CN112898799B - Carbazole organic dye and preparation method thereof, dye-sensitized titanium dioxide composite catalyst and preparation method and application thereof - Google Patents
Carbazole organic dye and preparation method thereof, dye-sensitized titanium dioxide composite catalyst and preparation method and application thereof Download PDFInfo
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- CN112898799B CN112898799B CN201911219076.2A CN201911219076A CN112898799B CN 112898799 B CN112898799 B CN 112898799B CN 201911219076 A CN201911219076 A CN 201911219076A CN 112898799 B CN112898799 B CN 112898799B
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- dye
- titanium dioxide
- carbazole
- composite catalyst
- dioxide composite
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 222
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000006731 degradation reaction Methods 0.000 claims abstract description 38
- 230000015556 catabolic process Effects 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 17
- 239000002351 wastewater Substances 0.000 claims abstract description 13
- 238000004873 anchoring Methods 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 165
- 239000000975 dye Substances 0.000 claims description 83
- 238000000034 method Methods 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 238000013329 compounding Methods 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 3
- 125000005647 linker group Chemical group 0.000 claims description 2
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 abstract description 13
- 231100000719 pollutant Toxicity 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 9
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 abstract description 4
- 230000004298 light response Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 125000006617 triphenylamine group Chemical group 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 66
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 51
- 150000001875 compounds Chemical class 0.000 description 48
- 230000015572 biosynthetic process Effects 0.000 description 35
- 238000003786 synthesis reaction Methods 0.000 description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 32
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 27
- 230000008569 process Effects 0.000 description 27
- 239000000243 solution Substances 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 24
- 238000010521 absorption reaction Methods 0.000 description 23
- 239000002994 raw material Substances 0.000 description 22
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].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.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 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 20
- 239000012046 mixed solvent Substances 0.000 description 20
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical group OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 description 18
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 17
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 description 16
- 230000008859 change Effects 0.000 description 15
- 239000003480 eluent Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 15
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- 238000006722 reduction reaction Methods 0.000 description 12
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- 125000003342 alkenyl group Chemical group 0.000 description 11
- 239000012043 crude product Substances 0.000 description 11
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 10
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- 238000010534 nucleophilic substitution reaction Methods 0.000 description 8
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- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
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- UESSERYYFWCTBU-UHFFFAOYSA-N 4-(n-phenylanilino)benzaldehyde Chemical compound C1=CC(C=O)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 UESSERYYFWCTBU-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000004043 dyeing Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- -1 thiophenethenyl Chemical group 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
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- 239000007858 starting material Substances 0.000 description 4
- 125000005504 styryl group Chemical group 0.000 description 4
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 4
- CMSYDJVRTHCWFP-UHFFFAOYSA-N triphenylphosphane;hydrobromide Chemical compound Br.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMSYDJVRTHCWFP-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 3
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 3
- UGAKJPMSFVMKEF-UHFFFAOYSA-N C=1C=CC=CC=1[P](C=1C=CC=CC=1)(Br)C1=CC=CC=C1 Chemical compound C=1C=CC=CC=1[P](C=1C=CC=CC=1)(Br)C1=CC=CC=C1 UGAKJPMSFVMKEF-UHFFFAOYSA-N 0.000 description 3
- 101100481895 Cochliobolus carbonum TOXC gene Proteins 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- TWWQCBRELPOMER-UHFFFAOYSA-N [4-(n-phenylanilino)phenyl]boronic acid Chemical compound C1=CC(B(O)O)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 TWWQCBRELPOMER-UHFFFAOYSA-N 0.000 description 3
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- GLGNXYJARSMNGJ-VKTIVEEGSA-N (1s,2s,3r,4r)-3-[[5-chloro-2-[(1-ethyl-6-methoxy-2-oxo-4,5-dihydro-3h-1-benzazepin-7-yl)amino]pyrimidin-4-yl]amino]bicyclo[2.2.1]hept-5-ene-2-carboxamide Chemical compound CCN1C(=O)CCCC2=C(OC)C(NC=3N=C(C(=CN=3)Cl)N[C@H]3[C@H]([C@@]4([H])C[C@@]3(C=C4)[H])C(N)=O)=CC=C21 GLGNXYJARSMNGJ-VKTIVEEGSA-N 0.000 description 2
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 2
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 2
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Images
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
-
- 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
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- 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
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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
- 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
- C02F2305/10—Photocatalysts
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- 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
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- 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
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Abstract
The invention belongs to the technical field of photocatalytic wastewater treatment, and particularly relates to a carbazole organic dye and a preparation method thereof, a dye-sensitized titanium dioxide composite catalyst and a preparation method and application thereof. The carbazole organic dye provided by the invention contains triphenylamine groups and carbazole groups, and the dye molecule has an anchoring group, so that the adsorption strength of the organic dye on the surface of a carrier can be improved, the photoresponse range can be widened, the hole-electron pair recombination can be slowed down, and the degradation effect of the dye-sensitized titanium dioxide composite catalyst on pollutants can be further enhanced. The dye molecule is used for preparing the dye-sensitized titanium dioxide composite catalyst, and in the obtained catalyst, the dye is adsorbed on the surface of titanium dioxide, the particles are uniformly distributed, the visible light response range of a titanium dioxide semiconductor is widened, the catalytic effect is good, the treatment efficiency of wastewater is improved, and the service life of photocatalytic particles is prolonged.
Description
Technical Field
The invention relates to the technical field of photocatalytic wastewater treatment, in particular to a carbazole organic dye and a preparation method thereof, a dye-sensitized titanium dioxide composite catalyst and a preparation method and application thereof.
Background
At present, the discharge of a large amount of industrial wastewater is one of the important reasons for the shortage of water resources, and the water pollution is about the life health and safety of people.
Printing and dyeing wastewater is one of typical organic pollutants in water. Acid black is one of common organic wastewater, and acid black 1(AB1) is commonly called naphthol black blue, also called acid black 10B or amino black 10B, is an artificially synthesized blue black dye, is black brown powder at normal temperature, is easy to dissolve in water and ethanol, has good stability and dyeing property, is mainly used for dyeing and printing wool, silk, chinlon and blended fabrics thereof, is widely applied to coloring paper, leather and wood, and is also widely used for manufacturing ink. AB1 belongs to an easily sensitized substance, can cause acute allergy to human bodies, and can cause damage to human organs after long-term contact. The AB1 has wide application range and large dosage, and a great amount of AB1 enters the nature in the production and use processes, which has potential threats to the ecological environment and human health, wherein the amount of the acidic black waste water generated in the printing and dyeing industry is the largest. Because the acid black printing and dyeing wastewater has high organic matter concentration, poor biodegradability and biotoxicity, the traditional biological method is difficult to achieve ideal effect on degradation. Therefore, the development of a novel degradation method for the acidic black water solution has important research value.
Compared with the traditional adsorption method for treating wastewater, the metal oxide semiconductor material photocatalytic degradation of pollutants in water has the advantages of mild conditions, no toxicity, no harm, complete degradation, convenient use, good regeneration performance and the like.
From Honda et al in Nature, published a TiO2From the article of photo-induced water splitting, TiO2Has attracted the attention of researchers as a photocatalyst. At present, TiO2The photocatalyst is already in the photovoltaic field and the photosynthesizing fieldThe method has wide application prospect in the aspects of wastewater and waste gas treatment and the like. TiO22The photocatalyst can decompose toxic and colored macromolecular pollutants into disposable micromolecules or CO under mild conditions2And the like, are considered to be the most green and effective pollutant treatment scheme. However, TiO2The catalytic performance of the catalyst is limited by the existence of objective factors such as low photo-generated electron transfer rate, easy recombination of current carriers and the like; in addition, the wide band gap determines TiO2The light response range of the light source is mainly concentrated in a high-energy light subarea, and the utilization rate of the sunlight on the earth surface is very low.
To overcome these deficiencies, researchers have adopted a variety of approaches to TiO2The catalyst was investigated for modification. The organic molecules have the advantages of easy modification, simple synthesis, convenient separation and purification and the like, and can be designed into specific functions according to requirements, so that the molecules with excellent light capture capability can be developed by a series of means; and because of the characteristics of low cost, light weight, small density, easy combination with inorganic materials and the like, the organic molecules are generated&TiO2A sensitizing catalyst system of (a). The photocatalyst of the system can expand the photoresponse range to the visible light region, realize the maximum utilization of the surface solar energy and realize the effective degradation of pollutants. When the dye-sensitized photocatalyst is irradiated with visible light, the sensitizer molecule absorbs the visible light to generate electrons. These photo-generated electrons are then transferred to TiO2Is captured by oxygen molecules adsorbed in the vicinity of the catalyst surface to produce O2-A free radical. At the same time, TiO2It can also absorb ultraviolet light energy to generate electrons and holes, and the electrons are transferred to TiO2Leaving holes in the TiO layer2The valence band position of (3) can react with water in the solution to generate OH radicals. Thus, the sensitizer molecule is supported on the TiO2After the surface treatment, the recombination of electrons and holes is avoided, the light energy utilization rate is improved, and the catalytic efficiency is also improved.
With TiO2The intrinsic photocatalysis process under the action of high-energy photons is different, and the dye-sensitized photocatalyst absorbs photons under the irradiation of visible light andexcited to anchor in the TiO2Organic molecules on the surface, followed by excited organic molecules to inject photo-generated electrons into the TiO2The oxygen is captured by the ground state oxygen (such as oxygen) adsorbed on the surface of the conduction band, the oxygen with high activity is released, and then pollutant molecules are attacked to initiate a series of catalytic reactions. In this process, TiO2The function of the organic sensitizer is to act as an adsorption matrix and a transmission medium of photo-generated electrons of the organic sensitizer in the whole catalytic pool system. Sunlight and ground state oxygen in a system are two inexhaustible resources, so that the construction of efficient organic sensitizer molecules becomes the key for determining the catalytic performance of the whole system.
Disclosure of Invention
The invention aims to provide a carbazole organic dye and a preparation method thereof, a dye-sensitized titanium dioxide composite catalyst and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a carbazole organic dye, which has a structure shown in a formula I:
wherein R is1、R2And R3Independently comprise C0～12An alkyl group;
l is a linking group, and L comprises an alkylene group, an aromatic alkylene group or C0～12An alkyl group;
the A is an anchoring group and comprises an acid group, a ketone group or a nitrogen-containing conjugated ring group.
Preferably, said C0～12Alkyl includes normal alkyl or isomeric alkyl; the L comprises vinyl, propenyl, butenyl, styryl or thiophenethenyl; said A comprises cyanoacetic acid group, benzyl group, benzaldehyde group, acrylic acid group, pyrrolyl group or pyridyl group。
Preferably, the carbazole-based organic dye includes:
the invention provides a preparation method of carbazole organic dye in the technical proposal,
when the L is an alkenyl group or an aromatic alkenyl group, the preparation method of the carbazole organic dye comprises the following steps:
1) mixing a compound with a structure shown in a formula II, a compound with a structure shown in a formula III, tetrakis (triphenylphosphine) palladium, toluene and a sodium carbonate aqueous solution, and carrying out Suzuki coupling reaction to obtain a first intermediate;
2) mixing the first intermediate, the organic mixed solvent and a sodium hydroxide solution of sodium borohydride to perform aldehyde reduction reaction to obtain a second intermediate;
3) mixing the second intermediate, dichloromethane and triphenyl phosphorus bromide to perform nucleophilic substitution reaction to obtain a third intermediate;
4) mixing the third intermediate with a compound with a structure shown in a formula IV, dichloromethane and DBU, and carrying out wittig reaction to obtain an organic dye intermediate;
5) mixing the organic dye intermediate, cyanoacetic acid, toluene, acetonitrile and piperidine, and carrying out Kenaoergel reaction to obtain a carbazole organic dye;
or, when said L is an alkenyl group or an aromatic alkenyl group, replacing said steps 1) and 2) with the following steps:
mixing 4-diphenylaminobenzaldehyde, an organic mixed solvent and a sodium hydroxide solution of sodium borohydride to perform aldehyde reduction reaction to obtain a second intermediate;
when the L is C0～12When the alkyl is adopted, the preparation method of the carbazole organic dye comprises the following steps:
mixing a compound with a structure shown in a formula V, a compound with a structure shown in a formula VI, tetrakis (triphenylphosphine) palladium, toluene and a sodium carbonate aqueous solution, and carrying out Suzuki coupling reaction to obtain an organic dye intermediate;
mixing the organic dye intermediate, cyanoacetic acid, toluene, acetonitrile and piperidine, and carrying out Kenaoergel reaction to obtain a carbazole organic dye;
preferably, the using amount ratio of the compound with the structure shown in the formula II, the compound with the structure shown in the formula III, the palladium tetrakis (triphenylphosphine), the toluene and the sodium carbonate aqueous solution is 1-2 mmol: 1.2-2.4 mmol: 0.1-0.3 g: 30-40 mL: 10-15 mL, and the concentration of the sodium carbonate aqueous solution is 2 mol/L; the temperature of the suzuki coupling reaction is 90 ℃, and the time is 48 hours;
the dosage ratio of the first intermediate, the organic mixed solvent and the sodium hydroxide solution of sodium borohydride is 0.1-0.5 g: 10-15 mL: 5-10 mL; the organic mixed solvent is a mixed solvent of THF and methanol, and the volume ratio of the THF to the methanol is 4: 1; the sodium hydroxide solution of sodium borohydride is prepared by dissolving 50-80 mg of sodium borohydride in 5-10 mL of sodium hydroxide aqueous solution, wherein the mass concentration of the sodium hydroxide aqueous solution is 4%; the temperature of the aldehyde reduction reaction is 0 ℃, and the time is 0.5-5 h.
Preferably, when the third intermediate is prepared, the using amount ratio of the second intermediate to dichloromethane to triphenyl phosphorus bromide is 0.2-0.5 g: 10-15 mL: 0.1-0.3 g, the temperature of the nucleophilic substitution reaction is room temperature, and the time is 24 hours;
and during the wittig reaction, the dosage ratio of the third intermediate to the compound with the structure shown in the formula IV, dichloromethane and DBU is 0.1-0.3 g: 20-30 mL: 0.5-1.5 mL, the wittig reaction temperature is room temperature, and the wittig reaction time is 0.5-5 h.
The invention provides a dye-sensitized titanium dioxide composite catalyst, which comprises titanium dioxide and carbazole organic dyes, wherein the carbazole organic dyes are loaded on the titanium dioxide, and the loading amount of the carbazole organic dyes is 0.01-2 wt%.
The invention provides a preparation method of the dye-sensitized titanium dioxide composite catalyst in the technical scheme, which comprises the following steps:
carbazole organic dye, dichloromethane and nano-grade TiO2Mixing the particles, and compounding to obtain the dye-sensitized titanium dioxide composite catalyst.
Preferably, the carbazole-based organic dye, dichloromethane and nano-scale TiO2The dosage ratio of the particles is 6 mu mol:10mL:500 mg; the temperature of the compounding is room temperature, and the compounding time is 24 h.
The invention provides an application of the dye-sensitized titanium dioxide composite catalyst prepared by the technical scheme or the dye-sensitized titanium dioxide composite catalyst prepared by the preparation method in the technical scheme in catalytic degradation of acid black in wastewater.
The invention provides a carbazole organic dye and a preparation method thereof, a dye-sensitized titanium dioxide composite catalyst and a preparation method and application thereof.
The dye molecule is used for preparing the dye-sensitized titanium dioxide composite catalyst, and in the obtained catalyst, the dye is adsorbed on the surface of titanium dioxide, the particles are uniformly distributed, the visible light response range of a titanium dioxide semiconductor is widened, the catalytic effect is good, the treatment efficiency of wastewater is improved, and the service life of photocatalytic particles is prolonged.
The synthesis process of the carbazole organic dye and the method for preparing the dye-sensitized titanium dioxide composite catalyst have the advantages of high yield, synthesis time and cost saving and low environmental pollution.
Drawings
FIG. 1 shows TEC @ TiO2A graph of the uv-vis spectrum change of degraded AB 1;
FIG. 2 is TOEC @ TiO2Ultraviolet-visible spectrum change diagram of catalyst degradation AB 1;
FIG. 3 is TSEC @ TiO2Ultraviolet-visible spectrum change diagram of catalyst degradation AB 1;
FIG. 4 is TTEC @ TiO2The ultraviolet-visible spectrum change diagram of catalyst degradation AB 1;
FIG. 5 is TXC @ TiO2Ultraviolet-visible spectrum change diagram of catalyst degradation AB 1;
FIG. 6 is TOXC @ TiO2Ultraviolet-visible spectrum change diagram of catalyst degradation AB 1;
FIG. 7 is TSXC @ TiO2Ultraviolet-visible spectrum change diagram of catalyst degradation AB 1;
FIG. 8 is TTXC @ TiO2The ultraviolet-visible spectrum change diagram of catalyst degradation AB 1;
FIG. 9 is a graph showing the comparative degradation performance of the dye-sensitized titanium dioxide composite catalysts prepared in examples 1 to 8 with respect to acid black;
FIG. 10 is a graph showing the catalytic degradation performance of the pure titanium dioxide of the comparative example to acid black.
Detailed Description
The invention provides a carbazole organic dye, which has a structure shown in a formula I:
wherein R is1、R2And R3Independently comprise C0～12An alkyl group;
l is a linking groupSaid L comprises an alkylene group, an aryl alkylene group or C0～12An alkyl group;
the A is an anchoring group and comprises an acid group, a ketone group or a nitrogen-containing conjugated ring group.
In the present invention, said C0～12The alkyl group preferably includes a normal alkyl group or an isomeric alkyl group, said C0～12Alkyl is preferably C2～8Alkyl, more preferably C5～6An alkyl group; said L preferably comprises ethenyl, propenyl, butenyl, styryl or thiophenethenyl; said a preferably comprises a cyanoacetic acid group, a benzyl group, a benzaldehyde group, an acrylic group, a pyrrolyl group or a pyridyl group.
In the present invention, the carbazole-based organic dye preferably includes:
the carbazole organic dye provided by the invention contains triphenylamine groups and carbazole groups, and nitrogen atoms in triphenylamine are sp3In the hybrid configuration, a single bond capable of freely rotating is formed between a nitrogen atom and a benzene ring, so that the triphenylamine molecule presents a non-planar propeller structure. Due to the structural particularity, the triphenylamine derivative has the characteristics of good electron donating performance and hole transmission performance, high light stability, low ionization potential and the like; the three para positions of the benzene ring of the triphenylamine are easy to generate electrophilic substitution reaction of the aromatic ring to generate various derivatives, so that the triphenylamine can be used for constructing various photoelectric molecules with different functions. The carbazole has a large conjugated system in a ring molecule, strong electron mobility in the molecule, high thermal stability and photochemical stability, and can form stable positive ions, electron donors commonly used in the field of photoelectrochemistry and a composition group of a hole transport material. 3,6 and 9 positions of the carbazole ring are easy to participate in chemical reaction to introduce functional groups, and further different condensation reactions are performedIntroducing other compounds into carbazole to form various functional structures; carbazole has strong absorption to high-energy photons, and the band gap (bandgap) of carbazole is about 3.2 eV. The dye molecule provided by the invention contains triphenylamine groups and carbazole groups, and the dye molecule with the structure can enhance the degradation effect of the dye-sensitized titanium dioxide composite catalyst on pollutants.
The invention provides a preparation method of carbazole organic dye in the technical proposal,
when the L is an alkenyl group or an aromatic alkenyl group, the preparation method of the carbazole organic dye comprises the following steps:
1) mixing a compound with a structure shown in a formula II, a compound with a structure shown in a formula III, tetrakis (triphenylphosphine) palladium, toluene and a sodium carbonate aqueous solution, and carrying out Suzuki coupling reaction to obtain a first intermediate;
2) mixing the first intermediate, the organic mixed solvent and a sodium hydroxide solution of sodium borohydride to perform aldehyde reduction reaction to obtain a second intermediate;
3) mixing the second intermediate, dichloromethane and triphenyl phosphorus bromide to perform nucleophilic substitution reaction to obtain a third intermediate;
4) mixing the third intermediate with a compound with a structure shown in a formula IV, dichloromethane and DBU, and carrying out wittig reaction to obtain an organic dye intermediate;
5) mixing the organic dye intermediate, cyanoacetic acid, toluene, acetonitrile and piperidine, and carrying out Kenaowerger reaction to obtain carbazole organic dye;
or, when said L is an alkenyl group or an aromatic alkenyl group, replacing said steps 1) and 2) with the following steps:
mixing 4-diphenylaminobenzaldehyde, an organic mixed solvent and a sodium hydroxide solution of sodium borohydride to perform aldehyde reduction reaction to obtain a second intermediate;
when it is at homeL is C0～12When the alkyl is adopted, the preparation method of the carbazole organic dye comprises the following steps:
mixing a compound with a structure shown in a formula V, a compound with a structure shown in a formula VI, tetrakis (triphenylphosphine) palladium, toluene and a sodium carbonate aqueous solution, and carrying out Suzuki coupling reaction to obtain a carbazole organic dye;
mixing the organic dye intermediate, cyanoacetic acid, toluene, acetonitrile and piperidine, and carrying out Kenaoergel reaction to obtain a carbazole organic dye;
in the present invention, unless otherwise specified, the starting materials for the preparation are commercially available products known to those skilled in the art or prepared by methods known in the art.
When the L is alkenyl or aromatic alkenyl, the preparation method of the carbazole organic dye comprises the following steps:
the method comprises the steps of mixing a compound with a structure shown in a formula II, a compound with a structure shown in a formula III, tetrakis (triphenylphosphine) palladium, toluene and a sodium carbonate aqueous solution, and carrying out Suzuki coupling reaction to obtain a first intermediate. In the invention, the compound with the structure shown in the formula II, the compound with the structure shown in the formula III, the tetrakis (triphenylphosphine) palladium, the toluene and the sodium carbonate aqueous solution are preferably used in a ratio of 1-2 mm ol: 1.2-2.4 mmol: 0.1-0.3 g: 30-40 mL: 10-15 mL, more preferably 1.5mmol:2mmol:0.2g:35mL:15mL, and the concentration of the sodium carbonate aqueous solution is preferably 2 mol/L. In the present invention, the mixing process is preferably that the compound having the structure shown in formula II, the compound having the structure shown in formula III and tetrakis (triphenylphosphine) palladium are mixed in a three-neck round-bottom flask, degassed toluene is injected into the three-neck round-bottom flask by a syringe under the protection of nitrogen, the stirring is started to dissolve the solid, and then an aqueous solution of sodium carbonate is injected. The stirring process is not particularly limited in the present invention, and a process well known in the art may be selected to dissolve the solid.
In the present invention, the Suzuki coupling reaction is preferably carried out at 90 ℃ for 48 hours.
After the Suzuki coupling reaction is completed, the sodium carbonate solution in the obtained mixture is neutralized by acid, adjusted to be neutral, the organic matter is extracted by dichloromethane, then the organic matter is washed by saturated saline solution for a plurality of times, finally the organic phase is dried by anhydrous sodium sulfate, toluene and dichloromethane are removed by a rotary evaporator after filtration, the obtained crude product is separated by a silica gel chromatographic column, and the mixed solvent of dichloromethane and petroleum ether (volume ratio) is used as eluent for elution, so as to obtain a first intermediate.
After the first intermediate is obtained, the first intermediate, the organic mixed solvent and a sodium hydroxide solution of sodium borohydride are mixed for aldehyde reduction reaction to obtain a second intermediate. In the invention, the dosage ratio of the first intermediate, the organic mixed solvent and the sodium hydroxide solution of sodium borohydride is preferably 0.1-0.5 g: 10-15 mL: 5-10 mL, more preferably 0.2-0.3 g: 12-14 mL: 6-8 mL, the organic mixed solvent is preferably a mixed solvent of THF and methanol, and the volume ratio of THF and methanol is preferably 4: 1; the sodium hydroxide solution of sodium borohydride is preferably prepared by dissolving 50-80 mg of sodium borohydride in 5-10 mL of sodium hydroxide solution, and the mass concentration of the sodium hydroxide solution is preferably 4%. In the present invention, the process of mixing is preferably that the first intermediate is placed in a round-bottom flask, the system is cooled to 0 ℃ and maintained, then a mixed solvent of THF and methanol is added, and a sodium hydroxide solution of sodium borohydride is dropped into the round-bottom flask.
In the invention, the temperature of the aldehyde reduction reaction is preferably 0 ℃, and the time is preferably 0.5-5 h, and more preferably 1 h. After the aldehyde reduction reaction is completed, transferring the obtained mixture to a separating funnel, extracting an organic matter by using dichloromethane, washing the organic matter by using deionized water, drying, filtering, removing the solvent by using a rotary evaporator, separating and purifying the obtained crude product by using a silica gel column chromatography, and eluting by using dichloromethane as an eluent to obtain a second intermediate.
Or, when said L is an alkenyl group or an aromatic alkenyl group, replacing said steps 1) and 2) with the following steps:
and mixing the 4-diphenylaminobenzaldehyde, the organic mixed solvent and a sodium hydroxide solution of sodium borohydride to perform aldehyde reduction reaction to obtain a second intermediate.
The dosage relationship of the 4-diphenylaminobenzaldehyde, the organic mixed solvent and the sodium hydroxide solution of sodium borohydride is the same as the dosage relationship of the first intermediate for preparing the second intermediate in the step 2), and the description is omitted here.
After the second intermediate is obtained, the second intermediate, dichloromethane and triphenyl phosphonium bromide are mixed for nucleophilic substitution reaction to obtain a third intermediate.
In the invention, the dosage ratio of the second intermediate, dichloromethane and triphenyl phosphonium bromide is preferably 0.2-0.5 g: 10-15 mL: 0.1-0.3 g, and more preferably 0.3-0.4 g: 12-14 mL: 0.1-0.2 g. In the present invention, the mixing process is preferably performed by adding the second intermediate into a round-bottom flask, displacing the air in the round-bottom flask with nitrogen, injecting dichloromethane, performing ultrasonic treatment to completely dissolve the solid, and adding triphenyl phosphonium bromide. The ultrasonic process is not particularly limited, and the solid can be completely dissolved.
In the invention, the temperature of the nucleophilic substitution reaction is room temperature, and the time is 24 h; the nucleophilic substitution reaction is carried out under the conditions of introducing nitrogen and stirring. The stirring process is not specially limited, and the smooth reaction can be ensured.
After the nucleophilic substitution reaction is completed, the solvent of the obtained material is preferably removed by using a rotary evaporator, the obtained crude product is subjected to silica gel column chromatography separation, dichloromethane is used as an eluent, all color bands capable of being eluted by the dichloromethane are washed away, and then a mixed solvent of dichloromethane and methanol in a volume ratio of 8.5:1.5 is used as the eluent to obtain a third intermediate.
After the third intermediate is obtained, the third intermediate, a compound with a structure shown in a formula IV, dichloromethane and DBU are mixed for wittig reaction, and the carbazole organic dye is obtained. In the invention, the dosage ratio of the third intermediate, the compound with the structure shown in the formula IV, dichloromethane and DBU is preferably 0.1-0.3 g, 20-30 mL, 0.5-1.5 mL, and more preferably 0.2g, 25mL and 1.5 mL. In the invention, the process of mixing preferably comprises the steps of firstly adding the third intermediate and the compound with the structure shown in the formula IV into a round-bottom three-neck flask, injecting freshly distilled dichloromethane into the round-bottom three-neck flask under the protection of nitrogen, stirring for 1-2 min, and slowly injecting DBU by using a syringe.
In the invention, the temperature of the wittig reaction is preferably room temperature, and the time is preferably 0.5-5 h, and more preferably 2 h. The progress of the reaction is preferably checked by TLC. After the wittig reaction is completed, the obtained product is preferably separated by silica gel column chromatography, and the separation ratio of dichloromethane, petroleum ether, 2:1 (volume ratio) mixed solvent is used as eluent for elution, the obtained solid is dissolved by dichloromethane, then deionized water and trifluoroacetic acid are added for stirring, the obtained mixture is poured into a beaker and neutralized by alkali, organic matters are extracted by dichloromethane, then saturated saline solution is used for washing for a plurality of times and drying, a crude product is separated by silica gel column chromatography, and dichloromethane is used as eluent for elution, so that an organic dye intermediate is obtained.
After an organic dye intermediate is obtained, mixing the organic dye intermediate, cyanoacetic acid, toluene, acetonitrile and piperidine, and carrying out a Kenaoergel reaction to obtain the carbazole organic dye.
In the present invention, the knoevenagel reaction is performed under nitrogen protection, and the ratio of the amount of the organic dye intermediate, cyanoacetic acid, toluene, acetonitrile and piperidine is preferably 30 mg: 83 mg: 15mL of: 5mL of acetonitrile: 0.5 mL. In the present invention, the temperature of the knoevenagel reaction is preferably 80 ℃ and the time is preferably 12 hours, and the knowenger reaction is preferably performed under reflux conditions.
After the Kenawenger reaction is finished, extracting the obtained material by using dichloromethane, washing the obtained material by using dilute hydrochloric acid aqueous solution, and separating the obtained material by using dichloromethane as an eluent through a silica gel column chromatography to obtain the carbazole organic dye.
When L is C0～12Alkyl, the carbazolesThe preparation method of the organic dye comprises the following steps:
mixing a compound with a structure shown in a formula V, a compound with a structure shown in a formula VI, tetrakis (triphenylphosphine) palladium, toluene and a sodium carbonate aqueous solution, and carrying out Suzuki coupling reaction to obtain an organic dye intermediate;
after an organic dye intermediate is obtained, mixing the organic dye intermediate, cyanoacetic acid, toluene, acetonitrile and piperidine, and carrying out a Kenaoergel reaction to obtain the carbazole organic dye.
In the present invention, the suzuki coupling reaction process is the same as the preparation process of the first intermediate, and the knowenger reaction process is the same as the preparation process of the carbazole-based organic dye, and is not described herein again.
The invention provides a dye-sensitized titanium dioxide composite catalyst, which comprises titanium dioxide and carbazole organic dyes, wherein the carbazole organic dyes are loaded on the titanium dioxide, and the loading amount of the carbazole organic dyes is 0.01-2 wt%. In the dye-sensitized titanium dioxide composite catalyst, an anchoring group of the carbazole organic dye and titanium dioxide form an ester-like bond to be attached to the surface of a semiconductor.
The invention provides a preparation method of the dye-sensitized titanium dioxide composite catalyst in the technical scheme, which comprises the following steps:
carbazole organic dye, dichloromethane and nano-grade TiO2Mixing the particles, and compounding to obtain the dye-sensitized titanium dioxide composite catalyst.
In the present invention, the nano-sized TiO2The preparation process of the particles preferably comprises the following steps: mixing tetraisobutyl titanate and isopropanol, and dropwise adding deionized water into the obtained mixture to obtain a colloidal suspension; carrying out gelation reaction on the colloidal suspension to obtain a colloidal material; washing, drying and calcining the colloidal material in sequence to obtain the nano-grade TiO2And (3) particles.
In the present invention, it is preferable to mix tetraisobutyl titanate and isopropyl alcohol, and to the resulting mixture, deionized water is added dropwise to obtain a colloidal suspension. In the present invention, the volume ratio of the tetraisobutyl titanate, the isopropanol and the deionized water is preferably 12.5:80: 4. The mixing process is not particularly limited in the present invention, and may be a process known to those skilled in the art.
After obtaining the colloidal suspension, the present invention preferably subjects the colloidal suspension to a gelation reaction to obtain a gummy material. In the present invention, the gelation reaction is preferably carried out under stirring conditions, and the stirring is not particularly limited in the present invention, and a process known to those skilled in the art may be selected; the temperature of the gelation reaction is preferably room temperature, and the time is preferably 6 hours.
After the colloidal material is obtained, the invention preferably washes, dries and calcines the colloidal material in turn to obtain the nano-grade TiO2And (3) particles. After the gelation reaction is completed, the invention preferably uses a Buchner funnel to collect the gelatinous material, then washes the gelatinous material with deionized water and absolute ethyl alcohol for three times respectively, and then dries the gelatinous material in a forced air drying oven at 90 ℃ for 5 hours; after drying, scraping the solid, and calcining the solid in a muffle furnace for 5 hours at 400 ℃; after calcination, the heating is closed, the hearth is naturally cooled to room temperature, and then a sample is taken out to obtain the nano TiO2And (3) granules. In the present invention, the nano-sized TiO2The particle size of the particles is preferably 15-80 nm.
In the invention, carbazole organic dye, dichloromethane and nano-grade TiO are mixed2Mixing the particles, and compounding to obtain the dye-sensitized titanium dioxide composite catalyst. In the invention, the carbazole organic dye, dichloromethane and nano-scale TiO2The amount ratio of the particles is preferably 6. mu. mol:10mL:500 mg. In the present invention, the mixing process is preferably performed by dissolving the carbazole-based organic dye in dichloromethane, and then adding the nano-sized TiO into the obtained solution2And (3) granules. In the invention, the compounding is preferably carried out under stirring conditions, and the rotation speed of the stirring is preferably 2000 rpm; the temperature of the compounding is preferably room temperature, and the time of the compounding is preferably 24 h. After the compounding is completed, the present invention preferably removes methylene chlorideAnd then vacuum drying is carried out for 24 hours at 35 ℃ to obtain the dye-sensitized titanium dioxide composite catalyst.
The invention provides application of the dye-sensitized titanium dioxide composite catalyst in the technical scheme in catalytic degradation of acid black in wastewater. The process of using the dye-sensitized titanium dioxide composite catalyst in catalytic degradation of acid black in wastewater is not particularly limited, and a process known by a person skilled in the art can be selected. In the embodiment of the invention, in order to determine the catalytic degradation performance of the dye-sensitized titanium dioxide composite catalyst on acid black, specifically, the dye-sensitized titanium dioxide composite catalyst (10mg) is mixed with an AB1 pollutant aqueous solution (10ppm), and the mixture is stirred in a dark box for 30min, so that the adsorption-desorption balance of the catalyst and the pollutant is achieved before illumination; after the illumination was started, a stopwatch was used for timing, samples were taken at 0s, 30s, 60s, 90s, 120s, 150s, 180s, 3min, 6min, 9min, 12min, 30min and 60min, respectively, and the samples were centrifuged to separate the supernatant and tested for UV-Vis.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
Compound 1: synthesis of 6- (4- (diphenylamino) phenyl) -9-ethylcarbazole-3-carbaldehyde (Suzuki coupling reaction):
433.5mg (1.5mmol) of 4-diphenylaminobenzeneboronic acid, 603mg (2mmol) of 3-bromo-6-formyl-9-ethylcarbazole and 0.2g of tetrakis (triphenylphosphine) palladium were added to a three-necked round-bottom flask, 35mL of degassed toluene was injected into the three-necked round-bottom flask by a syringe under nitrogen protection, the solid was dissolved by stirring, and 15mL of a 2mol/L aqueous solution of sodium carbonate was injected and reacted at 90 ℃ for 48 hours. After the reaction is finished, the sodium carbonate solution in the mixture is neutralized by acid. After adjusting to neutrality, the organic was extracted with dichloromethane, then washed several times with saturated brine, and finally the organic phase was dried over anhydrous sodium sulfate. After filtration, toluene and dichloromethane were removed by rotary evaporator to give a crude black product. The crude product was separated by silica gel column chromatography using dichloromethane and petroleum ether 2:1 as eluent to give the product as a bright yellow solid in 70% yield.
Synthesis of organic dye 2-cyano-3- (6- (4- (diphenylamino) phenyl) -9-ethyl-9H-carbazol-3-yl) acrylic acid (TEC) (Knoevenagel reaction):
under the protection of nitrogen, 30mg of compound 1 and 83mg of cyanoacetic acid are added into 0.5mL of piperidine in a mixed solution of 15mL of toluene and 5mL of acetonitrile, reflux is carried out for 12 hours at 80 ℃ under the protection of nitrogen, dichloromethane is extracted, a dilute hydrochloric acid aqueous solution is washed, dichloromethane is used as an eluent, and silica gel column chromatography is carried out to separate to obtain a solid product, namely TEC, with the yield of 89%.
In this embodiment, the synthesis process of the organic dye TEC is as follows:
preparing a dye-sensitized titanium dioxide composite catalyst: taking carbazole organic dye TEC6 mu mol, adding 10mL of dichloromethane for dissolution, and then adding 500mg of nano TiO2Stirring the particles for 24 hours, removing dichloromethane after the reaction is finished, and drying the particles for 24 hours in vacuum at 35 ℃ to obtain the dye-sensitized titanium dioxide composite catalyst, which is marked as TEC @ TiO2。
Example 2
Compound 2: synthesis of 4-Benzylbenzophenol (aldehyde reduction):
0.2g (0.74mmol) of 4-diphenylaminobenzaldehyde was added to a round-bottomed flask equipped with a magnetic stirrer, the system was cooled to 0 ℃ and maintained, then a mixed solvent of 10mL THF and methanol (volume ratio 4:1) was added, 60mg sodium borohydride was dissolved in 6mL 4% sodium hydroxide solution, and 8mL of the solution was slowly dropped into the round-bottomed flask described above. The reaction was monitored by TLC and after completion the mixture was transferred to a separatory funnel. The organics were extracted with dichloromethane, washed with copious amounts of deionized water and dried. After filtration, the solvent was removed by rotary evaporator to give a white crude product. The product was purified by silica gel column chromatography with dichloromethane as eluent to give a yellow liquid product in 90% yield.
Compound 3: synthesis of 4-diphenylaminobenzyl triphenylphosphonium bromide (nucleophilic substitution reaction): 0.4g (0.66mmol) of Compound 2 was added to a dry round bottom flask with a magnetic stir bar, the air in the round bottom flask was displaced with nitrogen, 13mL of dichloromethane were then injected, and the solid was completely dissolved by sonication. 0.2g of triphenylphosphine bromide was added thereto, and the mixture was stirred at room temperature under dry nitrogen for 24 hours. After the reaction is finished, the solvent is removed by a rotary evaporator to obtain a white crude product. The crude product is separated by silica gel column chromatography, dichloromethane is firstly used as eluent, and all color bands which can be eluted by dichloromethane are washed away. Then, a mixed solvent of dichloromethane and methanol at 8.5:1.5 was used as an eluent to obtain a white solid product with a yield of 30%.
Compound 4: synthesis of 6- (4- (diphenylamino) styryl) -9-ethylcarbazole-3-carbaldehyde (wittig reaction): 0.2g (0.80mmol) of 3, 6-dialdehyde carbazole and 0.2g of compound 3 were added into a dry round-bottom three-necked flask, 25mL of freshly distilled dichloromethane were injected into the round-bottom three-necked flask under the protection of nitrogen, stirred for 1min, 1.5mL of DBU was slowly injected by a syringe, reacted at room temperature, and the progress of the reaction was checked by TLC. After the reaction is finished, the crude product is separated by silica gel column chromatography, and a mixed solvent of dichloromethane and petroleum ether which is 2:1 is used as an eluent, so that a yellow solid is obtained. 10mL of dichloromethane was added to dissolve the mixture, and 3mL of deionized water and 10mL of trifluoroacetic acid were added thereto and vigorously stirred for 30 min. After stirring was completed, the mixture was poured into a beaker and neutralized with alkali, the organic matter was extracted with dichloromethane, then washed several times with saturated brine and dried, and the crude product was separated using silica gel column chromatography with dichloromethane as the eluent to give a pale yellow solid with a yield of 30%.
Synthesis of the organic dye 2-cyano-3- (6- (4- (diphenylamino) styryl) 9-ethyl-9H-carbazol-3-yl) acrylic acid (toe) (Knoevenagel reaction): the raw material is compound 4, and the synthesis method is the synthesis of compound TEC, and the specific process is as follows:
preparing a dye-sensitized titanium dioxide composite catalyst: according to the method of the embodiment 1, the carbazole organic dye TOEC is used as a raw material to prepare the dye-sensitized titanium dioxide composite catalyst which is marked as TOEC @ TiO2。
Example 3
Synthesis of Compound 5:4- (4-Diphenylaminobiphenyl) Formaldehyde (Suzuki coupling reaction): 433.5mg (1.5mmol) of 4-diphenylaminobenzeneboronic acid, 603mg (2mmol) of 4-bromobenzaldehyde and 200mg of tetrakis (triphenylphosphine) palladium were added to a three-necked round-bottomed flask, 35mL of degassed toluene was injected into the three-necked round-bottomed flask by a syringe under nitrogen protection, and stirring was started to dissolve the solid, and then 15mL of a 2mol/L aqueous solution of sodium carbonate was injected and reacted at 90 ℃ for 48 hours. After the reaction is finished, the sodium carbonate solution in the mixture is neutralized by acid. The mixture was neutralized, and the organic layer was extracted with dichloromethane, washed with saturated brine several times, and finally dried over anhydrous sodium sulfate. After filtration, toluene and dichloromethane were removed by rotary evaporator to give a crude black product. The crude product was separated by silica gel column chromatography using dichloromethane and petroleum ether 2:1 as eluent to give the product as a bright yellow solid in 70% yield.
Compound 6: synthesis of 4- (4-diphenylaminobiphenyl) methanol (aldehyde reduction reaction): compound 5 was used as a starting material, and the synthesis method was identical to that of compound 2.
Compound 7: synthesis of 4- (4-diphenylaminobiphenyl) methyl triphenyl phosphonium bromide (phosphorus ylide reagent preparation): the raw material is compound 6, and the synthesis method is the synthesis of compound 3.
Compound 8: synthesis of 6- (2- (4'- (diphenylamino) - [1,1' -biphenyl ] -4-yl) vinyl) -9-ethylcarbazole-3-carbaldehyde (wittig reaction): the raw materials are 3, 6-dialdehyde-9-ethyl carbazole and a compound 7, and the synthesis method is the synthesis of a compound 4.
Synthesis of the organic dye 2-cyano-3- (6- (2- (4'- (diphenylamino) - [1,1' biphenyl ] 4-yl) vinyl) 9-ethyl-9H-carbazol-3-yl) acrylic acid (TSEC) (Knoevenagel reaction): the raw material is compound 8, and the method is used for synthesizing compound TEC, and the specific process is as follows:
preparing a dye-sensitized titanium dioxide composite catalyst: according to the method of the embodiment 1, carbazole organic dye TSEC is used as a raw material to prepare the dye-sensitized titanium dioxide composite catalyst, which is recorded as TSEC @ TiO2。
Example 4
Compound 9: synthesis of 5- [2- (4-diphenylaminophenyl) thiophene ] carboxaldehyde (Suzuki coupling reaction): the raw materials are 5-aldehyde-2-thiopheneboronic acid and 4-bromotriphenylamine, and the synthesis method is the synthesis of the compound 5.
Compound 10: synthesis of 5- [2- (4-diphenylaminophenyl) thiophene ] methanol (aldehyde reduction reaction): compound 9 was used as a starting material, and the synthesis method was the same as that of compound 2.
Compound 11: synthesis of 5- [2- (4-diphenylaminophenyl) thiophene ] methyltriphenylphosphonium bromide (preparation of phosphonium ylide reagent): the starting material was compound 10, and the synthesis method was the synthesis of compound 3.
Synthesis of Compound 12:6- (2- (5- (4- (diphenylamino) phenyl) thiophen-2-yl) vinyl) -9-ethylcarbazole-3-carbaldehyde (wittig reaction): the raw materials are 3, 6-dicarboxyl-9-ethyl carbazole and a compound 11, and the synthesis method is the synthesis of a compound 4.
Synthesis of the organic dye 2-cyano-3- (6- (2- (5- (4- (diphenylamino) phenyl) thiophen-2-yl) vinyl) 9-ethyl-9H-carbazol-3-yl) acrylic acid (TTEC) (Knoevenagel reaction): the raw material is compound 12, and the method is used for synthesizing compound TEC, and the specific process is as follows:
preparing a dye-sensitized titanium dioxide composite catalyst: according to the method of the embodiment 1, the carbazole organic dye TTEC is used as a raw material to prepare the dye-sensitized titanium dioxide composite catalyst which is marked as TTEC @ TiO2。
Example 5
Compound 13: synthesis of 6- (4- (diphenylamino) phenyl) -9-hexylcarbazole-3-carbaldehyde (Suzuki coupling reaction): the raw materials are 3-bromine-6-aldehyde-N-hexyl carbazole and 4-diphenylamino phenylboronic acid, and the synthesis method is the synthesis of the compound 1.
Synthesis of the organic dye 2-cyano-3- (6- (4- (diphenylamino) phenyl) -9-hexyl-9H-carbazol-3-yl) acrylic acid (TXC) (Knoevenagel reaction): the raw material is compound 13, and the method is used for synthesizing compound TEC, and the specific process is as follows:
preparing a dye-sensitized titanium dioxide composite catalyst: according to the method of the embodiment 1, a carbazole organic dye TXC is used as a raw material to prepare a dye-sensitized titanium dioxide composite catalyst which is recorded as TXC @ TiO2。
Example 6
Compound 14: synthesis of 6- (4- (diphenylamino) styryl) -9-hexylcarbazole-3-carbaldehyde (wittig reaction): the raw materials are 3, 6-dialdehyde-N-hexyl carbazole and a compound 3, and the synthesis method is the synthesis of a compound 4.
Synthesis of the organic dye 2-cyano-3- (6- (4- (diphenylamino) styryl) 9-hexyl-9H-carbazol-3-yl) acrylic acid (TOXC) (Knoevenagel reaction): the raw material is compound 14, and the method is used for synthesizing compound TEC, and the specific process is as follows:
preparing a dye-sensitized titanium dioxide composite catalyst: according to the method of the embodiment 1, carbazole organic dye TOXC is used as a raw material to prepare a dye-sensitized titanium dioxide composite catalyst which is marked as TOXC @ TiO2。
Example 7
Compound 15: synthesis of 6- (2- (4'- (diphenylamino) - [1,1' -biphenyl ] -4-yl) vinyl) -9-hexylcarbazole-3-carbaldehyde (wittig reaction): the raw materials are 3, 6-dicarboxyl-N-hexyl carbazole and a compound 7, and the synthesis method is the synthesis of a compound 4.
Synthesis of the organic dye 2-cyano-3- (6- (2- (4'- (diphenylamino) - [1,1' biphenyl ] 4-yl) vinyl) 9-hexyl-9H-carbazol-3-yl) acrylic acid (TSXC) (Knoevenagel reaction): the raw material is compound 15, and the method is used for synthesizing compound TEC, and the specific process is as follows:
preparing a dye-sensitized titanium dioxide composite catalyst: according to the method of the embodiment 1, carbazole organic dye TSXC is used as a raw material to prepare a dye-sensitized titanium dioxide composite catalyst which is marked as TSXC @ TiO2。
Example 8
Compound 16: synthesis of 6- (2- (5- (4- (diphenylamino) phenyl) thiophen-2-yl) vinyl) -9-hexylcarbazole-3-carbaldehyde (wittig reaction): the raw materials are 3, 6-dialdehyde-N-hexyl carbazole and a compound 11, and the synthesis method is the synthesis of a compound 4.
Synthesis of the organic dye 2-cyano-3- (6- (2- (5- (4- (diphenylamino) phenyl) thiophen-2-yl) vinyl) 9-hexyl-9H-carbazol-3-yl) acrylic acid (TTXC) (Knoevenagel reaction): the raw material is compound 16, and the method is used for synthesizing compound TEC, and the specific process is as follows:
preparing a dye-sensitized titanium dioxide composite catalyst: according to the method of the embodiment 1, a carbazole organic dye TTXC is used as a raw material to prepare a dye-sensitized titanium dioxide composite catalyst which is marked as TTXC @ TiO2。
Performance testing
The degradation effects of the dye-sensitized titanium dioxide composite catalysts prepared in examples 1 to 8 were analyzed:
the photocatalytic performance of the dye-sensitized titanium dioxide composite catalyst was tested by using a xenon lamp, the degradation object was an AB1 contaminant aqueous solution (10ppm), the power of the xenon lamp was 300W, the distance from the solution was 10cm, and the catalytic activity of the dye-sensitized titanium dioxide composite catalyst prepared in examples 1 to 8 was tested at room temperature by using ventilation and heat dissipation.
The detection method comprises the following steps: the dye-sensitized titanium dioxide composite catalysts (TEC @ TiO) prepared in examples 1 to 8 were respectively added2、TOEC@TiO2、TSEC@TiO2、TTEC@TiO2、TXC@TiO2、TOXC@TiO2、TSXC@TiO2、TTXC@TiO2)10mg of the catalyst is added into 100mLAB1 pollutant aqueous solution (10ppm), and the obtained mixed solution is stirred for 30min in a dark box to ensure that the catalyst and the pollutant reach adsorption and desorption equilibrium before illumination; and then starting illumination, timing by using a stopwatch, sampling at 0s, 30s, 60s, 90s, 120s, 150s, 180s, 3min, 6min, 9min, 12min, 30min and 60min respectively, separating supernatant liquid from the samples by using a centrifugal machine, and testing UV-Vis, wherein ultraviolet-visible spectrum change graphs of AB1 of different dye-sensitized titanium dioxide composite catalysts under different xenon lamp irradiation times are shown in figures 1-8.
FIG. 1 shows TEC @ TiO2The ultraviolet-visible spectrum change chart (550-650 nm) of the degraded AB1 shows that the spectral absorption at about 600nm gradually decreases with the time as the characteristic absorption of AB1, which indicates that AB1 is gradually decomposed.
FIG. 2 is TOEC @ TiO2The ultraviolet-visible spectrum change graph (550-650 nm) of the catalyst degradation AB1 shows that the spectral absorption at about 600nm gradually decreases with the time as the characteristic absorption of AB1, which indicates that AB1 gradually decomposes.
FIG. 3 is TSEC @ TiO2The graph of the ultraviolet-visible spectrum change (300-800nm) of the catalyst degradation AB1 shows that the spectral absorption at about 600nm gradually decreases with the time as the characteristic absorption of AB1, which indicates that AB1 is gradually decomposed. Moreover, the spectral absorption at 300-350nm gradually increased with the passage of time; the spectral absorption around 400nm is highest at 90s and then gradually decreases; these indicate that AB1 has degradedSome small molecules with uv absorption may be generated.
FIG. 4 is TTEC @ TiO2The ultraviolet-visible spectrum change graph (300-800nm) of the catalyst degradation AB1 shows that the spectral absorption at about 600nm gradually decreases with the time as the characteristic absorption of AB1, which indicates that AB1 is gradually degraded by light; at 60min, the spectral absorption was essentially negligible.
FIG. 5 is TXC @ TiO2The ultraviolet-visible spectrum change diagram of the AB1 degraded by the catalyst is shown, when TXC @ TiO2 catalyzes AB1 pollutants to be photodegraded (550-650 nm), the diagram shows that the spectral absorption at about 600nm gradually decreases with the time as the characteristic absorption of AB1, which shows that AB1 is gradually decomposed.
FIG. 6 is TOXC @ TiO2The graph of the ultraviolet-visible spectrum change of the catalyst degradation AB1 shows that the spectrum absorption at about 600nm gradually decreases with the time as the characteristic absorption of AB1, which indicates that AB1 is gradually decomposed, and the spectrum absorption is basically negligible at 60 min.
FIG. 7 is TSXC @ TiO2The ultraviolet-visible spectrum of the catalyst degradation AB1 shows that, as the characteristic absorption of AB1, the spectral absorption around 600nm gradually decreases with time, indicating that AB1 gradually decomposes. At 60min, the spectral absorption was essentially negligible.
FIG. 8 is TTXC @ TiO2The ultraviolet-visible spectrum of the catalyst degradation AB1 shows that, as the characteristic absorption of AB1, the spectral absorption around 600nm gradually decreases with time, indicating that AB1 gradually decomposes. At 60min, the solution achieved decolorization.
FIG. 9 is a graph showing the comparison of the catalytic degradation performance of the dye-sensitized titanium dioxide composite catalysts prepared in examples 1 to 8 with respect to acid black, wherein C0For the initial concentration of AB1 after adsorption-desorption equilibrium, C is the concentration of AB1 at different irradiation time conditions. Degradation efficiency D of AB1, by the formula D ═ 1-C/C0) 100% were calculated. It can be found that the photodegradation effect of the dye-sensitized titanium dioxide composite catalyst is very obvious within the initial 5 minutes and then tends to beAnd (4) smoothening. From the viewpoint of the degradation effect, TTEC @ TiO2And TOXC @ TiO2Degradation of AB1 was substantially completely achieved at 60 minutes. TOEC @ TiO2And TSEC @ TiO2The degradation effect of (2) is the worst, only about 60% of AB1 can be degraded at 30 minutes, and 30% of degradation objects still exist in the water solution at 60 minutes.
Comparative example
The catalytic degradation performance of pure titanium dioxide as a photocatalyst on acid black was studied, and the results are shown in fig. 10.
Fig. 10 is a graph showing the catalytic degradation performance of pure titanium dioxide to acid black in a comparative example, and by comparing the degradation performance of a pure titanium dioxide catalyst in a visible light range with that of the dye-sensitized titanium dioxide composite catalyst of the present invention (fig. 10 is compared with fig. 1 to 8), it can be analyzed that the photoresponse range of a conventional inorganic semiconductor catalyst (pure titanium dioxide) is narrow, while the utilization rate of the whole dye-sensitized titanium dioxide composite catalyst of the present invention to visible light is significantly improved, and the degradation performance to pollutants is significantly better than that of a single titanium dioxide semiconductor. In addition, the sensitization effect of the organic dye on the titanium dioxide is obvious, and the dye is adsorbed on the surface of the titanium dioxide, so that the photoresponse range is widened, and the material has very good photocatalytic degradation performance on organic matters. The photocatalyst is used for degrading organic matters in sewage, has the advantages of simple equipment, low investment and the like, and has wide application prospect and important environmental protection significance.
The embodiments can show that the invention provides a carbazole organic dye and a preparation method thereof, a dye-sensitized titanium dioxide composite catalyst and a preparation method and application thereof. The dye molecule is used for preparing the dye-sensitized titanium dioxide composite catalyst, and in the obtained catalyst, the dye is adsorbed on the surface of titanium dioxide, the particles are uniformly distributed, the visible light response range of a titanium dioxide semiconductor is widened, the catalytic effect is good, the treatment efficiency of wastewater is improved, and the service life of photocatalytic particles is prolonged.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (5)
1. The dye-sensitized titanium dioxide composite catalyst is characterized by comprising titanium dioxide and carbazole organic dye, wherein the carbazole organic dye is loaded on the titanium dioxide, and the loading amount of the carbazole organic dye is 0.01-2 wt%;
the carbazole organic dye has a structure shown in a formula I:
wherein R is1、R2And R3Independently comprise C0～12An alkyl group;
l is a linking group, and L comprises an alkylene group, an aromatic alkylene group or C0～12An alkyl group;
the A is an anchoring group, and the A is 2-cyanoacrylate.
2. The dye-sensitized titanium dioxide composite catalyst according to claim 1, wherein said carbazole-based organic dye comprises:
3. the method for preparing the dye-sensitized titanium dioxide composite catalyst according to claim 1 or 2, comprising the steps of:
carbazole organic dye, dichloromethane and nano-scale TiO2Mixing the particles, and compounding to obtain the dye-sensitized titanium dioxide composite catalyst.
4. The method according to claim 3, wherein the carbazole-based organic dye, methylene chloride and nano-sized TiO are mixed with water2The dosage ratio of the particles is 6 mu mol:10mL:500 mg;
the compounding temperature is room temperature, and the compounding time is 24 h.
5. The use of the dye-sensitized titanium dioxide composite catalyst according to claim 1 or 2 or the dye-sensitized titanium dioxide composite catalyst prepared by the preparation method according to any one of claims 3 to 4 in catalytic degradation of acid black in wastewater.
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