CN106955718A - A kind of ZnS/Bi2O3Hetero-junctions molecular engram photocatalysis membrana and preparation method and purposes - Google Patents
A kind of ZnS/Bi2O3Hetero-junctions molecular engram photocatalysis membrana and preparation method and purposes Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 37
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims abstract description 62
- 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 claims abstract description 48
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000011941 photocatalyst Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000005266 casting Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 239000005083 Zinc sulfide Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 7
- 229920001661 Chitosan Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229920002301 cellulose acetate Polymers 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- BEAZKUGSCHFXIQ-UHFFFAOYSA-L zinc;diacetate;dihydrate Chemical compound O.O.[Zn+2].CC([O-])=O.CC([O-])=O BEAZKUGSCHFXIQ-UHFFFAOYSA-L 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 26
- 230000015556 catabolic process Effects 0.000 abstract description 22
- 238000006731 degradation reaction Methods 0.000 abstract description 22
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- 230000008569 process Effects 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- 239000000356 contaminant Substances 0.000 abstract description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 6
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- 238000002835 absorbance Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
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- 150000001875 compounds Chemical class 0.000 description 3
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- 230000002452 interceptive effect Effects 0.000 description 3
- 229960000907 methylthioninium chloride Drugs 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
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- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000002778 food additive Substances 0.000 description 2
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- 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 2
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- 239000003643 water by type Substances 0.000 description 2
- CCBICDLNWJRFPO-UHFFFAOYSA-N 2,6-dichloroindophenol Chemical compound C1=CC(O)=CC=C1N=C1C=C(Cl)C(=O)C(Cl)=C1 CCBICDLNWJRFPO-UHFFFAOYSA-N 0.000 description 1
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- 240000004343 Indigofera suffruticosa Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000005276 aerator Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
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- -1 hydrogen Sodium hydroxide Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000004005 microsphere 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
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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
- 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
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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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 provides a kind of ZnS/Bi2O3Hetero-junctions molecular engram photocatalysis membrana and preparation method and purposes, preparation method are as follows：Step 1, preparation Bi2O3Photochemical catalyst；Step 2, preparation ZnS/Bi2O3Heterojunction photocatalyst；Step 3, preparation ZnS/Bi2O3Hetero-junctions molecular engram photocatalysis membrana.The Photocatalytic Degradation Process that the present invention prepares the molecular engram catalytic membrane of degradation selectivity rhodamine B can effectively realize the purpose to target contaminant Selective recognition, absorption and catalytic degradation, post processing is simple and convenient, the efficiency of effective degraded to target substance is improved, there is stronger selectivity processing waste water from dyestuff.
Description
Technical field
Heterojunction structure semiconductor and dividing with photocatalysis are prepared the present invention relates to a kind of utilization phase-inversion technologies
The method of sub- trace catalytic membrane, specially a kind of ZnS/Bi of efficient degradation rhodamine B2O3Hetero-junctions molecular engram photocatalysis membrana
Preparation method and use, belong to material prepare and environmental pollution improvement technical field.
Background technology
Rhodamine B be a kind of artificial synthesized alkaline fluorescent dye simultaneously it be also a kind of common analytical reagent, extensively should
For environmental protection, mining industry, steel, medicine and other fields, it can also make cell fluorescence coloring agent in laboratory.Once it is used as food additives,
But experiment proves that rhodamine B can be carcinogenic, do not allow to be used as food additives and food is dyed.Because this kind of compound is arranged
Let out into water environment, as a kind of potential risk for endangering environment and human health, cause the extensive concern of environmental ecology,
Therefore, it is extremely urgent that foundation and development, which selectively remove rhodamine B residual in environment effectively with economic and practical processing means,
's.
Photocatalysis technology is to be excited using semiconductor or composite semiconductor under illumination condition, and producing has redox
The electron hole pair of function, so that a kind of method of degradation of contaminant.It is now widely used in dyestuff in research water environment
Residual.People improve its photocatalysis performance by being modified to photochemical catalyst, but still without selectivity, it is difficult to
Object is removed in the Complex water body that multiple pollutant coexists.Therefore, it is proposed that being urged using molecular imprinting technology with photoelectricity
Change technology is combined, and makes it have special identification function, and prioritizing selection removes target contaminant.
Molecular engram membrane technology is a kind of new selective seperation film to target molecule with single-minded recognition capability, can be with
The synthetic method of molecularly imprinted polymer is used in the preparation process of separation membrane material, can also be by being produced in seperation film
Microsphere is introduced in journey.Molecular engram membrane technology has coupled the advantage of molecular engram and membrane technology, can be by specific target
Molecule is efficiently separated from mixture and its analogue.
Molecular engram membrane technology is combined with photocatalysis technology, the molecule with degradation selectivity object is prepared
Trace catalytic membrane, the catalytic membrane can adsorbed target molecule, and preferential degradation first, the circulation of absorption degradation is realized after degraded again
System, and then reach collaboration and promote the purpose of selective photocatalysis degraded target contaminant.Therefore environment is selectively being removed
Had broad application prospects in terms of middle Rhodamine B Dyes residual.
The content of the invention
The present invention using phase-inversion technologies be preparation means, prepare it is a kind of have to target contaminant rhodamine B it is specific
The molecular engram catalytic membrane composite photo-catalyst of selectivity.One cyclic process of structure in system is the advantage is that, is realized
Catalytic degradation again is first adsorbed to target substance, then the cyclic process of absorption degradation again, and then effectively reach have using light source
The purpose of rhdamine B waste water in effect degraded environment.
The technical scheme is that：
A kind of ZnS/Bi2O3Hetero-junctions molecular engram photocatalysis membrana, the molecular engram photocatalysis membrana is by zinc sulphide spheroid
With the Bi of convex2O3What crystallization was composited, the Bi2O3Crystallization is carried on the zinc sulphide spherome surface.
A kind of ZnS/Bi2O3The preparation method of hetero-junctions molecular engram photocatalysis membrana, step is as follows：
Step 1, preparation Bi2O3Photochemical catalyst：Five water bismuth nitrates are dissolved in deionized water, bismuth nitrate solution is obtained；By hydrogen
Sodium hydroxide solution adds bismuth nitrate solution, adjusts pH, and stirring is reacted, centrifuges mixed liquor after reaction completely at room temperature,
Washed respectively with deionized water and absolute ethyl alcohol repeatedly, dry, obtain pale yellow powder A；Pale yellow powder A is placed in Muffle furnace
In, in calcining certain time under uniform temperature, obtain Bi2O3Photochemical catalyst, it is stand-by；
Step 2, preparation ZnS/Bi2O3Heterojunction photocatalyst：Zinc diacetate dihydrate is taken to be dissolved in deionization under being stirred with thiocarbamide
In water, and add Bi2O3Photochemical catalyst, obtains mixed liquid B；Mixed liquid B is moved into stainless steel high pressure water heating kettle, solvent heat is carried out
Reaction, obtains mixed liquor C after cooling；Mixed liquor C is filtered, and washs solid product, is ground after drying, obtains ZnS/Bi2O3Hetero-junctions
Photochemical catalyst, is stored in sampling pipe, standby；
Step 3, preparation ZnS/Bi2O3Hetero-junctions molecular engram photocatalysis membrana：Take ZnS/Bi2O3Heterojunction photocatalyst adds
Enter into dimethyl sulfoxide, ultrasonic disperse obtains ZnS/Bi2O3Heterojunction photocatalyst dispersion liquid；To ZnS/Bi2O3Hetero-junctions light is urged
Add and stirred and evenly mixed at cellulose acetate, chitosan and rhodamine B, 40 ± 5 DEG C in agent dispersion liquid, mechanical agitation is uniform, obtains
To casting solution；By casting solution in being incubated standing at 40 ± 5 DEG C, the bubble that stirring is produced is sloughed, a clean glass plate is then taken,
Casting solution is laid on glass plate, certain thickness is scraped with glass bar, places after a period of time, is slowly dipped in deionization
Soak after a period of time and take out in water, obtain blend film；Blend film is peeled from glass plate, methanol/acetic acid mixing is placed in and carries
Take in liquid, immersion a period of time is standby then by film room temperature storage in deionized water to remove template molecule.
In step 1, in bismuth nitrate solution, the mass ratio of used five water bismuth nitrate powder and deionized water is 9.7：
100；The concentration of used sodium hydroxide solution is 0.5mol/L, and the pH is 8；The calcining heat is 300 DEG C~500
℃；The calcination time is 2h~6h.
In step 2, during mixed liquid B processed, used Zinc diacetate dihydrate, thiocarbamide, Bi2O3Photochemical catalyst and deionized water
Mass ratio is 1.1:1.9:0.1:35；The temperature of the solvent thermal reaction is 170 DEG C~210 DEG C, and the time is 5h~24h；It is described
Dry temperature is 60 DEG C~80 DEG C, and drying time is 12h~24h.
In step 3, ZnS/Bi is prepared2O3During heterojunction photocatalyst dispersion liquid, used ZnS/Bi2O3Hetero-junctions is urged
The mass ratio of agent and dimethyl sulfoxide is 0.1~0.4:16.74~17.04；The time of the ultrasonic disperse is 1~2h；It is described
In casting solution, the mass fraction of the cellulose acetate is the 13% of casting solution, and the mass fraction of chitosan is casting solution
1.0%, the mass fraction of rhodamine B is the 0.3% of casting solution, and the churned mechanically time is 4h；Described insulation is stood
Time is 12~24h, and the thickness of blend film is 1.0mm；The time of described placement is at least 30s, soaks in deionized water
Time be at least 10min；In the methanol/acetic acid mixed extract, methanol, the volume ratio of acetic acid are 9:1.
Prepared ZnS/Bi2O3Hetero-junctions molecular engram photocatalysis membrana is used as photocatalyst for degrading rhodamine B.
Dimethyl sulfoxide described in above-mentioned technical scheme, it act as solvent, dissolving cellulose acetate and rhodamine B,
To prepare casting solution.
Cellulose acetate described in above-mentioned technical scheme, it act as matrix.
Chitosan described in above-mentioned technical scheme, it act as functional polymer.
Deionized water described in above-mentioned technical scheme, it act as non-solvent.
Methanol/acetic acid mixed extract described in above-mentioned technical scheme, it act as blocking template molecule and function
Hydrogen bond action between polymer, so that eluted template molecule.
The selective molecular engram of rhodamine B is catalyzed using what molecular engram membrane technology was prepared using the present invention
Film, has higher degradation selectivity effect to template molecule rhodamine B.
The preparation method of corresponding non-trace blend film (NIM) is same as described above, but is not added with template molecule rhodamine B.
Photocatalytic activity evaluation：Carried out in DW-01 type photochemical reaction instrument, it is seen that light light irradiation, 100mL is necessarily dense
The rhodamine B simulated wastewater of degree adds in reactor and determines its initial value, then adds a certain amount of blotting membrane and non-trace
Film photocatalyst, open aerator be passed through air, can provide in the oxygen in photocatalytic process, During Illumination at interval of
Supernatant liquor is taken after 30min sampling analyses, centrifugation in ultraviolet-visible spectrophotometer λmaxExtinction is determined at=554nm
Degree, and pass through formula：DC=[(A0-Ai)/A0] × 100% calculates degradation rate, wherein A0To reach rhodamine B during adsorption equilibrium
The absorbance of solution, AiThe absorbance of the rhodamine B solution determined for timing sampling.
The technological merit of the present invention：
First, ZnS and Bi2O3Photochemical catalyst is belonged to, but ZnS forbidden band is wider, only has catalysis under ultraviolet light conditions
Effect, and Bi2O3Forbidden band is narrower, can select both semiconductors combining to form heterojunction structure, energy by excited by visible light
The light induced electron of generation is enough set to inject another semiconductor from a kind of semiconductor, so that the compound of electron hole is effectively prevented,
Photocatalysis efficiency can be thus improved, the degradation rate to target substance is improved.Secondly, the technology uses hydrothermal synthesis method, step
It is relatively simple.Finally, the Photocatalytic Degradation Process of the molecular engram catalytic membrane of degradation selectivity rhodamine B can be realized effectively
To the purpose of target contaminant Selective recognition, absorption and catalytic degradation, post processing is simple and convenient, improves to target substance
The efficiency effectively degraded, has the advantages that stronger selectivity processing waste water from dyestuff.
Brief description of the drawings
Fig. 1 is ZnS, Bi2O3、ZnS/Bi2O3Scanning electron microscope (SEM) photograph, wherein, figure a be ZnS scanning electron microscope (SEM) photograph, figure b be
Bi2O3Scanning electron microscope (SEM) photograph, figure c be ZnS/Bi2O3Scanning electron microscope (SEM) photograph；
Fig. 2 is ZnS, Bi2O3、ZnS/Bi2O3XRD spectra.
Embodiment
With reference to specific implementation example, the present invention will be further described.
The present invention is so that casting solution gross mass is 20g as an example.
Embodiment 1：
(1)ZnS/Bi2O3The preparation of hetero-junctions catalyst
First, the water bismuth nitrates of 9.7g five are dissolved in 100mL deionized waters, obtain bismuth nitrate solution, Ran Houqu
500mL0.5mol·L-1Bismuth nitrate solution is added dropwise in sodium hydroxide solution, stirring, reacts at room temperature, obtains white or yellowish
Color is precipitated.Centrifuge, then washed respectively 3 times with deionized water and absolute ethyl alcohol, dry 12h after centrifugation at 60 DEG C,
Put the powder into Muffle furnace in calcining 2h at 400 DEG C, obtain Bi2O3Catalyst, it is stand-by.Take 2.2g Zinc diacetate dihydrates
It is dissolved in 3.8g thiocarbamides in 70mL deionized waters, then takes 0.2g Bi2O3Photochemical catalyst is scattered in above-mentioned solution, stands 0.5h
Afterwards, above-mentioned solution is transferred in stainless steel autoclave, heats 5h at 170 DEG C, be cooled to after room temperature, then leaked with Bu Shi
Bucket vacuum filtration is simultaneously washed 3 times respectively with deionized water and absolute ethyl alcohol, 12h~24h is dried in vacuo at 60 DEG C~80 DEG C, finally
Obtain ZnS/Bi2O3Hetero-junctions catalyst.
(2) preparation of molecular engram catalytic membrane
First, 0.1gZnS/Bi is taken2O3Hetero-junctions catalyst is added in 17.04g dimethyl sulfoxides (DMSO), and ultrasonic disperse 1~
2h obtains ZnS/Bi2O3Hetero-junctions catalyst dispersion, then adds 0.06g template molecules (rhodamine B), 2.6g membrane matrix (vinegar
Acid cellulose) and 0.2g functional polymers (chitosan), mechanical agitation 4h obtains casting film to being uniformly dissolved under the conditions of 40 ± 5 DEG C
Liquid, 12~24h is stood in insulation at 40 ± 5 DEG C, sloughs the bubble that stirring is produced, and a clean glass plate is then taken, by casting film
Liquid is laid on glass plate, is scraped and be slowly dipped in after the film of 1.0mm thickness, 30s in deionized water with glass bar, immersion
Taken out after 30min, produce molecular engram catalytic membrane and be stored in deionized water.The preparation method of non-blotting membrane is same as described above,
But it is not added with template molecule rhodamine B.Volume ratio is finally used for 9:1 methanol/acetic acid mixed solution is extract solution, to remove mould
Plate molecule rhodamine B, is washed with water and washs for several times to neutral, obtained molecular engram catalytic membrane is stored in deionized water, make
For contrast, the non-trace catalytic membrane of blank is synthesized with step in the same way, except being not added with template molecule in the course of the polymerization process
Rhodamine B.
(3) the photocatalytic activity experiment of molecular engram catalytic membrane
Take the sample prepared in 10g steps (2) to carry out photocatalytic degradation experiment in photochemical reaction instrument, add 100mL,
20mg·L-1Rhodamine B solution in, magnetic agitation secretly adsorbs 1h, opens source of recycled water, and light source carries out photocatalytic degradation real
Test, the photocatalytic degradation liquid in 4-6ml reactors is drawn per 30min, it is surveyed with ultraviolet-visible spectrophotometer at 554nm
Absorbance, and pass through formula：DC%=[(A0-Ai)/A0] × 100% calculates degradation rate, wherein A0To reach during adsorption equilibrium
The absorbance of rhodamine B solution, AiThe absorbance of the rhodamine B solution determined for timing sampling.Degradation rate represents preparation in (2)
Catalyst photocatalytic activity.
Fig. 1 is ZnS, Bi2O3、ZnS/Bi2O3Scanning electron microscope (SEM) photograph.It can be seen that from figure a, ZnS is spherical, and figure b is Bi2O3's
As can be seen that there is the Bi of convex around ZnS spheroids in crystalline state, figure c2O3Crystallization.
Fig. 2 is ZnS, Bi2O3And ZnS/Bi2O3The XRD spectra of composite.Bismuth oxide has sharp at 27 ° and 34 °
There is obvious diffraction maximum in characteristic peak, zinc sulphide, and correspond to (111) of zinc sulphide, (220) at 28.9 °, 48.8 ° and 57.2 °,
(311) crystal face, while finding out in compound XRD, hence it is evident that there are (220) of zinc sulphide, the diffraction maximum of (311) crystal face, and
(111) crystallographic plane diffraction peak is overlapped with the diffraction maximum of bismuth oxide.
Embodiment 2：
In the case of ensureing that other conditions are constant, contrast test is set up as follows：(1) Bi processed2O3During photochemical catalyst, calcining temperature
Degree takes 300 DEG C, calcination time 4h, hydro-thermal method synthesis ZnS/Bi2O3During heterojunction photocatalyst, reactor reaction temperature takes 210
DEG C, reaction time 5h after reaction terminates, is washed and dried with same procedure, and grinding obtains powder catalyst, stand-by.(2) make
Bi2O3During photochemical catalyst, calcining heat takes 500 DEG C, calcination time 6h, hydro-thermal method synthesis ZnS/Bi2O3Heterojunction photocatalyst
When, reactor reaction temperature takes 170 DEG C, and reaction time 24h after reaction terminates, is washed and dried with same procedure, grinding is obtained
Powder catalyst, it is stand-by.Obtained catalyst under obtained different condition, for rhodamine B degradation, observes and calculates degraded effect
Rate.
Embodiment 3：
(1) by changing ZnS/Bi2O3The consumption (0.2g, 0.3g, 0.4g) of heterojunction photocatalyst is thrown to examine or check catalyst
Influence of the dosage to photocatalytic degradation, is changing ZnS/Bi2O3While the consumption of heterojunction photocatalyst, change dimethyl sulfoxide
Consumption (16.94g, 16.84g, 16.74g), it is ensured that ZnS/Bi2O3The total mass fraction of heterojunction photocatalyst, dimethyl sulfoxide
For 85.7%, as a result show when catalyst amount is 0.4g that its degradation efficiency highest to rhodamine B can reach 90%
More than.So the catalyst amount selected in experiment is 0.4g.
(2) with the molecular engram catalytic membrane prepared by 0.4g photochemical catalysts under visible light catalytic degradation various concentrations (10,
20,30,40,50mgL-1) rhodamine B solution, examination in various concentrations drop of the molecular engram photocatalysis membrana to rhodamine B
Dynamics is solved, by calculating and being fitted kinetics equation, the process of molecular engram photocatalyst for degrading rhodamine B meets
Pseudo-first-order kinetic model, when rhodamine B initial concentration is 20mgL-1When, molecular engram photocatalysis membrana is put down to rhodamine B
Equal degradation rate is 0.048min-1。
Embodiment 4：
The rhodamine B of the photocatalysis membrana degraded same concentrations prepared respectively in (2) in use-case 1 and interfering material (methylene
Base is blue) mixed solution, by calculating the degradation efficiency to different material and then calculating its selectivity factor to different material.
Wherein C0, CeConcentration (mgL respectively after rhodamine B starting and degraded-1)；D is distribution coefficient, DCIP, DMPoint
Not Wei rhodamine B and interfering material distribution coefficient；α is selectivity factor, αi, αnRespectively trace and blank polymer light is urged
The selectivity factor of agent, αrIt is relative selectivity coefficient.
Test result indicate that, the thing that molecular engram photocatalysis membrana is contrasted to the degradation efficiency of rhodamine B apparently higher than other
Matter, selectivity factor is also both greater than other interfering materials, relative choosing of the molecular engram photocatalysis membrana to rhodamine B and methylene blue
It is respectively 3.28 and 1.57 to select property coefficient.The molecular engram catalytic membrane that explanation is synthesized with the method has preferable to rhodamine B
Selectivity, it is achieved thereby that the purpose degraded to target substance rhodamine B selective catalysis.
Embodiment 5：
(1) photochemical catalyst prepared in (2) first in use-case 1 individually adsorbs the rhodamine B of various concentrations, methylene
Indigo plant, the solution of methyl orange.Adsorption capacity of the trace catalytic membrane to different plant species is calculated according to formula.Q=(C0-Ce) * V/m, wherein
Q is the adsorption capacity (mgg of adsorbent-1), C0, CeConcentration (mgL respectively before rhodamine B absorption and after adsorption equilibrium-1), V is the volume (L) of rhodamine B solution, and m is the quality (g) of adsorbent.Experimental result shows, molecular engram photocatalysis membrana pair
The adsorption capacity of template molecule rhodamine B is generally several to this more than the adsorption capacity to other materials, rather than trace catalytic membrane
The adsorption capacity of material is more or less the same.
(2) photocatalysis membrana prepared in (2) respectively in use-case 1 adsorbs rhodamine B, methylene blue and the first of same concentrations
The mixed solution of base orange, by identical adsorption time, centrifuges aaerosol solution, the concentration of supernatant is determined, according to formula
Catalyst is calculated to the adsorption capacity of different plant species, its adsorptive selectivity to different material is then calculated.As a result molecule is shown
Trace photocatalysis membrana is to the adsorption capacity of rhodamine B apparently higher than it to methylene blue and the adsorption capacity of methyl orange, Er Feiyin
Mark catalytic membrane is little to the adsorption capacity difference of three, illustrates to improve absorption of the blotting membrane to rhodamine B in printing process
Capacity.
Claims (6)
1. a kind of ZnS/Bi2O3Hetero-junctions molecular engram photocatalysis membrana, it is characterised in that the molecular engram photocatalysis membrana be by
The Bi of zinc sulphide spheroid and convex2O3What crystallization was composited, the Bi2O3Crystallization is carried on the zinc sulphide spherome surface.
2. a kind of ZnS/Bi2O3The preparation method of hetero-junctions molecular engram photocatalysis membrana, it is characterised in that step is as follows：
Step 1, preparation Bi2O3Photochemical catalyst：Five water bismuth nitrates are dissolved in deionized water, bismuth nitrate solution is obtained；By hydroxide
Sodium solution adds bismuth nitrate solution, adjusts pH, and stirring is reacted, centrifuges mixed liquor after reaction completely, spend at room temperature
Ionized water and absolute ethyl alcohol are washed repeatedly respectively, are dried, are obtained pale yellow powder A；Pale yellow powder A is placed in Muffle furnace, in
Certain time is calcined under uniform temperature, Bi is obtained2O3Photochemical catalyst, it is stand-by；
Step 2, preparation ZnS/Bi2O3Heterojunction photocatalyst：Zinc diacetate dihydrate is taken to be dissolved in deionized water under being stirred with thiocarbamide
In, and add Bi2O3Photochemical catalyst, obtains mixed liquid B；Mixed liquid B is moved into stainless steel high pressure water heating kettle, solvent heat is carried out anti-
Should, mixed liquor C is obtained after cooling；Mixed liquor C is filtered, and washs solid product, is ground after drying, obtains ZnS/Bi2O3Hetero-junctions light
Catalyst, is stored in sampling pipe, standby；
Step 3, preparation ZnS/Bi2O3Hetero-junctions molecular engram photocatalysis membrana：Take ZnS/Bi2O3Heterojunction photocatalyst is added to two
In first sulfoxide, ultrasonic disperse obtains ZnS/Bi2O3Heterojunction photocatalyst dispersion liquid；To ZnS/Bi2O3Heterojunction photocatalyst point
Add and stirred and evenly mixed at cellulose acetate, chitosan and rhodamine B, 40 ± 5 DEG C in dispersion liquid, mechanical agitation is uniform, obtains casting film
Liquid；By casting solution in being incubated standing at 40 ± 5 DEG C, a clean glass plate is then taken, casting solution is laid on glass plate, is used
Glass bar scrapes certain thickness, places after a period of time, is slowly dipped in deionized water to soak and taken out after a period of time, obtains
To blend film；Blend film is peeled from glass plate, is placed in methanol/acetic acid mixed extract, immersion a period of time, then will
Film room temperature storage is standby in deionized water.
3. a kind of ZnS/Bi according to claim 22O3The preparation method of hetero-junctions molecular engram photocatalysis membrana, its feature
It is that step is as follows：In step 1, in bismuth nitrate solution, the mass ratio of used five water bismuth nitrate powder and deionized water is
9.7：100；The concentration of used sodium hydroxide solution is 0.5mol/L, and the pH is 8；The calcining heat be 300 DEG C~
500℃；The calcination time is 2h~6h.
4. a kind of ZnS/Bi according to claim 22O3The preparation method of hetero-junctions molecular engram photocatalysis membrana, its feature
It is, in step 2, during mixed liquid B processed, used Zinc diacetate dihydrate, thiocarbamide, Bi2O3Photochemical catalyst and deionized water quality
Than for 1.1:1.9:0.1:35；The temperature of the solvent thermal reaction is 170 DEG C~210 DEG C, and the time is 5h~24h；The drying
Temperature be 60 DEG C~80 DEG C, drying time be 12h~24h.
5. a kind of ZnS/Bi according to claim 22O3The preparation method of hetero-junctions molecular engram photocatalysis membrana, its feature
It is in step 3, to prepare ZnS/Bi2O3During heterojunction photocatalyst dispersion liquid, used ZnS/Bi2O3Hetero-junctions catalyst
Mass ratio with dimethyl sulfoxide is 0.1~0.4:16.74~17.04；The time of the ultrasonic disperse is 1~2h；The casting film
In liquid, the mass fraction of the cellulose acetate is the 13% of casting solution, and the mass fraction of chitosan is the 1.0% of casting solution,
The mass fraction of rhodamine B is the 0.3% of casting solution, and the churned mechanically time is 4h；Described insulation time of repose is
12~24h, the thickness of blend film is 1.0mm；The time of described placement is at least 30s, the time soaked in deionized water
At least 10min；In the methanol/acetic acid mixed extract, methanol, the volume ratio of acetic acid are 9:1.
6. ZnS/Bi prepared by the method described in Claims 1 to 5 any one2O3The use of hetero-junctions molecular engram photocatalysis membrana
On the way, it is characterised in that prepared ZnS/Bi2O3Hetero-junctions molecular engram photocatalysis membrana is used as photocatalyst for degrading rhodamine B.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107597194A (en) * | 2017-09-28 | 2018-01-19 | 东北林业大学 | A kind of preparation method of new ZnO/ fungies fiber optic catalytic composite material |
| CN107983390A (en) * | 2017-12-08 | 2018-05-04 | 吉林师范大学 | A kind of surface imprinted carbonitride/composite titania material photocatalysis membrana and preparation method and purposes |
| CN109589992A (en) * | 2018-12-03 | 2019-04-09 | 江苏大学 | A kind of MoS2/Bi2O3The preparation method and applications of p-n heterojunction photochemical catalyst |
| CN109590026A (en) * | 2018-11-30 | 2019-04-09 | 河海大学 | A kind of composite photocatalyst material and its preparation method and application |
| CN109967095A (en) * | 2019-04-17 | 2019-07-05 | 南昌航空大学 | A kind of holocrystalline bulk heterojunction catalysis material and its preparation method and application |
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| CN114700087A (en) * | 2022-04-28 | 2022-07-05 | 广西大学 | Efficient visible light photocatalytic material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001070802A (en) * | 1999-09-03 | 2001-03-21 | Toshiba Corp | Photocatalyst film and its production |
| JP2002346394A (en) * | 2001-05-25 | 2002-12-03 | Akiba:Kk | Highly efficient photocatalyst composition, paint and substrate using the same and method for coating object using the same |
| CN101204652A (en) * | 2007-12-19 | 2008-06-25 | 中国科学院上海硅酸盐研究所 | High efficiency semiconductor photocatalysis and preparation method thereof |
| CN102284284A (en) * | 2011-06-03 | 2011-12-21 | 南昌航空大学 | Method for preparing molecularly imprinted TiO2/WO3 composite photocatalyst with visible light response through direct method |
| CN103447095A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Molecular imprinting composite membrane for photocatalytic degradation of organic matter and preparation method thereof |
| CN104759263A (en) * | 2015-03-25 | 2015-07-08 | 江苏大学 | A preparing method of a multiwalled carbon nanotube doped salicylic acid blend imprinted membrane |
-
2017
- 2017-02-27 CN CN201710107689.1A patent/CN106955718B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001070802A (en) * | 1999-09-03 | 2001-03-21 | Toshiba Corp | Photocatalyst film and its production |
| JP2002346394A (en) * | 2001-05-25 | 2002-12-03 | Akiba:Kk | Highly efficient photocatalyst composition, paint and substrate using the same and method for coating object using the same |
| CN101204652A (en) * | 2007-12-19 | 2008-06-25 | 中国科学院上海硅酸盐研究所 | High efficiency semiconductor photocatalysis and preparation method thereof |
| CN102284284A (en) * | 2011-06-03 | 2011-12-21 | 南昌航空大学 | Method for preparing molecularly imprinted TiO2/WO3 composite photocatalyst with visible light response through direct method |
| CN103447095A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Molecular imprinting composite membrane for photocatalytic degradation of organic matter and preparation method thereof |
| CN104759263A (en) * | 2015-03-25 | 2015-07-08 | 江苏大学 | A preparing method of a multiwalled carbon nanotube doped salicylic acid blend imprinted membrane |
Non-Patent Citations (1)
| Title |
|---|
| ZHUDONG WU等: ""Controlled synthesis of Bi2S3/ZnS microspheres by an in situ ion-exchange process with enhanced visible light photocatalytic activity"", 《DALTON TRANSACTIONS》 * |
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| CN107597194A (en) * | 2017-09-28 | 2018-01-19 | 东北林业大学 | A kind of preparation method of new ZnO/ fungies fiber optic catalytic composite material |
| CN107983390A (en) * | 2017-12-08 | 2018-05-04 | 吉林师范大学 | A kind of surface imprinted carbonitride/composite titania material photocatalysis membrana and preparation method and purposes |
| CN109590026A (en) * | 2018-11-30 | 2019-04-09 | 河海大学 | A kind of composite photocatalyst material and its preparation method and application |
| CN109590026B (en) * | 2018-11-30 | 2021-09-24 | 河海大学 | Composite photocatalytic material and preparation method and application thereof |
| CN109589992A (en) * | 2018-12-03 | 2019-04-09 | 江苏大学 | A kind of MoS2/Bi2O3The preparation method and applications of p-n heterojunction photochemical catalyst |
| CN109967095A (en) * | 2019-04-17 | 2019-07-05 | 南昌航空大学 | A kind of holocrystalline bulk heterojunction catalysis material and its preparation method and application |
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| CN110947401A (en) * | 2019-12-30 | 2020-04-03 | 四川大学 | Bi2WO6/ZnS heterojunction photocatalyst and preparation method thereof |
| CN114700087A (en) * | 2022-04-28 | 2022-07-05 | 广西大学 | Efficient visible light photocatalytic material and preparation method and application thereof |
| CN114700087B (en) * | 2022-04-28 | 2023-09-29 | 广西大学 | Efficient visible light photocatalytic material and preparation method and application thereof |
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