CN106582812A - Composite photocatalyst with titanium dioxide axially functionalized by metallic zinc porphyrin and preparation method thereof - Google Patents
Composite photocatalyst with titanium dioxide axially functionalized by metallic zinc porphyrin and preparation method thereof Download PDFInfo
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- CN106582812A CN106582812A CN201610982744.7A CN201610982744A CN106582812A CN 106582812 A CN106582812 A CN 106582812A CN 201610982744 A CN201610982744 A CN 201610982744A CN 106582812 A CN106582812 A CN 106582812A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- YIYFFLYGSHJWFF-UHFFFAOYSA-N [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Zn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 YIYFFLYGSHJWFF-UHFFFAOYSA-N 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- 239000002351 wastewater Substances 0.000 claims abstract description 5
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 4
- 231100000719 pollutant Toxicity 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- FUTVBRXUIKZACV-UHFFFAOYSA-J zinc;3-[18-(2-carboxylatoethyl)-8,13-bis(ethenyl)-3,7,12,17-tetramethylporphyrin-21,24-diid-2-yl]propanoate Chemical compound [Zn+2].[N-]1C2=C(C)C(CCC([O-])=O)=C1C=C([N-]1)C(CCC([O-])=O)=C(C)C1=CC(C(C)=C1C=C)=NC1=CC(C(C)=C1C=C)=NC1=C2 FUTVBRXUIKZACV-UHFFFAOYSA-J 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 37
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims description 10
- 238000007146 photocatalysis Methods 0.000 claims description 10
- 239000003495 polar organic solvent Substances 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000000376 reactant Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- 238000007306 functionalization reaction Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 235000019628 coolness Nutrition 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 3
- 239000000975 dye Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 229920001778 nylon Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 150000004032 porphyrins Chemical class 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 6
- 230000000593 degrading effect Effects 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 10
- 229940043267 rhodamine b Drugs 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000003403 water pollutant Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000010919 dye waste Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 208000000058 Anaplasia Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 244000178870 Lavandula angustifolia Species 0.000 description 1
- 235000010663 Lavandula angustifolia Nutrition 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000001102 lavandula vera Substances 0.000 description 1
- 235000018219 lavender Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
-
- 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
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of photocatalytic materials for degrading dye wastewater pollutants, and discloses a composite photocatalyst with titanium dioxide axially functionalized by metallic zinc porphyrin and a preparation method thereof. The method includes the synthesis steps that anatase type titanium dioxide and metallic zinc porphyrin are proportionally mixed in an organic solvent, heating reflux is conducted, and then the photocatalyst with titanium dioxide sensitized by metallic zinc porphyrin is obtained after filtering, washing and drying. The synthesis method is simple, and the prepared composite photocatalyst is stable in property, high in photocatalytic activity and capable of being used as an environment purifying material used for photocatalytic treatment of dye wastewater pollutants.
Description
Technical field
The invention belongs to the catalysis material technical field of degradation of dye waste water pollutant, and in particular to one kind is new " to be had
Composite photo-catalyst of machine-inorganic " metal zinc protoporphyrin axial direction functionalized titanic oxide and preparation method thereof.
Background technology
With the quickening of the fast-developing and process of industrialization of social economy, problem of environmental pollution is increasingly serious, big to quantify
The consumption and discharge of work raw material, makes the living environment around people go from bad to worse.Wherein, the colourity of organic dyestuff sewage is deep, dense
Degree is high, toxicity is big, it is difficult to degrade under field conditions (factors), it has also become a great problem of water treatment field.Therefore, develop a kind of easy
It is human society urgent problem that effectively method carrys out degradable organic pollutant.In recent years, it is organic in photocatalytic degradation water
Pollutant provide new thinking for the improvement of waste water.Photocatalytic method reaction condition is gentle, equipment is simple, secondary pollution is little, easy
It is low in operational control, operating cost, it is a kind of very promising water pollution control technology, more and more widely closed by people
Note.
In at present photocatalysis research, most study, while be also regarded as optimal material is titanium dioxide, due to its tool
Have the advantages that photocatalytic activity is high, fast light corrosivity strong, it is good stability, environmental friendliness, relative low price, nontoxic to human body,
Show to be widely applied prospect in emerging fields such as information, the energy, environment.But, titanium dioxide itself also shortcoming, its band gap
Wide, spectral response range is narrow, can only ultraviolet light of the absorbing wavelength less than 387.5nm, be only 4% to the utilization rate of solar energy.
Spectral response range of the titanium dioxide in visible region how is expanded, is allowed to visible light activity, and improve it to sunlight
Total utilization ratio be restrict optically catalytic TiO 2 technology key issue.
By the use of metalloporphyrin as sensitizer sensitized titanium dioxide be improve its visible light catalytic effect effective way it
One.Metalloporphyrin and titanium dioxide are formed into complex, just can make under conditions of illumination the electronics that metalloporphyrin is produced by
Sensitizer is delivered to the conduction band of titanium dioxide semiconductor, so that the excitation wavelength of complex systems is widened to visible-range,
So that the utilization to visible ray and near infrared region is possibly realized.
The content of the invention
It is an object of the invention to develop the new visible light photocatalysis for degradation of dye waste water pollutant of a class answer
Closing light catalyst, to improve catalysis material to visible ray and the spectrum utilization factor of near infrared region.
The invention provides a kind of preparation method of metal zinc protoporphyrin axial direction functionalized titanic oxide composite photo-catalyst, step
It is rapid simple, easily to realize, the composite photo-catalyst photocatalysis performance of preparation is good.
The composite photo-catalyst of a kind of metal zinc protoporphyrin axial direction functionalized titanic oxide, by titanium dioxide and metal zinc protoporphyrin
Composition, the metal zinc protoporphyrin axially modifies the titanium dioxide surface in .gamma.-pyridinecarboxylic acid covalent functionalization；Zinc protoporphyrin axial direction work(
Can the structure of composite photo-catalyst of oxide/titanium dioxide be：
The preparation method of the composite photo-catalyst of a kind of metal zinc protoporphyrin axial direction functionalized titanic oxide, including following step
Suddenly：
Step A1：By titanium dioxide ultrasonic disperse in polar organic solvent A, after being uniformly dispersed, add .gamma.-pyridinecarboxylic acid and
N, N '-dicyclohexylcarbodiimide, esterification is carried out, after reaction terminates, by reactant Jing coolings, filter, wash, do
It is dry, obtain white powder product, the as titanium dioxide of .gamma.-pyridinecarboxylic acid covalent functionalization；
Step A2：Under ultrasound, by step A1 products therefrom and metal zinc protoporphyrin ultrasonic dissolution in polar organic solvent B,
Under nitrogen protection, reaction kinetic is carried out, after reaction terminates, by reactant Jing coolings, filter, wash, be dried, obtain zinc protoporphyrin
The composite photo-catalyst ZnTpp/TiO of axial functionalized titanic oxide2。
In the preparation method, the polar organic solvent A of step A1 is tetrahydrofuran, the polar organic solvent B of step A2
For N, N '-dimethyl Methanamide.
The crystal formation of the titanium dioxide is Detitanium-ore-type；
In step A1, the titanium dioxide .gamma.-pyridinecarboxylic acid and N, N ' mass ratio of-dicyclohexylcarbodiimide is 3:10:
2；
In step A2, step A1 product and zinc protoporphyrin mass ratio be 8:5.
Ultrasonic time is half an hour in the preparation method.
The temperature of step A1 esterification is 66 DEG C, and the response time is 3 days；The temperature of step A2 reaction kinetic is 80
DEG C, the response time is 2 days.
Described being filtered into is filtered reactant liquor with 0.45 μm of nylon membrane；The washing for respectively deionized water and
Dichloromethane is washed；The drying is to be dried 12 hours under vacuum room temperature.
A kind of purposes of the composite photo-catalyst of metal zinc protoporphyrin axial direction functionalized titanic oxide of the present invention, it is special
Levy and be, using the composite catalyst as photocatalysis treatment waste water from dyestuff pollutant, such as rhodamine B.
It is an advantage of the invention that：
(1) simply, reaction condition is gentle, and process is easily controllable for preparation method of the invention, is adapted to wanting for extension production
Ask；
(2) the composite photo-catalyst light and heat stability prepared by the present invention, activity is high, can repeatedly use；
(3) catalyst prepared by the present invention has absorption well to visible ray, to organic contamination under visible light conditions
Thing rhodamine B has good degradation effect；
(4) the prepared composite photo-catalyst of the present invention shows to compare metal in visible region to organic pollution rhodamine B
Zinc protoporphyrin and the more preferable photocatalysis performance of titanium dioxide, are that Future Development preparation method is simple, and photocatalysis performance is high to be combined
Catalyst provides new approach.
Description of the drawings
Fig. 1 is ZnTpp/TiO prepared by the inventive method2Composite photo-catalyst and metal zinc protoporphyrin ZnTpp, it is not sensitized
TiO2The infrared comparison diagram of photocatalyst；
Fig. 2 is ZnTpp/TiO prepared by the inventive method2Composite photo-catalyst and the TiO not being sensitized2The XRD of photocatalyst
Comparison diagram；
Fig. 3 is ZnTpp/TiO prepared by the inventive method2Composite photo-catalyst and metal zinc protoporphyrin ZnTpp, it is not sensitized
TiO2The UV-Vis DRS spectrum comparison diagram of photocatalyst；
Fig. 4 is ZnTpp/TiO prepared by the inventive method2Composite photocatalyst for degrading rhodamine B aqueous solution anaplasia at any time
The UV-visible spectrum of change；
Fig. 5 is ZnTpp/TiO prepared by the inventive method2Composite photo-catalyst and metal zinc protoporphyrin ZnTpp, it is not sensitized
TiO2Photocatalyst for degrading rhodamine B aqueous solution degradation rate time history plot.
Specific embodiment
Below by way of specific embodiment, present invention is described or is further described, and gives detailed reality
Mode and specific operating process are applied, its object is to more fully understand the technical connotation of the present invention, but the protection model of the present invention
Enclose and be not limited to following embodiments.
Embodiment metal zinc protoporphyrin axial direction functionalized titanic oxide composite photo-catalyst ZnTpp/TiO2Preparation：
By titanium dioxide (0.15g) ultrasonic disperse in polar organic solvent tetrahydrofuran (10mL), after being uniformly dispersed, then
Add .gamma.-pyridinecarboxylic acid (0.5g) and N, N '-dicyclohexylcarbodiimide (0.1g), carry out esterification.After reaction terminates, treat anti-
Answer liquid to be cooled to room temperature, reactant liquor is filtered with 0.45 μm of nylon membrane, then respectively deionized water and dichloromethane are washed
Wash, then room temperature in vacuo is dried and obtains within 12 hours white powder product, the as titanium dioxide of .gamma.-pyridinecarboxylic acid covalent functionalization；It is super
Under sound, above-mentioned steps products therefrom and metal zinc protoporphyrin (25mg) are dissolved in into polar organic solvent N, N '-dimethyl Methanamide
In, under nitrogen protection, carry out reaction kinetic 2 days.Reactant liquor cooled and filtered, the lavender solid for obtaining uses respectively deionization
Water, dichloromethane, methanol and washing with alcohol, are then dried in a vacuum and overnight obtain zinc protoporphyrin axial direction functionalized titanic oxide
Composite photo-catalyst ZnTpp/TiO2。
The infrared spectrum of Fig. 1 shows that metal zinc protoporphyrin ZnTpp is modified in titanium dioxide TiO2Surface.
The XRD spectra of Fig. 2 shows that metal zinc protoporphyrin ZnTpp is modified in titanium dioxide TiO2Surface.
The UV-Vis DRS spectrogram of Fig. 3 shows that metallic zinc porphyrin ZnTpp is modified in titanium dioxide TiO2Surface,
And the introducing of metal zinc protoporphyrin ZnTpp extends titanium dioxide TiO2In the absorption of visible region.
Metal zinc protoporphyrin axial direction functionalized titanic oxide nanometer of the comparative example below by comparative example to preparation in the present invention
Composite photo-catalyst illustrates the effect of composite photocatalyst material to the degraded percentage rate of rhodamine B aqueous solution under visible light.
In order to verify metal zinc protoporphyrin axial direction functionalized titanic oxide nano composite photo-catalyst prepared by the present invention
ZnTpp/TiO2Potential application, inventor is by itself and Detitanium-ore-type TiO2, metal zinc protoporphyrin ZnTpp same light source radiate
Under, do a series of contrasts.With rhodamine B aqueous solution as target solution, the light source that photocatalysis experiment is adopted is for 350W halogen tungsten lamps.Mesh
Mark solution is placed in 100mL beakers, and beaker is disposed vertically with lamp, and distance therebetween is 15 centimetres.According to sieve before and after illumination
The change calculations of red bright B aqueous solutions absorbance obtain percentage rate of degrading, and comparing result is as shown in Figure 5.
The spectrogram of Fig. 4 shows that rhodamine B is progressively decomposed under light illumination, and almost all degraded after 105 minutes.
The spectrogram of Fig. 5 shows ZnTpp/TiO2Composite photo-catalyst has than the metal zinc protoporphyrin ZnTpp and TiO not being sensitized2
The photocatalysis effect of more preferable rhodamine B degradation.
Fig. 5 is with 50mg metals zinc protoporphyrin axial direction functionalized titanic oxide nano composite photo-catalyst ZnTpp/TiO2Degraded
50mL10mg/L rhodamine Bs solution time dependent curve of solution absorptance under light source.From figure 5 it can be seen that
Metal zinc protoporphyrin sensitized titanium dioxide composite photo-catalyst ZnTpp/ under the conditions of 350W halogen tungsten light irradiations, prepared by the present invention
TiO2Have than metal zinc protoporphyrin ZnTpp and without porphyrin and be sensitized catalyst titanium dioxide TiO2Higher catalytic effect.As can be seen that
It is sensitizer and anatase titanium dioxide under the synergism of carrier, the nanometer prepared by the present invention is answered in metal zinc protoporphyrin
Compared with existing catalyst, photocatalysis effect is significantly improved closing light catalyst.
Claims (8)
1. the composite photo-catalyst of a kind of metal zinc protoporphyrin axial direction functionalized titanic oxide, it is characterised in that by titanium dioxide and
Metal zinc protoporphyrin is constituted, and the metal zinc protoporphyrin axially modifies the titanium dioxide surface in .gamma.-pyridinecarboxylic acid covalent functionalization；The zinc
The structure of composite photo-catalyst of porphyrin axial direction functionalized titanic oxide is：
2. the preparation of the composite photo-catalyst of a kind of metal zinc protoporphyrin axial direction functionalized titanic oxide according to claim 1
Method, it is characterised in that comprise the steps：
Step A1：By titanium dioxide ultrasonic disperse in polar organic solvent A, after being uniformly dispersed .gamma.-pyridinecarboxylic acid and N, N are added '-
Dicyclohexylcarbodiimide, carries out esterification, after reaction terminates, by reactant Jing coolings, filters, washs, and is dried, and obtains
White powder product, the as titanium dioxide of .gamma.-pyridinecarboxylic acid covalent functionalization；
Step A2：Under ultrasound, by step A1 products therefrom and metal zinc protoporphyrin ultrasonic dissolution in polar organic solvent B, nitrogen
Under protection, reaction kinetic is carried out, after reaction terminates, by reactant Jing coolings, filter, wash, be dried, obtain zinc protoporphyrin axial direction
The composite photo-catalyst ZnTpp/TiO of functionalized titanic oxide2。
3. the preparation of the composite photo-catalyst of a kind of metal zinc protoporphyrin axial direction functionalized titanic oxide according to claim 2
Method, it is characterised in that in the preparation method, the polar organic solvent A of step A1 is tetrahydrofuran, and the polarity of step A2 has
Machine solvent B be N, N '-dimethyl Methanamide.
4. the preparation of the composite photo-catalyst of a kind of metal zinc protoporphyrin axial direction functionalized titanic oxide according to claim 2
Method, it is characterised in that the crystal formation of the titanium dioxide is Detitanium-ore-type；
In step A1, the titanium dioxide .gamma.-pyridinecarboxylic acid and N, N ' mass ratio of-dicyclohexylcarbodiimide is 3:10:2；
In step A2, step A1 product and zinc protoporphyrin mass ratio be 8:5.
5. the preparation of the composite photo-catalyst of a kind of metal zinc protoporphyrin axial direction functionalized titanic oxide according to claim 2
Method, it is characterised in that ultrasonic time is half an hour in the preparation method.
6. the preparation of the composite photo-catalyst of a kind of metal zinc protoporphyrin axial direction functionalized titanic oxide according to claim 2
Method, it is characterised in that the temperature of step A1 esterification is 66 DEG C, the response time is 3 days；The temperature of step A2 reaction kinetic
Spend for 80 DEG C, the response time is 2 days.
7. the preparation of the composite photo-catalyst of a kind of metal zinc protoporphyrin axial direction functionalized titanic oxide according to claim 2
Method, it is characterised in that described being filtered into is filtered reactant liquor with 0.45 μm of nylon membrane；The washing is to spend respectively
Ionized water and dichloromethane are washed；The drying is to be dried 12 hours under vacuum room temperature.
8. the use of the composite photo-catalyst of a kind of metal zinc protoporphyrin axial direction according to claim 1 functionalized titanic oxide
On the way, it is characterised in that using the composite catalyst as photocatalysis treatment waste water from dyestuff pollutant.
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| CN107362833A (en) * | 2017-07-28 | 2017-11-21 | 浙江理工大学 | A kind of preparation method of animal hair class photochemical catalyst |
| CN107899618A (en) * | 2017-10-23 | 2018-04-13 | 中山大学 | A kind of hybrid material based on macrocyclic compound light-sensitive coloring agent and titanium dioxide and preparation method thereof and the application in photocatalysis |
| CN108940380A (en) * | 2018-07-27 | 2018-12-07 | 中国石油大学(华东) | A kind of preparation method of the visible light-responded photochemical catalyst based on dye-sensitized titania |
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| CN115192705A (en) * | 2021-04-13 | 2022-10-18 | 中国科学院化学研究所 | Zwitterionic covalent organic polymer/titanium dioxide nanocomposite and preparation method and application thereof |
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