CN108479831A - A kind of preparation method of photocatalytic degradation Microcystin composite material and application - Google Patents
A kind of preparation method of photocatalytic degradation Microcystin composite material and application Download PDFInfo
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- CN108479831A CN108479831A CN201810105977.8A CN201810105977A CN108479831A CN 108479831 A CN108479831 A CN 108479831A CN 201810105977 A CN201810105977 A CN 201810105977A CN 108479831 A CN108479831 A CN 108479831A
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- SRUWWOSWHXIIIA-UKPGNTDSSA-N Cyanoginosin Chemical compound N1C(=O)[C@H](CCCN=C(N)N)NC(=O)[C@@H](C)[C@H](C(O)=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](C)NC(=O)C(=C)N(C)C(=O)CC[C@H](C(O)=O)N(C)C(=O)[C@@H](C)[C@@H]1\C=C\C(\C)=C\[C@H](C)[C@@H](O)CC1=CC=CC=C1 SRUWWOSWHXIIIA-UKPGNTDSSA-N 0.000 title abstract description 13
- 108010067094 microcystin Proteins 0.000 title abstract description 12
- 238000013033 photocatalytic degradation reaction Methods 0.000 title description 5
- 239000000463 material Substances 0.000 claims abstract description 42
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 239000003053 toxin Substances 0.000 claims abstract description 9
- 231100000765 toxin Toxicity 0.000 claims abstract description 9
- 108700012359 toxins Proteins 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 230000000593 degrading effect Effects 0.000 claims abstract description 3
- 239000011941 photocatalyst Substances 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- DIDLWIPCWUSYPF-UHFFFAOYSA-N microcystin-LR Natural products COC(Cc1ccccc1)C(C)C=C(/C)C=CC2NC(=O)C(NC(CCCNC(=N)N)C(=O)O)NC(=O)C(C)C(NC(=O)C(NC(CC(C)C)C(=O)O)NC(=O)C(C)NC(=O)C(=C)N(C)C(=O)CCC(NC(=O)C2C)C(=O)O)C(=O)O DIDLWIPCWUSYPF-UHFFFAOYSA-N 0.000 claims description 10
- 229910020700 Na3VO4 Inorganic materials 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000006303 photolysis reaction Methods 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- HCITUYXHCZGFEO-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.N=C1NC(=N)NC(=N)N1 HCITUYXHCZGFEO-UHFFFAOYSA-N 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000003814 drug Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 21
- 230000001699 photocatalysis Effects 0.000 abstract description 18
- 230000015556 catabolic process Effects 0.000 abstract description 12
- 238000006731 degradation reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 4
- 238000009388 chemical precipitation Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 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
- 241000192700 Cyanobacteria Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- OTLLEIBWKHEHGU-UHFFFAOYSA-N 2-[5-[[5-(6-aminopurin-9-yl)-3,4-dihydroxyoxolan-2-yl]methoxy]-3,4-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-3,5-dihydroxy-4-phosphonooxyhexanedioic acid Chemical compound C1=NC=2C(N)=NC=NC=2N1C(C(C1O)O)OC1COC1C(CO)OC(OC(C(O)C(OP(O)(O)=O)C(O)C(O)=O)C(O)=O)C(O)C1O OTLLEIBWKHEHGU-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 108010049746 Microcystins Proteins 0.000 description 1
- 241000192710 Microcystis aeruginosa Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 231100000776 exotoxin Toxicity 0.000 description 1
- 239000002095 exotoxin Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 210000005229 liver cell Anatomy 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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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
- C02F1/30—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
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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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Abstract
The invention belongs to photocatalytic environmental-protection fields, and in particular to a kind of Ag of catalytic degradation Microcystin3VO4/g‑C3N4Composite visible light catalytic material and the preparation method and application thereof.Photocatalysis technology of the present invention is compared to traditional treatment process, with non-secondary pollution, processing is thorough, safety and stability, the advantages that at low cost, to there is significant degradation effect with the toxic organic pollutant that Microcystin (MC LR) is representative, and there are not the open related ends reported.The present invention to convention polymerization methods by preparing g C3N4Method improve, change calcining presoma and its mixture ratio, prepare the nanometer sheet with high crystalline, high catalytic performance；Successfully synthesized by chemical precipitation method different quality than Ag3VO4/g‑C3N4Composite material.The composite material can effectively reduce the compound probability of photo-generate electron-hole, improve photocatalysis efficiency, have preferable application prospect to degrading microcystic toxins.
Description
Technical field：
The invention belongs to photocatalytic environmental-protection fields, and in particular to a kind of Ag of catalytic degradation Microcystin3VO4/g-C3N4
Composite visible light catalytic material and the preparation method and application thereof.
Background technology：
In recent years, with the development of human society, environmental problem also occurs therewith, in evolution, largely containing N, P
Stain disease is discharged into water body, is caused body eutrophication, is especially broken out, can be released with Microcystis aeruginosa in summer cyanobacterial bloom
A variety of toxin based on toxin (Microcystin), this toxin can be using liver cells as target cell, to the liver of animal and the mankind
Damage is caused even to cause death.Microcystin (MC) is a kind of biologically active monocycle polypeptide compound, structure
In Adda structures determine the physiological activity of toxin.MC properties are stablized, acid and alkali-resistance, and general heating is boiled all cannot be by it effectively
Removal.Conventional coagulation-precipitation-filtration combination technique eliminates cyanobacteria Exotoxin does not have effect substantially, but also can destroy
Cells of Blue-green Algae and promote toxin to discharge；Activated carbon adsorption, membrane filtration and mesoporous material can not destroy MC toxic groups；High dose
Ozone, chlorine and potassium permanganate oxidation method it is with high costs, intermediate by-products are easy tod produce in removal process, cause secondary dirt
Dye.Therefore, develop efficient, safety, the method that low cost removes MC in water removal has become weight urgently to be resolved hurrily in Research of Environmental Sciences
Want one of problem.Studies have found that the Adda groups in Microcystin structure can be destroyed by photocatalysis, reach the effect of degradation
Fruit.And photocatalysis treatment technology, because of its non-secondary pollution, safety and stability thorough to pollutant removal, lower-cost advantage obtains
Extensive concern has been arrived, has been one of putative most promising green environment purification techniques.
Photocatalysis mainly generates active material and Microcystin molecule under light illumination using semiconductor light-catalyst
The technology that redox makes it degrade occurs, therefore the semiconductor light-catalyst for developing efficient stable becomes photocatalysis treatment technology
Critical issue.Class graphitic nitralloy carbon (g-C3N4) be used as nonmetallic organic polymer semiconductor material, due to its energy gap compared with
Narrow (Eg=2.70eV), chemical stability is good, is easy modified and has the advantages that higher photocatalysis performance, it is made to be led in photocatalysis
Domain has received widespread attention.But single g-C3N4Light induced electron and hole-recombination rate it is higher, lead to its light-catalysed effect
Fruit is unsatisfactory.It, can be by g-C in order to inhibit the compound of photo-generate electron-hole pair3N4It is compound with other materials, utilize the two
It acts synergistically to improve its photocatalytic activity.
Ag3VO4Low energy valence band (valent band) by the 4d of Ag10The 2p of track and O6Orbital hybridization forms, and it is high
Energy conduction band (conduction band) is made of the 5s tracks of Ag and the 3d orbital hybridizations of V.The valence band structure of hydridization has than list
The 2p of one O6More active energy level results in narrower energy gap.The design feature makes Ag3VO4The response range of light is expanded
Exhibition becomes another extremely promising visible light responsive photocatalyst to visible region.The present invention is by novel narrow gap semiconductor
Ag3VO4With nonmetallic organic semiconductor g-C3N4It carries out compound, Ag is prepared3VO4/g-C3N4Compound visible light catalytic material
Material.Up to the present, about Ag3VO4/g-C3N4Composite photocatalyst material to the report of Microcystins in Water (MC-LR) also
Without reference to.
Invention content：
The purpose of the present invention is to provide a kind of Ag of catalytic degradation Microcystin3VO4/g-C3N4Composite photocatalyst material
The preparation method of material.The present invention to convention polymerization methods by preparing g-C3N4Method improve, using change calcining presoma and its
Mixture ratio has prepared the nanometer sheet with high crystalline, high catalytic performance；It is successfully synthesized not by chemical precipitation method
Homogenous quantities than Ag3VO4/g-C3N4Composite material.
Another object of the present invention is to provide a kind of Ag3VO4/g-C3N4Composite photocatalyst material Visible Light Induced Photocatalytic micro-capsule
The technology of algae toxin.The advantages that technology has non-secondary pollution, thorough to pollutant removal, safety and stability, cost is relatively low, it is right
Degrading microcystic toxins have preferable application prospect.
In order to realize first above-mentioned purpose, present invention employs technical solutions below：
A kind of Ag3VO4/g-C3N4Composite visible light responsible photocatalytic material is by Ag3VO4And g-C3N4The complex light of composition
Catalysis material, Ag in composite catalyzing material3VO4Mass ratio be 10wt%~30wt%.
1, a kind of Ag3VO4/g-C3N4The preparation method of composite visible light catalytic material, includes the following steps：
(1) g-C is prepared3N4Powder：The mass ratio for weighing urea (Urea) and melamine (Melamine) is respectively to urinate
Element：Melamine=1:0,4:1,3:2,1:1,2:3,1:4,0:1 mixing, ground and mixed is uniform, is put into crucible, is placed in Muffle
Blowing air is calcined in stove, is taken out, is ground into powder, hereinafter referred to as CN after cooled to room temperature, and photochemical catalyst point is obtained
It Wei not CN (10), CN (41), CN (32), CN (11), CN (23), CN (14) and CN (01).The experimental results showed that the crystalline substance of CN (32)
Interplanar distance is more than the interplanar distance of other samples, is more advantageous to the compound of medicament；
(2)Ag3VO4/g-C3N4The preparation of composite photocatalyst material：CN (32) powder that 1g has been prepared is weighed, is put into super
It is dissolved in pure water, makes powder is evenly dispersed to obtain light yellow suspension in the solution.Take 0.2049g AgNO3It is dissolved in 100mL
Ultra-pure water in；Weigh 0.74g Na3VO4·6H2O is dissolved in 100mL ultra-pure waters, then by Na3VO4Solution is slowly dropped into
AgNO3With in CN (32) mixed liquor stir after centrifuge, take out sediment, respectively washed 4 times with absolute ethyl alcohol and ultra-pure water；Finally
It is positioned over vacuum drying chamber, completes Ag3VO4The preparation process of/CN (32) catalysis material.
2, in the above method, step (1) heating uses Muffle furnace to be warming up to 550 DEG C with the speed of 2.3 DEG C/min, and
Constant temperature keeps natural cooling after 4h.
3, in the above method, step (2) dispersion uses ultrasonic disperse 30min.
4, in the above method, step (2) described Ag3VO4/g-C3N4Ag in composite visible light catalytic material3VO4Mass ratio
For 10wt%~30wt%.
5, in the above method, step (2) described stirring condition is to be protected from light magnetic agitation 4h, to avoid Ag3VO4Photodissociation.
6, in the above method, step (2) vacuum drying condition is dry 10h at 60 DEG C.
Compared with prior art, the invention has the advantages that：
(1) preparation method of the invention have simple for process, mild condition, stability it is good, it is of low cost, can efficiently utilize
A kind of monomer need to only be mixed with another monomer, composite wood generated by simple chemical precipitation method by the advantages that solar energy
Material；
(2) composite photocatalyst material prepared by preparation method through the invention is laminated structure, has larger ratio table
Area is conducive to the fast transferring of photo-generated carrier, to have high photocatalytic activity, with g-C3N4Single phase ratio,
Ag3VO4/g-C3N4Composite photocatalyst material further improves the response to visible light, has higher degradation efficiency；
(3) under the irradiation of 350W xenon lamps, which shows good drop to Microcystin (MC-LR)
Effect is solved, is had potential application in decomposing toxic organic pollutant treatment technology using solar energy photocatalytic.
Description of the drawings：
Fig. 1 is Ag of the present invention3VO4The scanning electron microscope (SEM) photograph (SEM) of/CN (32) composite visible light catalytic material.
Fig. 2 is Ag of the present invention3VO4The X-ray diffractogram (XRD) of/CN (32) composite visible light catalytic material.
Fig. 3 is the pure CN (32) of the present invention, Ag3VO4/ CN (32) composite visible light catalytic materials are to Microcystin (MC-LR)
Photocatalytic degradation effect figure.
Specific implementation mode：
The following describes the present invention in detail with reference to examples, so that those skilled in the art more fully understand this hair
It is bright, but the invention is not limited in following embodiments.
Embodiment 1：
Ag3VO4/g-C3N4The preparation of composite photocatalyst material：CN (32) powder that 1g has been prepared is weighed, is put into ultrapure
It is dissolved in water, and ultrasound 0.5h, makes powder is evenly dispersed to obtain light yellow suspension in the solution.Take 0.1025g AgNO3It is molten
Solution is in the ultra-pure water of 100mL.Weigh 0.37g Na3VO4·6H2O is dissolved in 100mL ultra-pure waters, then by Na3VO4Solution
It is slowly dropped into AgNO3With CN (32) mixed liquor, it is protected from light magnetic agitation 4h, avoids Ag3VO4Photodissociation, centrifuge, it is heavy to take out
Starch is respectively washed 4 times with absolute ethyl alcohol and ultra-pure water.It is finally positioned over vacuum drying chamber, the dry 10h in 60 DEG C.Finally, it is made
Ag3VO4/ CN (32) catalysis material, wherein Ag3VO4Mass ratio in composite photocatalyst material is 10wt%.
Fig. 1 show different composite than Ag3VO4The SEM of/CN (32) characterizes sample drawing.Fig. 1 is Ag3VO4/ CN's (32)
SEM spectrum, to CN (32) analyze, can be clearly seen that there is nano particle on CN (32) surface, described in document can
With pure Ag3VO4Be that the particle agglomeration of nm regime forms a diameter of several microns of bulk together, and in figure this it appears that
Diametrically size is that the nano particle of 60-90nm is dispersed in the surface of (32) CN, it is believed that Ag3VO4Successfully CN is loaded to
(32) surface.
Fig. 2 show different composite than Ag3VO4The XRD spectrum of/CN (32) material.It can be seen from the figure that being in 2 θ
Two characteristic peaks at 13.1 ° and 27.7 ° belong to CN (32).And 2 θ be 19.2 °, 30.9 °, 32.4 °, 35.1 °,
Characteristic peak at 35.9 °, 38.9 °, 41.4 °, 48.3 °, 51.2 ° and 54.1 °, correspond to respectively (011), (- 121), (121),
(301), (202), (022), (400), (- 322), (132) and (331) lattice, with Ag3VO4Standard PDF cards (JCPDS：
43-0542) it is consistent.And in the XRD spectrum after being doped on CN (32), CN (32) does not disappear corresponding characteristic peak,
Illustrate Ag3VO4After forming hetero-junctions with CN (32), the characteristic peak of system does not change substantially, not formation between them
Chemical bond.Ag3VO4The principal character peak of/CN (32) composite material is in Ag3VO4With the compound rear not significant change evidences of CN (32)
This is it is found that Ag3VO4Successfully it has been supported on the surface of (32) CN.
The Ag of preparation3VO4/ CN (32) composite visible light catalytic material in 100min to Microcystin (MC-LR) can
Light-exposed degradation rate result is shown in Fig. 3.
Embodiment 2：
Except for the following differences, remaining is the same as embodiment 1 for operating process.
Weigh 0.2049g AgNO3、0.74g Na3VO4·6H2CN (32) powder of gained in O and 1.0g embodiments 1,
Middle Ag3VO4Mass ratio in composite photocatalyst material is 20wt%.
The XRD analysis result of sample is shown in Fig. 2.The sem analysis result of sample is similar to Example 1.Sample is in 100min
Fig. 3 is shown in the Visible Light Induced Photocatalytic rate result of Microcystin.
Embodiment 3：
Except for the following differences, remaining is the same as embodiment 2 for operating process.
Weigh 0.3074g AgNO3、1.11g Na3VO4·6H2CN (32) powder of gained in O and 1.0g embodiments 1,
Middle Ag3VO4Mass ratio in composite photocatalyst material is 30wt%.
The XRD analysis result of sample is shown in Fig. 2.The sem analysis result of sample is similar to Example 2.Sample is in 100min
Fig. 3 is shown in the Visible Light Induced Photocatalytic rate result of Microcystin.
Embodiment 4：
Photocatalytic activity evaluation：Light-catalyzed reaction is visible light photocatalytic degradation device (the XPA series in 26 DEG C of a constant temperature
Photochemical reactor, Xujiang Electromechanical Plant, Nanjing, China) in carry out.The CN (32) that 50mg is weighed in reaction process, is added to 10mL's
In MC-LR (15mg/L) reaction solution.In order to exclude the influence of suction-operated, suspension is carried out in the dark before reaction starts
60min magnetic stirs dark reaction, reaches adsorption/desorption balance, light source (350W xenon lamps, wavelength model are opened after dark reaction
Enclose for 360nm-760nm), optical filter is added on reactor, filters off the part light that wavelength is less than 420nm, and cold in quartz
The sodium nitrite solution of 5g/L is added in trap, in order to filter off ultraviolet light.1mL mixed solutions are taken every 30min in reaction process, so
After pass sequentially through centrifugation, (0.45 μm) of micro porous filtration removing catalyst granules, then use MC-LR in liquid chromatogram measuring solution
Solubility.
The experimental results showed that within the reaction time of 100min, with the increase in reaction time, degradation efficiency improves,
In, CN (32) is 18.98% to the degradation rate of Microcystin in Xenon light shining 100min.
Embodiment 5：
Except for the following differences, remaining is the same as embodiment 4 for operating process.
Ag is added3VO4/ CN (32) composite photocatalyst material 50mg.
The experimental results showed that with Ag in sample3VO4The increase of content, the degradation rate to MC-LR are in first increases and then decreases
Trend, wherein Ag3VO4The effect of the visible light photocatalytic degradation MC-LR of/CN (32) is best, can reach 85.4%, is single CN
(32) 4.5 times of degradation rate.Ag3VO4/ CN (32) has significant degradation effect to MC-LR.
The embodiment is the preferred embodiments of the present invention, but present invention is not limited to the embodiments described above, not
Away from the present invention substantive content in the case of, those skilled in the art can make it is any it is conspicuously improved, replace
Or modification all belongs to the scope of protection of the present invention.
Claims (7)
1. a kind of Ag3VO4/g-C3N4The preparation method of composite visible light catalytic material, which is characterized in that include the following steps：
(1) g-C is prepared3N4Powder：The mass ratio for weighing urea (Urea) and melamine (Melamine) is respectively urea：Three
Poly cyanamid=1:0,4:1,3:2,1:1,2:3,1:4,0:1 mixing, ground and mixed is uniform, is put into crucible, is placed in Muffle furnace
Blowing air is calcined, and is taken out, is ground into powder, hereinafter referred to as CN, obtaining photochemical catalyst is respectively after cooled to room temperature
CN (10), CN (41), CN (32), CN (11), CN (23), CN (14) and CN (01).The experimental results showed that the interplanar of CN (32)
Away from the interplanar distance more than other samples, it is more advantageous to the compound of medicament；
(2)Ag3VO4/g-C3N4The preparation of composite photocatalyst material：CN (32) powder that 1g has been prepared is weighed, ultra-pure water is put into
Middle dissolving makes powder is evenly dispersed to obtain light yellow suspension in the solution；Take 0.2049g AgNO3It is dissolved in the super of 100mL
In pure water；Weigh 0.74g Na3VO4·6H2O is dissolved in 100mL ultra-pure waters, then by Na3VO4Solution is slowly dropped into AgNO3
With in CN (32) mixed liquor stir 4h after centrifuge, take out sediment, respectively washed 4 times with absolute ethyl alcohol and ultra-pure water；Finally put
It is placed in vacuum drying chamber, completes Ag3VO4/g-C3N4The preparation process of catalysis material.
2. Ag according to claim 13VO4/g-C3N4The preparation method of composite visible light catalytic material, which is characterized in that
Step (1) heating uses Muffle furnace to be warming up to 550 DEG C with the speed of 2.3 DEG C/min, and constant temperature keeps natural cooling after 4h.
3. Ag according to claim 13VO4/g-C3N4The preparation method of composite visible light catalytic material, which is characterized in that
Step (2) dispersion uses ultrasonic disperse 30min.
4. Ag according to claim 13VO4/g-C3N4The preparation method of composite visible light catalytic material, which is characterized in that
Step (2) described Ag3VO4/g-C3N4Ag in composite visible light catalytic material3VO4Mass ratio be 10wt%~30wt%.
5. Ag according to claim 13VO4/g-C3N4The preparation method of composite visible light catalytic material, which is characterized in that
Step (2) stirring is is protected from light magnetic force, to avoid Ag3VO4Photodissociation.
6. Ag according to claim 13VO4/g-C3N4The preparation method of composite visible light catalytic material, which is characterized in that
Step (2) vacuum drying condition is dry 10h at 60 DEG C.
7. a kind of Ag being prepared according to claim 13VO4/g-C3N4The application of composite photocatalyst material, which is characterized in that
Application of the catalysis material in degrading microcystic toxins (MC-LR).
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