CN108855046B - Zinc tungstate/stannous tungstate composite photocatalyst with core-shell structure and preparation and application thereof - Google Patents
Zinc tungstate/stannous tungstate composite photocatalyst with core-shell structure and preparation and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 45
- 239000011258 core-shell material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000011701 zinc Substances 0.000 title claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 6
- 229910052725 zinc Inorganic materials 0.000 title claims description 6
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title description 6
- 239000002073 nanorod Substances 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 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 9
- 229940043267 rhodamine b Drugs 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- 239000002957 persistent organic pollutant Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- XYZSNCGFOMVMIA-UHFFFAOYSA-N 1,3-dioxa-2$l^{2}-stanna-4$l^{6}-tungstacyclobutane 4,4-dioxide Chemical compound O=[W]1(=O)O[Sn]O1 XYZSNCGFOMVMIA-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 7
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 7
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 7
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000001119 stannous chloride Substances 0.000 claims description 5
- 235000011150 stannous chloride Nutrition 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- 230000015556 catabolic process Effects 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 description 18
- 239000000463 material Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000000843 powder Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- 239000005907 Indoxacarb Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- VBCVPMMZEGZULK-NRFANRHFSA-N indoxacarb Chemical compound C([C@@]1(OC2)C(=O)OC)C3=CC(Cl)=CC=C3C1=NN2C(=O)N(C(=O)OC)C1=CC=C(OC(F)(F)F)C=C1 VBCVPMMZEGZULK-NRFANRHFSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 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 1
- 229940012189 methyl orange Drugs 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- 231100000175 potential carcinogenicity Toxicity 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses ZnWO with a core-shell structure4@SnWO4The composite photocatalyst is one-dimensional ZnWO prepared by a hydrothermal method, and preparation and application thereof4The nano-rod is used as a nuclear layer, and SnWO is introduced by an in-situ synthesis method4As a shell, wherein SnWO4And ZnWO4The molar ratio of (A) is 0.05-0.3. The composite photocatalyst has high catalytic activity on rhodamine B under the action of visible light, the degradation rate of the rhodamine B reaches 100% when the illumination time lasts for 2 hours, and the preparation method is simple, easy to operate, low in raw material cost and suitable for industrial popularization and application.
Description
Technical Field
The invention belongs to the field of preparation of photocatalytic materials, and particularly relates to ZnWO with a core-shell structure4@SnWO4A composite photocatalyst and preparation and application thereof.
Background
Rhodamine B, methyl orange, methylene blue and the like are toxic organic dyes which are difficult to degrade and are widely applied to the industries of textile, dye, food, pharmacy and the like. The organic dye has potential toxicity, carcinogenicity and mutagenicity, can cause canceration after a human body contacts the organic dye for a long time, has high chroma, is an important source for causing water eutrophication, and can cause great harm to human health and ecological environment. Therefore, the development of an effective organic dye pollutant treatment technology is urgently needed. At present, the treatment technology of organic dye pollutants comprises a physical adsorption method, a biological method, a Fenton method, a photocatalytic oxidation method and the like, wherein the photocatalytic oxidation technology utilizes solar energy as a driving force to degrade organic pollutants, and the technology is clean and efficient and becomes a research hotspot of an organic pollutant treatment technology.
At present, TiO is a commonly used semiconductor photocatalytic material2、ZnO、ZnWO4And the like and complexes thereof. Among them, ZnWO4Materials are of great interest because of their unique electronic structure and good optical properties, as well as their strong catalytic properties. ZnWO is used in China4Method for successfully degrading organic pollutants under ultraviolet irradiationThe following reports (see "artificial lens journal" 2009, 38 vol. 1/65 p.).
Yongfa Zhu et al reported a ZnWO4And ZnWO doped with F4Photocatalytic material (Fluorination of ZnWO)4 Photocatalyst and Influence on the Degradation Mechanism for 4-Chlorophenol. Environ. Sci. technol., 2008, 42(22): 8516-8521; ZnWO4photocatalyst with high activity for degradation of organic pollutants J. alloy. Comp, 2007, 432(1-2): 269-276.), which exhibits good photocatalytic degradation activity for organic pollutants under the excitation of ultraviolet light, including degradation of RhB, formaldehyde and p-chlorophenol. However, it is only a single ZnWO4The material can only be excited under the condition of ultraviolet light, and the photocatalysis efficiency of the material is low.
Chinese patent CN 102935360A discloses ZnWO4The invention relates to a preparation method of a nanorod photocatalytic material, which adopts a microwave hydrothermal method to quickly synthesize ZnWO with photocatalytic property4And (3) nanorods, and the degradation performance of the nanorods on rhodamine B is investigated.
Chinese patent CN 108101147A discloses p-trifluoroanisidine in indoxacarb wastewater catalytic degradation by a novel catalytic material, which takes apatite as a carrier, nitric acid hexahydrate, zinc nitrate hexahydrate and sodium tungstate dihydrate as raw materials, and a nickel salt modified zinc tungstate photocatalytic material is prepared by hydrothermal reaction and is used for degrading the p-trifluoroanisidine in the indoxacarb wastewater.
Chinese patent CN 107224972A discloses a flower-ball-shaped ZnO/ZnWO4The synthesis method of the photocatalyst prepares ZnO/ZnWO through microwave radiation reaction of a microwave reactor4The composite photocatalyst is used for degrading organic pollutant malachite green and photolyzing water to produce hydrogen.
The above documents and patent reports show a single ZnWO4Or a compound thereof, and the performance of the compound for degrading organic pollutants by photocatalysis is examined. However, the photoresponsive region of the photocatalytic materials is only ultraviolet light, and the photocatalytic efficiency is low, which greatly restricts the printing of photocatalytic oxidation technologyThe practical application in the field of dyeing wastewater.
SnWO4The energy band structure is unique, and rich resources are utilized, so that the energy band structure is widely concerned. Wherein, SnWO4The band gap of the composite material is 1.7-1.8 eV, the visible light response range is large, and the composite material can completely compensate ZnWO4The photocatalysis material is not enough, and the photocatalysis material has matched energy band positions, is convenient for the separation and transfer of photon-generated carriers, is also tungstate, is easier to prepare and regulate the structure and the appearance of a compound thereof, and the composition of the two materials is favorable for widening the ZnWO4The light absorption range and the separation and transfer of photon-generated carriers, thereby further achieving the purpose of improving the photocatalytic activity. Through extensive literature and patent investigations, for ZnWO4And SnWO4The preparation of the compound and the research of applying the compound to photocatalytic degradation of organic pollutants are few.
Disclosure of Invention
The invention aims to provide ZnWO with a core-shell structure4@SnWO4Composite photocatalyst, preparation and application thereof, and preparation of one-dimensional ZnWO through simple hydrothermal reaction4The nano rod is prepared into ZnWO with a one-dimensional core-shell structure by an in-situ compounding method4@SnWO4Composite, ZnWO of one-dimensional core-shell structure constructed by the composite4@SnWO4The compound has visible light absorption capacity and shows excellent photocatalytic performance on degradation of an organic pollutant RhB.
In order to achieve the purpose, the invention adopts the following technical scheme:
ZnWO with core-shell structure4@SnWO4The composite photocatalyst is one-dimensional ZnWO prepared by a hydrothermal synthesis method4Nanorods followed by one-dimensional ZnWO4The nano-rod is used as a matrix, and SnWO is introduced by adopting an in-situ compounding method4As a shell structure, a ZnWO with a one-dimensional core-shell structure is constructed4@SnWO4A composite photocatalyst;
wherein SnWO4/ZnWO4The molar ratio of (A) is 0.05-0.3.
ZnWO of the core-shell structure4@SnWO4Composite lightThe preparation method of the catalyst comprises the following steps:
1) one-dimensional ZnWO4Preparation of nanorods
0.5-1.5g of zinc source and 1.0g of Na are added2WO4•2H2Adding O into the lining of a 50ml reaction kettle, adding 28ml deionized water, continuously stirring for 30 minutes, then adjusting the pH to 7 by using 0.5M NaOH, and continuously stirring for 1 hour; transferring the stirred solution into a 50ml high-pressure reaction kettle, and carrying out hydrothermal reaction at 160-180 ℃ for 24-48 hours; taking out after the reaction is finished, cooling to room temperature in the air, centrifuging, and drying at 80 ℃ to obtain ZnWO4The white powder of (4);
2) core-shell structure ZnWO4@SnWO4Preparation of composite photocatalyst
0.63g of ZnWO4And 80ml of deionized water were added to a 150ml Erlenmeyer flask, followed by addition of 0.1M HCl to adjust the pH to 5, and addition of 0.04-0.4g of a tin source and 0.5-4ml, 0.2M Na2WO4•2H2O to regulate SnWO4/ZnWO4The molar ratio of the ZnWO to the ZnWO is 0.05-0.3, the ZnWO with the core-shell structure is obtained by stirring and refluxing for 3-6 hours at the temperature of 120-140 ℃, centrifuging and drying at the temperature of 60 DEG C4@SnWO4A yellow powder of the composite photocatalyst.
The zinc source comprises any one or more of zinc nitrate, zinc chloride, zinc sulfate and zinc acetate. The tin source is at least one of stannous chloride, stannous nitrate and stannous sulfate.
The core-shell structure ZnWO4@SnWO4The composite photocatalyst can be applied to the visible light degradation of organic pollutants, particularly rhodamine B.
The invention has the following remarkable advantages:
(1) the invention aims at the problems of the existing organic pollutant treatment technology, in particular to ZnWO4The photocatalytic material has the problems of narrow light absorption range, low photocatalytic efficiency and the like, and provides the in-situ synthesized ZnWO with the core-shell structure4@SnWO4A composite photocatalyst is provided. The composite photocatalyst has a uniform core-shell structure, and has high activity on degradation of rhodamine B under the induction of visible light. And the degradation rate of the rhodamine B reaches 100 percent by continuously illuminating for 2 hours by adopting visible light with the wavelength of more than 420 nm.
(2) The catalyst of the invention has simple preparation method, easy operation and low raw material cost, and is suitable for industrialized popularization and application.
Drawings
FIG. 1 shows ZnWO with core-shell structure prepared in example 14@SnWO4And (3) a transmission electron microscope image of the composite photocatalyst.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
EXAMPLE 1 one-dimensional ZnWO4Preparation of nanorods
0.90g of Zn (NO)3)2•6H2O and 1.0g Na2WO4•2H2Adding O into the lining of a 50ml reaction kettle, adding 28ml deionized water, continuously stirring for 30 minutes, then adjusting the pH to 7 by using 0.5M NaOH, and continuously stirring for 1 hour; transferring the stirred solution into a 50ml high-pressure reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 48 hours; taking out after the reaction is finished, cooling to room temperature in the air, centrifuging, and drying at 80 ℃ to obtain ZnWO4The white powder of (1) is numbered.
Example 2
1) One-dimensional ZnWO4Preparation of nanorods
0.90g of Zn (NO)3)2•6H2O and 1.0g Na2WO4•2H2Adding O into the lining of a 50ml reaction kettle, adding 28ml deionized water, continuously stirring for 30 minutes, then adjusting the pH to 7 by using 0.5M NaOH, and continuously stirring for 1 hour; transferring the stirred solution into a 50ml high-pressure reaction kettle, and carrying out hydrothermal reaction at 180 ℃ for 48 hours; taking out after the reaction is finished, cooling to room temperature in the air, centrifuging, and drying at 80 ℃ to obtain ZnWO4The white powder of (4);
2) core-shell structure ZnWO4@SnWO4Preparation of composite photocatalyst
0.63g of ZnWO4And 80ml of deionized water were added to a 150ml Erlenmeyer flask, followed by addition of 0.1M HCl to adjust the pH to 5, and addition of 0.045g SnCl2•2H2O and 1ml of 0.2M Na2WO4•2H2O to regulate SnWO4/ZnWO4The molar ratio of (1: 10) is stirred and refluxed for 3 hours at the temperature of 120 ℃, and then the mixture is centrifuged and dried at the temperature of 60 ℃ to obtain ZnWO with a core-shell structure4@SnWO4A yellow powder of composite photocatalyst, numbered 2.
Example 3
1) One-dimensional ZnWO4Preparation of nanorods
0.90g of Zn (NO)3)2•6H2O and 1.0g Na2WO4•2H2Adding O into the lining of a 50ml reaction kettle, adding 28ml deionized water, continuously stirring for 30 minutes, then adjusting the pH to 7 by using 0.5M NaOH, and continuously stirring for 1 hour; transferring the stirred solution into a 50ml high-pressure reaction kettle, and carrying out hydrothermal reaction at 160 ℃ for 24 hours; taking out after the reaction is finished, cooling to room temperature in the air, centrifuging, and drying at 80 ℃ to obtain ZnWO4The white powder of (4);
2) core-shell structure ZnWO4@SnWO4Preparation of composite photocatalyst
0.63g of ZnWO4And 80ml of deionized water were added to a 150ml Erlenmeyer flask, followed by addition of 0.1M HCl to adjust the pH to 5, and addition of 0.09g SnCl2•2H2O and 2ml of 0.2M Na2WO4•2H2O to regulate SnWO4/ZnWO4The molar ratio of (1) is 2:10, stirring and refluxing are carried out for 6 hours at the temperature of 120 ℃, then centrifugation and drying are carried out at the temperature of 60 ℃ to obtain ZnWO with a core-shell structure4@SnWO4The composite photocatalyst is yellow powder, and is numbered 3.
Example 4
SnCl used in example 22•2H2Changing O into SnSO4The rest of the steps are the same as the example 2 to obtain ZnWO4@SnWO4The composite photocatalyst is numbered 4.
Example 5
Zn (NO) used in example 23)2•6H2Changing O into ZnCl2The rest of the steps are the same as the example 2 to obtain ZnWO4@SnWO4The composite photocatalyst is numbered 5.
Example 6
The hydrothermal reaction time of the example 2 is changed from 48 hours to 24 hours, and the rest steps are the same as the example 2, so as to obtain ZnWO4@SnWO4The composite photocatalyst is numbered 6.
Example 7
The temperature of stirring reflux in the example 2 is changed from 120 ℃ to 140 ℃, and the rest steps are the same as the example 2, thus obtaining ZnWO4@SnWO4The composite photocatalyst is numbered 7.
Example 8
The stirring reflux time of the example 2 is changed from 3 hours to 6 hours, and the rest steps are the same as the example 2 to obtain ZnWO4@SnWO4The composite photocatalyst is numbered as 8.
Example 9
The amount of stannous chloride added in example 2 was adjusted so that SnWO4/ZnWO4The molar ratio of the raw materials is changed from 1:10 to 1:20, and the rest steps are the same as the example 2 to obtain ZnWO4@SnWO4The composite photocatalyst is numbered 9.
Example 10
The amount of stannous chloride added in example 2 was adjusted so that SnWO4/ZnWO4The molar ratio of the raw materials is changed from 1:10 to 3:10, and the rest steps are the same as the example 2 to obtain ZnWO4@SnWO4The composite photocatalyst is numbered 10.
Example 11
The amount of stannous chloride added in example 2 was adjusted so that SnWO4/ZnWO4The molar ratio of the raw materials is changed from 1:10 to 4:10, and the rest steps are the same as the example 2 to obtain ZnWO4@SnWO4The composite photocatalyst is numbered 11.
Example 12
The stirring reflux time of the example 3 is changed from 6 hours to 3 hours, and the rest steps are the same as the example 3, so as to obtain ZnWO4@SnWO4Composite photocatalyst, weavingNumber 12.
Example 13
The temperature of stirring reflux in the example 3 is changed from 120 ℃ to 140 ℃, and the rest steps are the same as the example 3, thus obtaining ZnWO4@SnWO4The composite photocatalyst is numbered 13.
Visible light photocatalytic degradation of RhB
80mg of the composite photocatalyst prepared in the example was added to 80ml of 10ppm RhB solution, and stirring and dark adsorption were continued for 60 minutes to ensure the adsorption/desorption equilibrium of the catalyst. After the dark adsorption is finished, starting a xenon lamp for illumination for 2 hours, then taking the reaction liquid for centrifugation, taking the supernatant for testing on an ultraviolet-visible spectrophotometer, and the results are shown in table 1.
TABLE 1 different ZnWO4@SnWO4Degradation condition of composite photocatalyst on rhodamine B
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (7)
1. ZnWO with core-shell structure4@SnWO4The composite photocatalyst is characterized in that: one-dimensional ZnWO prepared by hydrothermal synthesis method4Nanorods followed by one-dimensional ZnWO4The nano-rod is used as a matrix, and SnWO is introduced by adopting an in-situ compounding method4As a shell structure, a ZnWO with a one-dimensional core-shell structure is constructed4@SnWO4A composite photocatalyst; wherein SnWO4/ZnWO4The molar ratio of (A) is 0.05-0.3;
the specific preparation method of the composite photocatalyst comprises the following steps:
1) one-dimensional ZnWO4Preparation of nanorods
0.5-1.5g of zinc source and 1.0g of Na are added2WO4•2H2O was added to 28ml of deionized water, stirred for 30 minutes and then adjusted with 0.5M NaOHAdjusting the pH value to 7, and continuously stirring for 1 hour; transferring the stirred solution into a high-pressure reaction kettle for hydrothermal reaction; taking out after the reaction is finished, cooling to room temperature, centrifuging and drying to obtain ZnWO4；
2) Core-shell structure ZnWO4@SnWO4Preparation of composite photocatalyst
0.63g of ZnWO4Adding into 80ml deionized water, adding 0.1M HCl to adjust pH to 5, adding 0.04-0.4g tin source and 0.5-4ml 0.2M Na2WO4•2H2O to regulate SnWO4/ZnWO4The molar ratio of (A) is 0.05-0.3, and the ZnWO with the core-shell structure is obtained after the centrifugation and the drying after the reflux reaction4@SnWO4A composite photocatalyst is provided.
2. ZnWO core-shell structure according to claim 14@SnWO4The composite photocatalyst is characterized in that: the zinc source in the step 1) comprises any one or more of zinc nitrate, zinc chloride, zinc sulfate and zinc acetate.
3. ZnWO core-shell structure according to claim 14@SnWO4The composite photocatalyst is characterized in that: the temperature of the hydrothermal reaction in the step 1) is 160-180 ℃, and the reaction time is 24-48 hours.
4. ZnWO core-shell structure according to claim 14@SnWO4The composite photocatalyst is characterized in that: in the step 2), the tin source is at least one of stannous chloride, stannous nitrate and stannous sulfate.
5. ZnWO core-shell structure according to claim 14@SnWO4The composite photocatalyst is characterized in that: the temperature of the reflux reaction in the step 2) is 120-140 ℃, and the time is 3-6 hours.
6. ZnWO of core-shell structure according to claim 14@SnWO4The composite photocatalyst is degraded in visible lightApplication in organic pollutants.
7. ZnWO core-shell structure according to claim 64@SnWO4The application of the composite photocatalyst is characterized in that: the organic pollutant is rhodamine B.
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