which has the following reaction formula:
the preparation method comprises the following steps:
1) dissolving equal amount of 3-bromo-N, N-diphenylaniline and 4-formylphenylboronic acid in N, N-dimethylformamide DMF, and adding trace amount of 1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride Pd (dppf) Cl2And K2CO3Heating and refluxing for 2 hours under the protection of nitrogen; cooling the reaction liquid, and performing column separation to obtain a compound B;
2) dissolving the compound B and (3,5, 5-trimethylcyclohex-2-enylidene) malononitrile in absolute ethyl alcohol, adding a small amount of piperidine, heating and refluxing for 0.5-3 hours, cooling overnight, filtering, and washing to obtain a red target compound A.
The palladium catalyst described in step 1) may be bis (diphenylphosphino) ferrocene ] dichloropalladium, bis (triphenylphosphine) dichloropalladium, 1, 2-bis (diphenylphosphino) ethane dichloropalladium (II) or 1, 2-bis (diphenylphosphino) ethane dichloropalladium (II).
The mass ratio of the compound B and the (3,5, 5-trimethylcyclohex-2-enylidene) malononitrile in the step 2) is 1: 1.
The heating reflux time in the step 2) is 2 hours.
The reaction solvent in the step 2) is methanol, ethanol or isopropanol, preferably ethanol.
Compared with the traditional photosensitization material, the material has stable chemical property, good fat solubility and strong photobleaching resistance, and compared with dyes such as eosin, the material has the advantages of more red shift of an absorption spectrum, stronger absorption in a range of 450-750nm in a visible light region, good biocompatibility, small cytotoxicity and the like. The photosensitization material of the invention generates active oxygen free radicals under the irradiation of visible light, and is hopeful to be used for photocatalytic sewage treatment.
Drawings
FIG. 1 is a UV-VIS absorption spectrum of a dye photosensitizer in accordance with the present invention.
FIG. 2 shows the degradation activity of the dye photosensitizers of the present invention on methylene blue under visible light irradiation.
FIG. 3 shows the sewage purifying activity of the dye photosensitizers of the present invention under visible light irradiation.
Detailed Description
Example 1
Equal amounts of 3-bromo-N, N-diphenylaniline (0.324g,1mmol) and 4-formylphenylboronic acid (0.149g,1mmol) were dissolved in 20mL of N, N-dimethylformamide DMF and the catalyst 1,1' -bis (diphenylphosphino) ferrocene was added]Palladium dichloride Pd (dppf) Cl2(8.16mg,1 mol%) and K2CO3(1.18g,10mmol), refluxing at 100 ℃ for 2 hours under nitrogen protection, cooling the reaction mixture, rotary evaporating, and separating the concentrated solution by silica gel column (petroleum ether: dichloromethane ═ 1:1) to obtain compound B.1H NMR(600MHz,CDCl3):10.05(s,1H),7.95(d,J＝8.04Hz,2H),7.76(d,J＝8.10Hz,2H),7.55(d,J＝8.54Hz,2H),7.32(t,J＝7.64Hz,4H),7.18(d,J＝2.69Hz,3H),7.17(d,J＝3.07Hz,3H),7.10(t,J＝7.32Hz,2H)。
An equal amount of compound B (349mg,1mmol) and (3,5, 5-trimethylcyclohex-2-enylidene) malononitrile (186mg,1mmol) was dissolved in anhydrous ethanol, a drop of piperidine was added, heated under reflux for 2 hours, cooled overnight, filtered, and washed to give red target compound a (185mg, 36%). Chemical name: (E) -2- (3- (2- (4'- (diphenylamine) - [1,1' -biphenyl)]-4-yl) vinyl) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile.1H NMR(600MHz,CDCl3):7.64(d,J＝5.84Hz 2H),7.58(d,J＝5.16Hz,2H),7.52(d,J＝6.54Hz,2H),7.30(d,J＝7.93Hz,4H),7.28(t,J＝3.32Hz,2H),7.16(t,J＝3.48Hz,4H),7.09(d,J＝10.38Hz,2H),7.06(s,1H),7.03(s,1H),6.88(s,1H),2.63(s,2H),2.51(s,2H),1.11(s,6H)。13C NMR(150MHz,CDCl3):169.22,153.93,147.82,147.48,141.94,136.75,134.07,133.49,129.36,128.74,128.13,127.59,126.98,124.68,124.57,123.49,123.25,113.59,112.82,43.03,39.25,32.07,28.06. ESI mass spectrum with M/z 518.2585[ M + H ]]+,[M+H]+The calculated value was 518.2591.
Has stronger absorption in the region of 450-750nm in the visible light region, and the maximum absorption is at 580nm (see figure 1).
Example 2
Taking 10mg of prepared compound A and 10mg of nano TiO2Adding the sol into 50mL of 20mg/L methylene blue solution, and dissolving and mixing uniformly by water bath ultrasonic treatment at 40 ℃ for 30 min. Magnetically stirring for 30 minutes under the condition of keeping out of the sun to ensure that the reactants reach adsorption and desorption equilibrium, and then reacting under the illumination of a xenon lamp with the wavelength of 360 and 800nm (the distance between a light source and the reaction vessel is 36cm), and simultaneously keeping the temperature of the reactor at 25 ℃. Under illumination, samples were taken every 5-10 minutes, centrifuged, the supernatant was taken, and the change in methylene blue absorbance was measured by an ultraviolet-visible absorption spectrometer, the results being shown in FIG. 2.
Example 3
Taking 10mg of prepared compound A and 10mg of nano TiO2Adding the sol into 50mL of inferior V sewage (COD: 50mg/L and BOD: 10mg/L), and carrying out ultrasonic treatment in water bath at 40 ℃ for 30min to dissolve and mix uniformly. Magnetically stirring for 30min in dark condition to make the reactant reach adsorptionDesorbing for equilibrium, and then reacting under the illumination of 360-800nm xenon lamp (the light source is 36cm away from the reaction vessel) while the temperature of the reactor is kept at 25 ℃. Under illumination, samples were taken every 10 minutes, centrifuged, and the supernatant was collected and analyzed by water quality analyzer (environmental protection JC-501B type) to determine the changes in COD and BOD of the wastewater, the results are shown in FIG. 3.
Claims (1)
1. The chemical name of the dye photosensitizer is (E) -2- (3- (2- (4'- (diphenylamine) - [1,1' -biphenyl) to treat sewage through photocatalysis]-4-yl) vinyl) -5, 5-dimethylcyclohex-2-en-1-ylidene) malononitrile having the formula C37H31N3The structural formula is as follows:
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