CN108371958A - A kind of Asia phthalocyanine/titanium dioxide nano photocatalysis agent and its preparation method and application - Google Patents
A kind of Asia phthalocyanine/titanium dioxide nano photocatalysis agent and its preparation method and application Download PDFInfo
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- CN108371958A CN108371958A CN201810059432.8A CN201810059432A CN108371958A CN 108371958 A CN108371958 A CN 108371958A CN 201810059432 A CN201810059432 A CN 201810059432A CN 108371958 A CN108371958 A CN 108371958A
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- titanium dioxide
- phthalocyanine
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 37
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 33
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 32
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 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 title claims description 24
- PMJMHCXAGMRGBZ-UHFFFAOYSA-N subphthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(=N3)N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C3=N1 PMJMHCXAGMRGBZ-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000006731 degradation reaction Methods 0.000 claims abstract description 38
- 230000015556 catabolic process Effects 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000975 dye Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 20
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical class N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000002114 nanocomposite Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- ZMJPCIAEJKVKMQ-UHFFFAOYSA-M [4-[[4-[benzyl(methyl)amino]phenyl]-[4-(dimethylamino)phenyl]methylidene]cyclohexa-2,5-dien-1-ylidene]-dimethylazanium;chloride Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC(=CC=1)N(C)CC=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 ZMJPCIAEJKVKMQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 230000005070 ripening Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- 150000004818 1,2-dichlorobenzenes Chemical class 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000003755 preservative agent Substances 0.000 claims description 3
- 230000002335 preservative effect Effects 0.000 claims description 3
- 229910015845 BBr3 Inorganic materials 0.000 claims description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Substances BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 11
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 abstract description 10
- RZUBARUFLYGOGC-MTHOTQAESA-L acid fuchsin Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=C(N)C(C)=CC(C(=C\2C=C(C(=[NH2+])C=C/2)S([O-])(=O)=O)\C=2C=C(C(N)=CC=2)S([O-])(=O)=O)=C1 RZUBARUFLYGOGC-MTHOTQAESA-L 0.000 abstract description 9
- 239000011941 photocatalyst Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000003504 photosensitizing agent Substances 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 239000010936 titanium Substances 0.000 abstract description 3
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000007385 chemical modification Methods 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 9
- 229940012189 methyl orange Drugs 0.000 description 9
- 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 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229960000907 methylthioninium chloride Drugs 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical class ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of sub- phthalocyanine/titanium dioxide nano photocatalysis agent and its preparation method and application, which is to be added a small amount of sub- phthalocyanine based on titanium dioxide as photosensitizer, nano-photocatalyst is synthesized using chemical modification method, to improve TiO2Photocatalysis performance under visible light.Preparation method includes preparing titanium dioxide, the sub- phthalocyanine of solvent-thermal method preparation and sub- phthalocyanine/titanium dioxide nano photocatalysis agent by sol-gal process.The present invention organically combines sub- phthalocyanine and titanium dioxide, titanium deoxide catalyst is improved in visible light-responded range, modified optically catalytic TiO 2 has preferable degradation effect under the visible light of wavelength ＞ 400nm to acid and alkaline organic dyestuff aqueous solution, and 97% and 99% are respectively reached to the degradation rate of acid fuchsin and bromophenol blue；The present invention has many advantages, such as that preparation method is simple, required raw material is few and pollution-free recyclable, of low cost, is suitable for industrialized production.
Description
Technical field
The invention belongs to photocatalysis technology fields, and in particular to it is a kind of Asia phthalocyanine/titanium dioxide nano photocatalysis agent and its
Preparation method and application.
Background technology
With the rapid development of economy, water pollution problem getting worse, the persistent organic pollutants being discharged into water
Great harm is constituted to the health of environment and the mankind.Titanium dioxide is found for the first time from Fujishima and Honda in 1972 etc.
(TiO2) have the function of under ultraviolet light decompose water after, the substance just because its stabilization physicochemical property, be easy to modify
The advantages that property, hypotoxicity, low cost, become the clean and effective catalysis material with huge potential using value.However, due to
TiO2Forbidden band broadband be about 3.2eV, electron-hole pair only could be generated less than the ultraviolet excitation of 387.5nm by wavelength,
So its photocatalysis efficiency under natural light irradiation is very low.
Sub- phthalocyanine (SubPc) is a kind of Functional dye of function admirable, has width in visible region (550nm~650nm)
Photovoltaic response band, have excellent chemical stability and light, electricity, magnetic property, it is equal in fields such as optics, electricity, catalysis, medicine
It has broad application prospects.
Currently, researcher improves TiO by the methods of ion doping, noble metal loading, photosensitizer, semiconductors coupling2
The photocatalysis performance of compound, but there is not yet utilize sub- phthalocyanine-sensitized TiO2The research report of photocatalysis degradation organic contaminant
Road.
Invention content
The purpose of the present invention is to provide a kind of synthetic method of sub- phthalocyanine and based on its nano-photocatalyst and its system
Preparation Method and application.
The present invention is to be achieved through the following technical solutions：
The invention discloses a kind of sub- phthalocyanine/titanium dioxide nano photocatalysis agent, which urges
Agent is the nanocomposite being combined by sub- phthalocyanine and nano-titanium dioxide, wherein nano-titanium dioxide and sub- phthalocyanine
Mass ratio be (25~200)：1.
Preferably, the mass ratio of nano-titanium dioxide and sub- phthalocyanine is 200:1、100:1、75:1、50:1 or 25:1.
The invention also discloses a kind of preparation methods of sub- phthalocyanine/titanium dioxide nano photocatalysis agent, include the following steps：
1) sub- phthalocyanine is configured to SubPc (Br) solution of 0.5g/L, then presses the matter of nano-titanium dioxide and sub- phthalocyanine
Amount is than being (25~200)：Nano-titanium dioxide, 1~3h of stirring ultrasonic reaction are added into SubPc (Br) solution for 1 ratio；
2) after the mixed solution after reacting step 1) is covered with preservative film, the ripening 4d at 70 DEG C is then open
It is dried at 120 DEG C, nano-photocatalyst is made.
Preferably, the sub- phthalocyanine synthesizes according to the following steps：
(1) 1,2- dicyanobenzenes are added in reaction vessel, in N2Under gas atmosphere, 1,2- dichloros are injected into reaction vessel
Benzene, being sufficiently stirred keeps stock dispersion uniform, and BBr is then added into reaction vessel3, return stirring reaction, until reaction solution by
Rufous becomes atropurpureus；
Wherein, 1,2- dicyanobenzenes, 1,2- dichloro-benzenes and BBr3Amount ratio be (1.0~1.5) g：(30~50) mL：
(1.5~3.0) mL；
(2) the sub- phthalocyanine powder of brilliant violet color is made by reflow treatment, filtration treatment in vacuum distillation removal solvent, crude product
End.
It is further preferred that reaction whole process is first carried out in stringent anhydrous and oxygen-free condition, reaction is set to hold by vacuum line apparatus
N is full of in device2Gas.
Preferably, in step (1), the return stirring reaction time is 10~15h.
In step (2), reflow treatment is by crude product successively at n-hexane, dichloromethane, chloroform, alcohol reflux
Reason, flows back for 24 hours every time；Filtration treatment is carried out using G4 sand core funnels.
Preferably, nano-titanium dioxide used is obtained in accordance with the following methods：
Step1：Under stirring, tetrabutyl titanate is slowly added dropwise into absolute ethyl alcohol, triethanolamine is then added,
Mixture is made；After stirring the mixture for 30~60min of reaction, ethanol water is added dropwise into system, it is anti-to then proceed to stirring
Uniform clear orange-yellow colloidal sol should be obtained up to tetrabutyl titanate complete hydrolysis；
Wherein, the volume ratio of tetrabutyl titanate, absolute ethyl alcohol and triethanolamine is 17:67:6；Ethanol water is by anhydrous
Ethyl alcohol presses 10 with deionized water:1 volume ratio is formulated；
Step2：By after orange-yellow colloidal sol ripening at 450 DEG C high-temperature calcination 5h, obtain titanium dioxide granule, finally
Titanium dioxide granule is ground into powdery to get to nano-titanium dioxide white powder.
The invention also discloses above-mentioned sub- phthalocyanine/titanium dioxide nano photocatalysis agent as degradation of organic dyes catalyst
Application.
Preferably, the sub- phthalocyanine/titanium dioxide nano photocatalysis agent can be quick under the visible light of wavelength ＞ 400nm
Organic pollution in efficient degradation water
Compared with prior art, the present invention has technique effect beneficial below：
Asia phthalocyanine/titanium dioxide nano photocatalysis agent disclosed by the invention, based on nano-titanium dioxide, addition is a small amount of
Sub- phthalocyanine as photosensitizer, in the Asia phthalocyanine/titanium dioxide nano photocatalysis agent, it is seen that light irradiation can excite sub- phthalocyanine point
Son, then light induced electron is to TiO2Conduction band transfer, realize that the charge of sub- Phthalocyanine efficiently separates.Light induced electron and TiO2Table
The H of face absorption2O、OH-、O2React, the hydroxyl radical free radical with strong oxidizing property and superoxide radical of generation can with it is organic
Molecule reacts, to achieve the purpose that degradable organic pollutant.
The present invention organically combines sub- phthalocyanine and titanium dioxide, improves titanium deoxide catalyst and is rung in visible light
Range is answered, modified optically catalytic TiO 2 is under the visible light of wavelength ＞ 400nm to acid and alkaline organic dyestuff water
Solution (methyl orange, methylene blue, acid fuchsin and bromophenol blue) has preferable degradation effect, wherein to acid fuchsin and bromophenol blue
Degradation rate respectively reach 97% and 99%, while the composite material has that preparation method is simple, required raw material is few and nothing
The advantages that recyclable, of low cost is polluted, industrialized production is suitable for.
The present invention utilizes organic-inorganic hybrid nanocomposite technology by SubPc (Br) and nano-TiO2Carry out it is compound, using chemistry
Modification method prepares TiO2- SubPc (Br) nanocomposite, i.e. nano-photocatalyst.Preparation method includes passing through sol-gel
Method prepares titanium dioxide, solvent-thermal method prepares sub- phthalocyanine and sub- phthalocyanine/titanic oxide nano compound material.The preparation of the present invention
Technological operation is simple, and yield is high, low for equipment requirements, is suitble to industrial-scale production.
Description of the drawings
Fig. 1 is the synthetic route chart of axial direction bromo Asia phthalocyanine SubPc (Br)；
Fig. 2 is the powder x-ray diffraction analysis of sub- phthalocyanine/titanic oxide nano compound material；
Fig. 3 is the ultraviolet-visible light spectrum analysis of sub- phthalocyanine/titanic oxide nano compound material；
Fig. 4 is the FTIR spectrum analysis of sub- phthalocyanine/titanic oxide nano compound material；
Fig. 5 is the scanning electron microscope analysis of sub- phthalocyanine/titanic oxide nano compound material；Wherein, (a) is TiO2:
SubPc (Br)=25:1, (b) is TiO2:SubPc (Br)=50:1, (c) is TiO2:SubPc (Br)=75:1, (d) is TiO2:
SubPc (Br)=100:1, (e) is TiO2:SubPc (Br)=200:1, (f) is TiO2；
Fig. 6 be different quality than TiO2Degradation property of-SubPc (Br) catalyst to methyl orange；
Fig. 7 be different quality than TiO2Degradation property of-SubPc (Br) catalyst to methylene blue；
Fig. 8 be different quality than TiO2Degradation property of-SubPc (Br) catalyst to acid fuchsin；
Fig. 9 be different quality than TiO2Degradation property of-SubPc (Br) catalyst to bromophenol blue.
Specific implementation mode
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
It is the synthetic route chart of axial direction bromo Asia phthalocyanine SubPc (Br) disclosed by the invention referring to Fig. 1, reacting whole needs
It is carried out under the conditions of stringent anhydrous and oxygen-free：
Dry 1,2- dicyanobenzenes (10mmol, 1.28g) are added in Schlenk bottles of 100mL, it is traditional thread binding by vacuum
Setting makes to be full of N in system2Gas.In N21,2- dichloro-benzenes (40mL) is injected under gas shielded into system, being sufficiently stirred makes stock dispersion
Uniformly.BBr is added into system3(2.1mL), return stirring 12h, reaction solution become atropurpureus from rufous.Vacuum distillation removes
Solvent, crude product is gone to use n-hexane, dichloromethane, chloroform, alcohol reflux for 24 hours successively, the filtering of G4 sand core funnels obtains brilliant violet
Color Asia phthalocyanine SubPc (Br) powder 0.3923g, yield 25.03%；m.p.>300℃；C24H12BBrN6, elemental analysis (%) meter
Calculation value (experiment value)：C 60.67 (60.62), H 2.55 (2.57), N 17.69 (17.77).
Asia phthalocyanine/titanium dioxide nano photocatalysis agent disclosed by the invention, i.e., sub- phthalocyanine/titanic oxide nano compound material
Photochemical catalyst, the Asia phthalocyanine/titanium dioxide nano photocatalysis agent are the nanometers being combined by sub- phthalocyanine and nano-titanium dioxide
Composite material；
Wherein, the mass ratio of nano-titanium dioxide and sub- phthalocyanine is (25~200)：1.
Specific embodiment proportioning is as shown in table 1 below：
Table 1 reacts embodiment
| Serial number | Nano-titanium dioxide：The mass ratio of sub- phthalocyanine |
| Embodiment 1 | 200:1 |
| Embodiment 2 | 100:1 |
| Embodiment 3 | 75:1 |
| Embodiment 4 | 50:1 |
| Embodiment 5 | 25:1 |
The preparation method of above-mentioned Asia phthalocyanine/titanium dioxide nano photocatalysis agent, includes the following steps：
S1, it takes 67mL absolute ethyl alcohols to be placed in 100mL beakers, 17mL tetrabutyl titanates is slowly added dropwise under stirring
To wherein, 6mL triethanolamines are added afterwards, to inhibit the fast hydrolyzing of tetrabutyl titanate.Add dropwise after stirring the mixture for 50min
Enter absolute ethyl alcohol：Deionized water=10:1 (volume ratio) mixed liquor, reaction system, which continues stirring 3h, makes the complete water of tetrabutyl titanate
Solution obtains uniform clear orange-yellow colloidal sol.Colloidal sol ageing is placed in Muffle furnace, 450 DEG C of high-temperature calcination 5h obtain dioxy
Change titanium particle.Gained titanium dioxide granule is finally ground into powdery to get to nano-TiO2White powder.
S2, reaction whole process need to carry out under the conditions of stringent anhydrous and oxygen-free, and reaction route is as shown in Figure 1.By dry 1,2-
Dicyanobenzenes (10mmol, 1.28g) are added in Schlenk bottles of 100mL, make to be full of N in system by vacuum line apparatus2Gas.
N21,2- dichloro-benzenes (40mL) is injected under gas shielded into system, being sufficiently stirred keeps stock dispersion uniform.BBr is added into system3
(2.1mL), return stirring 12h, reaction solution become atropurpureus from rufous.Vacuum distillation removes solvent, and crude product is used just successively
For 24 hours, the filtering of G4 sand core funnels obtains brilliant violet color Asia phthalocyanine SubPc (Br) powder for hexane, dichloromethane, chloroform, alcohol reflux
0.3923g。
S3：TiO2The TiO prepared in advance is weighed respectively by the dosage that table 1 is recorded with SubPc (Br) mass ratioes2Powder, quickly
It is added into 0.5g/L SubPc (Br) solution, is carried out at the same time stirring and ultrasound 2h.Then the mixed solution of preparation is poured into
In beaker, covered with preservative film, be aged 4 days in 70 DEG C of baking ovens, then open wide sealing at 120 DEG C dry to get to series not
Homogenous quantities than TiO2- SubPc (Br) nanocomposite.
In order to verify the photocatalysis of the nano-photocatalyst based on sub- phthalocyanine modifying titanium dioxide made from present patent application
Degradation characteristic, has carried out degradation property testing experiment, and test method and result are as follows：
1, test method
Organic dyestuff (methyl orange, methylene blue, the acidity of a concentration of 10mg/L of 100mL are sequentially added in beaker respectively
Pinkish red, bromophenol blue) aqueous solution and 0.1g different quality ratios (Examples 1 to 5) TiO2- SubPc (Br) photochemical catalyst, is being protected from light
Under the conditions of stirring 0.5h with reach adsorption-desorption balance (cloudy, turbid phase).Xenon lamp adds edge filter (model UVCUT400)
To filter out the light beam of wavelength ＜ 400nm, under away from fluorescent tube 10cm irradiation stirrings (photoreaction stage), 5mL samples are taken every 0.5h
Product centrifuge 6min in the centrifuge of 9000r/min.Supernatant liquor is taken, wherein has engine dyeing using ultraviolet-visible spectrometer measurement
The absorbance of material.
Photocatalysis effect quality judges it is using degradation rate as foundation, and sample degradation rate calculation formula is as follows：
Degradation rate=[(A0-A)/A0] × 100%；
Wherein, A0For the absorbance of sample before illumination, the absorbance of A is light application time when being t sample.
The maximum absorption band wavelength of methyl orange is λmax=463nm surveys its absorbance A at λ max0=0.71.Methylene
Blue maximum absorption band wavelength is λmax=664nm surveys its absorbance A at λ max0=1.7175.The maximum of acid fuchsin is inhaled
Receive a length of λ of spikemax=543nm, in λmaxPlace surveys its absorbance A0=0.7166.The maximum absorption band wavelength of bromophenol blue is λmax
=592nm, in λmaxPlace surveys its absorbance A0=0.972.
2, test result
1)TiO2- SubPc (Br) photochemical catalysts test the degradation property of methyl orange
Different quality adulterates the TiO of ratio2- SubPc (Br) catalyst is to the degradation of methyl orange as shown in fig. 6, by surveying
Test result is it is found that the TiO not being sensitized2Only have 18.6% to the degradation rate of methyl orange, and with the doping of SubPc (Br), catalysis
Agent catalytic efficiency is obviously improved.It is embodied in：TiO after SubPc (Br) sensitizations2Catalyst exists to the degradation process of methyl orange
Reacting has high reaction rate in the 0.5h after starting, tend towards stability after 3h.Mass ratio is 25:1、50:1、75:1、100:1 and
200:1 TiO2- SubPc (Br) catalyst is respectively 91.06% to the degradation rate of methyl orange in 3h, 80.7%, 72.5%,
88.6% and 35.1%, wherein TiO2:SubPc (Br)=25:1 catalyst effect is optimal, TiO2:SubPc (Br)=200:
1 catalyst effect relative disadvantage.
2)TiO2- SubPc (Br) photochemical catalysts test the degradation property of methylene blue
Different quality adulterates the TiO of ratio2- SubPc (Br) catalyst is as shown in Figure 7 to the degradation of methylene blue.By
Test result is it is found that the TiO not being sensitized2Only have 44.79% to the degradation rate of methylene blue, and the TiO after SubPc (Br) sensitizations2
Catalyst promotion with obvious effects, reaction still have good degradation trend after starting 3h.Mass ratio is 25:1、50:1、75:1、
100:1 and 200:1 TiO2- SubPc (Br) catalyst is respectively 75.5% to the degradation rate of methylene blue in 3h,
74.1%, 73.9%, 70.1% and 68.5%, activity difference is less obvious, but still TiO2:SubPc (Br)=25:1 effect
It is optimal, TiO2:SubPc (Br)=200:1 effect relative disadvantage.
3)TiO2- SubPc (Br) photochemical catalysts test the degradation property of acid fuchsin
Different quality adulterates the TiO of ratio2- SubPc (Br) catalyst is as shown in Figure 8 to the degradation of acid fuchsin.By
Test result it is found that SubPc (Br) sensitization after TiO2Catalyst is to the degradation of acid fuchsin in the 0.5h after reaction starts
Up to 56% or more, and the TiO not being sensitized2Degradation rate is only 33.2%.Mass ratio is 25:1、50:1、75:1、100:1 and
200:1 TiO2- SubPc (Br) catalyst is respectively 96.92% to the degradation rate of acid fuchsin in 3h, 91.6%,
97.4%, 94.6% and 91.5%.
4)TiO2- SubPc (Br) photochemical catalysts test the degradation property of bromophenol blue
Different quality adulterates the TiO of ratio2- SubPc (Br) catalyst is as shown in Figure 9 to the degradation of bromophenol blue.By surveying
Test result it is found that SubPc (Br) sensitization after TiO2Catalyst is to the degradation of bromophenol blue in the 1h that reaction starts up to 90%
More than, and the TiO not being sensitized2Degradation rate is only 40.9%.Mass ratio is 25:1、50:1、75:1、100:1 and 200:1 TiO2-
SubPc (Br) catalyst is respectively 99.2%, 97.7%, 96.7%, 95.98% and to the degradation rate of bromophenol blue in 3h
95.05%, TiO2:SubPc (Br)=25:1 effect is optimal.
TiO2, nano-photocatalyst (TiO in figure2- SubPc (Br)) and SubPc (Br) powder x-ray diffraction collection of illustrative plates such as
Shown in Fig. 2；TiO2, nano-photocatalyst (TiO2:SubPc (Br)=25:1) and the UV-visible spectrum of SubPc (Br) such as
Shown in Fig. 3；TiO2, nano-photocatalyst (TiO2:SubPc (Br)=25:And infrared spectrogram such as Fig. 4 institutes of SubPc (Br) 1)
Show.
Meanwhile being electron scanning micrograph referring to Fig. 5；Wherein, (a) is TiO2:SubPc (Br)=25:1、(b)
For TiO2:SubPc (Br)=50:1, (c) is TiO2:SubPc (Br)=75:1, (d) is TiO2:SubPc (Br)=100:1、
(e) it is TiO2:SubPc (Br)=200:1, (f) is TiO2；
As can be seen that in TiO2During-SubPc (Br) catalyst tests the photocatalytic degradation of organic dyestuff, TiO2:SubPc
(Br)=25:1 catalyst has optimal catalytic activity, in conjunction with ultraviolet-visible and scanning electron microscope test interpretation of result,
Due to increasing for SubPc (Br) dopings, TiO2Reunite between particle and be gradually reduced, dispersing uniformity gradually increases, and makes TiO2-
SubPc (Br) catalyst is easier to contact with organic dyestuff.
Claims (10)
1. a kind of Asia phthalocyanine/titanium dioxide nano photocatalysis agent, which is characterized in that the Asia phthalocyanine/titanium dioxide nano photocatalysis
Agent is the nanocomposite being combined by sub- phthalocyanine and nano-titanium dioxide, wherein nano-titanium dioxide and sub- phthalocyanine
Mass ratio is (25~200)：1.
2. Asia phthalocyanine/titanium dioxide nano photocatalysis agent according to claim 1, which is characterized in that nano-titanium dioxide
Mass ratio with sub- phthalocyanine is 200:1、100:1、75:1、50:1 or 25:1.
3. a kind of preparation method of Asia phthalocyanine/titanium dioxide nano photocatalysis agent, which is characterized in that include the following steps：
1) sub- phthalocyanine is configured to SubPc (Br) solution of 0.5g/L, then presses the mass ratio of nano-titanium dioxide and sub- phthalocyanine
For (25~200)：Nano-titanium dioxide, 1~3h of stirring ultrasonic reaction are added into SubPc (Br) solution for 1 ratio；
2) after the mixed solution after reacting step 1) is covered with preservative film, ripening 4d, is then open to 120 at 70 DEG C
It is dried at DEG C, Asia phthalocyanine/titanium dioxide nano photocatalysis agent is made.
4. the preparation method of Asia phthalocyanine/titanium dioxide nano photocatalysis agent according to claim 3, which is characterized in that institute
Sub- phthalocyanine is stated to synthesize according to the following steps：
(1) 1,2- dicyanobenzenes are added in reaction vessel, in N2Under gas atmosphere, 1,2- dichloro-benzenes is injected into reaction vessel, is filled
Divide stirring to keep stock dispersion uniform, BBr is then added into reaction vessel3, return stirring reaction, until reaction solution is by rufous
Become atropurpureus；
Wherein, 1,2- dicyanobenzenes, 1,2- dichloro-benzenes and BBr3Amount ratio be (1.0~1.5) g：(30~50) mL：(1.5~
3.0)mL；
(2) the sub- phthalocyanine powder of brilliant violet color is made by reflow treatment, filtration treatment in vacuum distillation removal solvent, crude product.
5. the preparation method of Asia phthalocyanine/titanium dioxide nano photocatalysis agent according to claim 4, which is characterized in that anti-
It answers whole process first to be carried out in stringent anhydrous and oxygen-free condition, makes to be full of N in reaction vessel by vacuum line apparatus2Gas.
6. the preparation method of Asia phthalocyanine/titanium dioxide nano photocatalysis agent according to claim 4, which is characterized in that step
Suddenly in (1), the return stirring reaction time is 10~15h.
7. the preparation method of Asia phthalocyanine/titanium dioxide nano photocatalysis agent according to claim 4, which is characterized in that step
Suddenly in (2), reflow treatment is that crude product is used to n-hexane, dichloromethane, chloroform, alcohol reflux processing successively, every time
Reflux is for 24 hours；Filtration treatment is carried out using G4 sand core funnels.
8. the preparation method of Asia phthalocyanine/titanium dioxide nano photocatalysis agent according to claim 3, which is characterized in that institute
It is obtained in accordance with the following methods with nano-titanium dioxide：
Step1：Under stirring, tetrabutyl titanate is slowly added dropwise into absolute ethyl alcohol, triethanolamine is then added, is made
Mixture；After stirring the mixture for 30~60min of reaction, ethanol water is added dropwise into system, then proceedes to be stirred to react straight
To tetrabutyl titanate complete hydrolysis, uniform clear orange-yellow colloidal sol is obtained；
Wherein, the volume ratio of tetrabutyl titanate, absolute ethyl alcohol and triethanolamine is 17:67:6；Ethanol water is by absolute ethyl alcohol
10 are pressed with deionized water:1 volume ratio is formulated；
Step2：By after orange-yellow colloidal sol ripening at 450 DEG C high-temperature calcination 5h, titanium dioxide granule is obtained, finally by two
Titan oxide particles are ground into powdery to get to nano-titanium dioxide white powder.
9. Asia phthalocyanine/titanium dioxide nano photocatalysis agent as claimed in claim 1 or 2 is answered as degradation of organic dyes catalyst
With.
10. application as claimed in claim 9, which is characterized in that the Asia phthalocyanine/titanium dioxide nano photocatalysis agent is in wavelength
Organic pollution in degradation water that can be rapidly and efficiently under the visible light of ＞ 400nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109205731A (en) * | 2018-11-12 | 2019-01-15 | 内蒙古民族大学 | A kind of method of new bio photosensitive fuel Degradation of Organo-pollutants in Water with Photo-catalysis in conjunction with titanium dioxide |
| CN114870905A (en) * | 2022-06-08 | 2022-08-09 | 四川大学 | Method for in-situ preparation of titanium dioxide/cellulose nano composite microspheres |
| CN117483010A (en) * | 2024-01-03 | 2024-02-02 | 山东海化集团有限公司 | Modified nano TiO 2 Preparation method and application of catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1124255A (en) * | 1997-07-01 | 1999-01-29 | Mitsui Chem Inc | Visible light-setting resin composition and its use |
| CN102936260A (en) * | 2012-11-05 | 2013-02-20 | 西北大学 | Subphthalocyanine compound and preparation method and application thereof |
| CN103480414A (en) * | 2013-04-23 | 2014-01-01 | 西北大学 | Preparation method and application of subphthalocyanine bonded graphene oxide |
| JP2014051453A (en) * | 2012-09-07 | 2014-03-20 | Nagoya Institute Of Technology | Procedures for synthesis of subphthalocyanine with 3,5-bis(pentafluorosulfanyl)-phenyl group and novel subphthalocyanine with 3,5-bis(pentafluorosulfanyl)-phenyl group |
| CN104923310A (en) * | 2015-05-12 | 2015-09-23 | 常州大学 | Preparation method for soluble amino phthalocyanine-titanium dioxide near-infrared photocatalyst |
-
2018
- 2018-01-22 CN CN201810059432.8A patent/CN108371958A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1124255A (en) * | 1997-07-01 | 1999-01-29 | Mitsui Chem Inc | Visible light-setting resin composition and its use |
| JP2014051453A (en) * | 2012-09-07 | 2014-03-20 | Nagoya Institute Of Technology | Procedures for synthesis of subphthalocyanine with 3,5-bis(pentafluorosulfanyl)-phenyl group and novel subphthalocyanine with 3,5-bis(pentafluorosulfanyl)-phenyl group |
| CN102936260A (en) * | 2012-11-05 | 2013-02-20 | 西北大学 | Subphthalocyanine compound and preparation method and application thereof |
| CN103480414A (en) * | 2013-04-23 | 2014-01-01 | 西北大学 | Preparation method and application of subphthalocyanine bonded graphene oxide |
| CN104923310A (en) * | 2015-05-12 | 2015-09-23 | 常州大学 | Preparation method for soluble amino phthalocyanine-titanium dioxide near-infrared photocatalyst |
Non-Patent Citations (1)
| Title |
|---|
| 朱琳 等: "二氧化钛酞菁镁可见光催化降解的研究", 《安徽农业科学》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109205731A (en) * | 2018-11-12 | 2019-01-15 | 内蒙古民族大学 | A kind of method of new bio photosensitive fuel Degradation of Organo-pollutants in Water with Photo-catalysis in conjunction with titanium dioxide |
| CN109205731B (en) * | 2018-11-12 | 2021-06-18 | 内蒙古民族大学 | Method for photocatalytic degradation of organic pollutants in water by combining biological photosensitive dye and titanium dioxide |
| CN114870905A (en) * | 2022-06-08 | 2022-08-09 | 四川大学 | Method for in-situ preparation of titanium dioxide/cellulose nano composite microspheres |
| CN114870905B (en) * | 2022-06-08 | 2023-08-11 | 四川大学 | Method for preparing titanium dioxide/cellulose nano composite microsphere in situ |
| CN117483010A (en) * | 2024-01-03 | 2024-02-02 | 山东海化集团有限公司 | Modified nano TiO 2 Preparation method and application of catalyst |
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