CN105664920A - Cs2W3O10 (cesium tungstate) powder, preparation method and application thereof - Google Patents
Cs2W3O10 (cesium tungstate) powder, preparation method and application thereof Download PDFInfo
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- CN105664920A CN105664920A CN201610063159.7A CN201610063159A CN105664920A CN 105664920 A CN105664920 A CN 105664920A CN 201610063159 A CN201610063159 A CN 201610063159A CN 105664920 A CN105664920 A CN 105664920A
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- wolframic acid
- cesium
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- 229910052792 caesium Inorganic materials 0.000 title claims abstract description 39
- 239000000843 powder Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title abstract 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title abstract 2
- 239000000126 substance Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000003836 solid-state method Methods 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 46
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 claims description 44
- 239000002253 acid Substances 0.000 claims description 40
- 239000011941 photocatalyst Substances 0.000 claims description 20
- 238000000227 grinding Methods 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 15
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 12
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 239000008139 complexing agent Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- KOPBYBDAPCDYFK-UHFFFAOYSA-N Cs2O Inorganic materials [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 9
- AKUNKIJLSDQFLS-UHFFFAOYSA-M dicesium;hydroxide Chemical compound [OH-].[Cs+].[Cs+] AKUNKIJLSDQFLS-UHFFFAOYSA-M 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- -1 tungsten ion Chemical class 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 5
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910003893 H2WO4 Inorganic materials 0.000 claims description 3
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 2
- 230000004298 light response Effects 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000012254 powdered material Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 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 abstract description 30
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 30
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- VPXSRGLTQINCRV-UHFFFAOYSA-N dicesium;dioxido(dioxo)tungsten Chemical compound [Cs+].[Cs+].[O-][W]([O-])(=O)=O VPXSRGLTQINCRV-UHFFFAOYSA-N 0.000 abstract 1
- 238000009826 distribution Methods 0.000 abstract 1
- 230000005855 radiation Effects 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 description 24
- 238000006731 degradation reaction Methods 0.000 description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 239000000975 dye Substances 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000012913 prioritisation Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910020030 Cs2WO4 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- 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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses Cs2W3O10 (cesium tungstate) powder, a preparation method and an application thereof and belongs to the technical field of inorganic photocatalytic materials. The chemical formula of the cesium tungstate powder is Cs2W3O10, and the Cs2W3O10 powder is prepared with a high-temperature solid state method or a chemical solution method. The Cs2W3O10 powder material is uniform in particle size distribution and good in chemical stability, can effectively degrade methylene blue under ultraviolet light radiation, can be applied to treatment of environmental pollution, can effectively degrade organic pollutants in water and is an ideal photocatalytic material. The preparation method of the Cs2W3O10 powder is simple to operate, pollution-free and low in energy consumption and cost and has the prospect of large-scale industrial production.
Description
Technical field
The present invention relates to a kind of inorganic photocatalyst material, its preparation method and application thereof, it is specifically related to a kind of photocatalyst Cs that can be used for degradable organic pollutant2W3O10And its preparation method, belong to inorganic field of photocatalytic material.
Background technology
In industrial production and daily life, people unavoidably have manufactured a large amount of pollutent, and wherein waste water from dyestuff problem as one of pollution source of water body is the most outstanding. Along with the progress of civilization of human society and the development of industrial production, surrounding enviroment and quality of life are also had higher requirement by people while standard of living significantly improves. All the more serious problem of environmental pollution seriously affects the existence of the mankind and the Sustainable development of society, and thus, the control of environmental pollution is very urgent. Since photocatalysis technology found from 1967, because the pollutent of the harmful Stability Analysis of Structures of human body and environment is become one of global environmental pollution main method administering field by this technology major part of effectively degrading.
Photocatalysis technology can convert solar energy into chemical energy and non-secondary pollution, receives much concern in Pollution abatement field as the eco-friendly purification techniques of one. It is that a kind of self does not change under the irradiation of light as the photocatalyst material of photocatalyst core, but can promote thus in waste water control, as the catalyzer of a kind of environmental protection, there is very important status by the material that chemical reaction carries out. Traditional photocatalyst material is with titanium dioxide TiO2It is main with zinc oxide ZnO, and it is widely used. In recent years, but the research of novel photocatalysis agent constantly receives the concern of investigators.
Chinese invention patent application CN104925867A reports a kind of nanometer wolframic acid caesium powder body and its preparation method and application. Wolframic acid caesium (Cs2WO4) as the novel heat insulation material found in recent years, obtain the great attention of the famous paint company such as Germany, the U.S., Japan, carried out research energetically. But wolframic acid caesium have not been reported in the application of photocatalysis field.
Summary of the invention
It is an object of the invention to provide that a kind of preparation method is simple, photocatalysis efficiency height, the wolframic acid caesium powder, preparation method and the application thereof that have a extensive future.
For reaching above object, the technical solution used in the present invention is: a kind of wolframic acid caesium powder, its chemical formula is Cs2W3O10。
Technical solution of the present invention comprises described wolframic acid caesium (Cs2W3O10) two kinds of preparation methods of powder, one adopts high temperature solid-state method, comprises the steps:
(1) by general formula Cs2W3O10The stoichiometric ratio of middle corresponding element weighs a kind of containing tungsten ion W respectively6+Compound with a kind of containing cesium ion Cs+Compound, grind, mix;
(2) mixture that step (1) obtains being carried out precalcining process in air atmosphere, precalcining temperature is 400～800 DEG C, and calcination time is 4～15 hours, after naturally cooling to room temperature, grinds, mixes;
(3) mixture that step (2) obtains being carried out calcination processing in air atmosphere, calcining temperature is 800～1200 DEG C, and calcination time is 4～15 hours, and after naturally cooling to room temperature, grinding evenly, obtains a kind of wolframic acid caesium Cs2W3O10Powder body material.
A prioritization scheme of step (2) is: calcining temperature is 450～750 DEG C, and calcination time is 5～14 hours; A prioritization scheme of step (3) is: calcining temperature is 850～1150 DEG C, and calcination time is 5～14 hours.
Another kind adopts chemical solution method, comprises the steps:
(1) by chemical formula Cs2W3O10In the stoichiometric ratio of each element, first take a kind of containing tungsten ion W6+Compound be dissolved in appropriate dilute nitric acid solution, heating, under agitation condition to dissolving completely, then add appropriate complexing agent and stir after evenly, obtain solution A; Take a kind of containing cesium ion Cs again+Compound be dissolved in appropriate dilute nitric acid solution, heating, under agitation condition to dissolving completely, then add appropriate complexing agent and stir after evenly, obtain solution B; By solution A, solution B mixing, stir process 1～5 hour when temperature is 70～100 DEG C, obtains wolframic acid caesium Cs2W3O10Precursor solution;
(2) by wolframic acid caesium Cs2W3O10Precursor solution when temperature is 50～100 DEG C ageing and dry;
(3) after naturally cooling, taking out presoma, carry out calcination processing in air atmosphere, calcining temperature is 750～1150 DEG C, and calcination time is 5～13 hours, and after naturally cooling, grinding evenly, namely obtains a kind of wolframic acid caesium Cs2W3O10Powdered material.
A prioritization scheme of step (3) is: calcining temperature is 800～1100 DEG C, and calcination time is 6～12 hours.
In technical solution of the present invention, described contains tungsten ion W6+Compound be Tungsten oxide 99.999 WO3, wolframic acid H2WO4, ammonium tungstate (NH4)10W12O41, ammonium metawolframate 3 (NH4)2O·7WO3·6H2O and ammonium paratungstate (NH4)2WO4In one; Described contains cesium ion Cs+Compound be Cs2O Cs2O, cesium nitrate CsNO3, cesium carbonate Cs2CO3, cesium hydroxide CsOH and cesium chloride CsCl one; Described complexing agent is citric acid or oxalic acid.
Technical solution of the present invention also comprises described wolframic acid caesium (Cs2W3O10) application of powder, as the photocatalyst of ultraviolet light response.
Compared with prior art, the advantage of technical solution of the present invention is:
1, the Cs of preparation2W3O10The photocatalytic activity of photocatalyst is better, and the degradation rate of 240 minutes photocatalytic degradation methylene blues can reach 91.47%, can effectively realize photocatalytic degradation methylene blue.
2, Cs is prepared2W3O10The raw material sources of photocatalyst is abundant and cheap, and preparation method is simple and less energy-consumption, low cost. Meanwhile, obtained sample thing is compared pure, and particle is tiny and is evenly distributed.
3, the present invention discharges without waste gas and waste liquid, Cs2W3O10Photocatalyst is the inorganic photocatalyst material of a kind of green safety.
Accompanying drawing explanation
Fig. 1 is the Cs obtained by the embodiment of the present invention 12W3O10The X-ray powder diffraction pattern of sample;
Fig. 2 is the Cs obtained by the embodiment of the present invention 12W3O10The diffuse-reflectance collection of illustrative plates of sample;
Fig. 3 is the Cs obtained by the embodiment of the present invention 12W3O10The SEM figure of sample;
Fig. 4 is the Cs obtained by the embodiment of the present invention 12W3O10Sample when illumination to the degradation curve of organic dye methylene blue;
Fig. 5 is the Cs obtained by the embodiment of the present invention 12W3O10The kinetic curve figure of sample degradation methylene blue;
Fig. 6 is the Cs obtained by the embodiment of the present invention 52W3O10The X-ray powder diffraction pattern of sample;
Fig. 7 is the Cs obtained by the embodiment of the present invention 52W3O10The diffuse-reflectance collection of illustrative plates of sample;
Fig. 8 is the Cs obtained by the embodiment of the present invention 52W3O10The SEM figure of sample;
Fig. 9 is the Cs obtained by the embodiment of the present invention 52W3O10The TEM figure of sample;
Figure 10 is the Cs obtained by the embodiment of the present invention 52W3O10Sample when illumination to the degradation curve of organic dye methylene blue;
Figure 11 is the Cs obtained by the embodiment of the present invention 52W3O10The kinetic curve figure of sample degradation methylene blue.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is further described. For the concrete scheme of each embodiment, some explanation following of special do:
1, in order to obtain the composite oxides used in the present invention, can first using solid-phase synthesis to prepare powder, the stoichiometric ratio namely raw material formed according to target mixes, then synthesizes in air atmosphere at ambient pressure.
2, in order to effectively utilize light, the size of the photocatalyst in the present invention is preferably in micron level, or even nanoparticle, and specific surface area is bigger. The oxide powder prepared with solid-phase synthesis, its particle is relatively big and surface-area is less, by adopting sol-gel method to prepare photocatalyst, particle dia is diminished.
3, in the present invention, photocatalytic degradation methylene blue activity rating adopts self-control photocatalytic reaction device, illuminator is 500 watts of cylindrical shape xenon lamps, the cylindrical light catalyzed reaction instrument that reactive tank use pyrex is made, illuminator is inserted in reactive tank, and lead to into water of condensation cooling, during reaction, temperature is room temperature. Catalyst levels 100 milligrams, liquor capacity 250 milliliters, the concentration of methylene blue is 10 mg/litre. Catalyzer is placed in reaction solution, and catalysis time is set as 240 minutes, starts illumination after opening water of condensation, a sample is got at set intervals after illumination, centrifugal, get its supernatant liquor, measure the absorbancy of methylene blue solution with ultraviolet-visible spectrophotometer in wavelength 664～666 nanometers. According to Law of Lambert-Beer, the absorbancy of solution is directly proportional to concentration, therefore concentration can be replaced to calculate clearance by absorbancy, as the clearance of methylene blue solution. Calculation formula: degradation rate=(1-C/C0) × 100%=(1-A/A0) × 100%, wherein C0, C be respectively the concentration before and after photocatalytic degradation, A0, A respectively be degraded before and after absorbance.
Embodiment 1:
According to chemical formula Cs2W3O10, take Tungsten oxide 99.999 WO respectively3: 6.956 grams, Cs2O Cs2O:2.818 gram, add in agate mortar appropriate acetone mixed grinding evenly after, the air atmosphere of 450 DEG C carries out precalcining process, the pre-calcination time is 5 hours, after naturally cooling to room temperature with stove, takes out sample; By the sample of precalcining that obtains again in mortar with the abundant mixed grinding of same procedure evenly after, the air atmosphere of 850 DEG C carries out calcination processing, calcination time is 5 hours, and after being cooled to room temperature, grinding obtains photocatalyst wolframic acid caesium Cs2W3O10。
FIGS 1, it is the X-ray powder diffraction pattern by sample prepared by the present embodiment technical scheme, and XRD test result shows, prepared wolframic acid caesium Cs2W3O10Degree of crystallinity is better, without assorted phase.
FIGS 2, it is the diffuse reflection spectrum by sample prepared by the present embodiment technical scheme, and as can be seen from the figure, this sample has stronger absorption in UV light region.
FIGS 3, it is the SEM(scanning electronic microscope by sample prepared by the present embodiment technical scheme) collection of illustrative plates, as can be seen from the figure, the sample particle of gained is evenly distributed, and median size is 0.50 micron.
FIGS 4, it is to the degradation curve of organic dye methylene blue by sample prepared by the present embodiment technical scheme. As can be seen from the figure, the degradation rate of this sample photocatalytic degradation methylene blue reaches 87.46% in 240 minutes, and the wolframic acid caesium Cs preparing is described2W3O10Material has good photocatalytic activity.
FIGS 5, it is the kinetic curve figure by sample degradation methylene blue prepared by the present embodiment technical scheme, draws through the Fitting Calculation, and the apparent kinetics rate constant of this sample photocatalytic degradation methylene blue is 0.00242 minute-1。
Embodiment 2:
According to chemical formula Cs2W3O10, take ammonium tungstate (NH respectively4)10W12O41: 7.606 grams, cesium hydroxide CsOH:2.998 gram, add in agate mortar appropriate acetone mixed grinding evenly after, the air atmosphere of 550 DEG C carries out precalcining, calcination time is 8 hours, after naturally cooling to room temperature with stove, takes out sample; The sample of precalcining is again even with the abundant mixed grinding of identical method, the air atmosphere of 950 DEG C carries out calcination processing, calcination time is 8 hours, and after being cooled to room temperature, grinding obtains photocatalyst wolframic acid caesium Cs2W3O10。
Its main structure and morphology, diffuse reflection spectrum, SEM collection of illustrative plates, the degradation rate of methylene blue is similar to embodiment 1 with the kinetic curve of degradation of methylene blue.
Embodiment 3:
According to chemical formula Cs2W3O10, weigh ammonium paratungstate (NH respectively4)2WO4: 4.259 grams, cesium chloride CsCl:1.684 gram, add in agate mortar appropriate acetone mixed grinding evenly after, the air atmosphere of 650 DEG C carries out precalcining process, calcination time is 11 hours, after naturally cooling to room temperature with stove, takes out sample; The sample of precalcining is again even with the abundant mixed grinding of identical method, the air atmosphere of 1050 DEG C carries out calcination processing, calcination time is 11 hours, and after being cooled to room temperature, grinding obtains photocatalyst wolframic acid caesium Cs2W3O10。
Its main structure and morphology, diffuse reflection spectrum, SEM collection of illustrative plates, the degradation rate of methylene blue is similar to embodiment 1 with the kinetic curve of degradation of methylene blue.
Embodiment 4:
According to chemical formula Cs2W3O10, take ammonium metawolframate 3 (NH respectively4)2O·7WO3·6H2O:2.696 gram, cesium carbonate Cs2CO3: 1.086 grams, add in agate mortar appropriate acetone mixed grinding evenly after, 750 DEG C of air atmospheres carry out precalcining process, calcination time is 14 hours, after naturally cooling to room temperature with stove, takes out sample; The sample of precalcining is again even with the abundant mixed grinding of identical method, the air atmosphere of 1150 DEG C carries out calcination processing, calcination time is 14 hours, and after being cooled to room temperature, grinding obtains urging photochemical dose of wolframic acid caesium Cs2W3O10。
Its main structure and morphology, diffuse reflection spectrum, SEM collection of illustrative plates, the degradation rate of methylene blue is similar to embodiment 1 with the kinetic curve of degradation of methylene blue.
Embodiment 5:
According to chemical formula Cs2W3O10, take Tungsten oxide 99.999 WO respectively3: 1.391 grams, cesium nitrate CsNO3: 0.975 gram, add respectively in dilute nitric acid solution, stir until dissolve completely, then add appropriate citric acid and make complexing agent, obtain A, B solution after magnetic agitation for some time respectively, by A, B solution mixing, continue to stir for some time. The mixing solutions obtained is placed in 80 DEG C of baking ovens dry 12 hours, naturally cools to room temperature, take out presoma. Carrying out calcination processing in the air atmosphere of 800 DEG C, calcination time is 6 hours, and after being cooled to room temperature, grinding obtains photocatalyst wolframic acid caesium Cs2W3O10Powder.
FIGS 6, it is the X-ray powder diffraction pattern by sample prepared by the present embodiment technical scheme, and XRD test result shows, prepared wolframic acid caesium Cs2W3O10Also being monophase materials, degree of crystallinity is very good.
FIGS 7, it is the diffuse reflection spectrum by sample prepared by the present embodiment technical scheme, and as can be seen from the figure, this sample has very strong absorption in UV light region.
FIGS 8, it is the SEM(scanning electronic microscope by sample prepared by the present embodiment technical scheme) collection of illustrative plates, as can be seen from the figure, gained sample particle is uniformly dispersed.
FIGS 9, it is by the TEM(transmission electron microscopy figure of sample prepared by the present embodiment technical scheme) collection of illustrative plates, as can be seen from the figure, gained sample particle is uniformly dispersed, and granularity is less, and its median size is 0.08 micron.
FIGS 10, it is to the degradation curve of organic dye methylene blue by sample prepared by the present embodiment technical scheme. As can be seen from the figure, the degradation rate of this sample photocatalytic degradation methylene blue can reach 91.47% in 240 minutes, and the wolframic acid caesium Cs preparing is described2W3O10Material has higher photocatalytic activity.
FIGS 11, it is the kinetic curve figure by sample degradation methylene blue prepared by the present embodiment technical scheme, draws through the Fitting Calculation, and the apparent kinetics rate constant of this sample photocatalytic degradation methylene blue is 0.01146 minute-1。
Embodiment 6:
According to chemical formula Cs2W3O10, take ammonium tungstate (NH respectively4)10W12O41: 1.268 grams, Cs2O Cs2O:0.470 gram, add respectively in dilute nitric acid solution, stir until dissolve completely, then add appropriate citric acid and make complexing agent, obtain A, B solution after magnetic agitation for some time respectively, by A, B solution mixing, continue to stir for some time. The mixing solutions obtained being placed in 80 DEG C of baking ovens dry 12 hours, after naturally cooling to room temperature, take out presoma, carry out calcination processing in the air atmosphere of 900 DEG C, calcination time is 8 hours, and after being cooled to room temperature, grinding obtains photocatalyst wolframic acid caesium Cs2W3O10Powder.
Its main structure and morphology, diffuse reflection spectrum, SEM collection of illustrative plates, TEM collection of illustrative plates, the degradation rate of methylene blue is similar to embodiment 5 with the kinetic curve of degradation of methylene blue.
Embodiment 7:
According to chemical formula Cs2W3O10, take ammonium paratungstate (NH respectively4)2WO4: 1.065 grams, cesium nitrate CsNO3: 0.487 gram, add respectively in dilute nitric acid solution, stir until dissolve completely, then add appropriate citric acid and make complexing agent, obtain A, B solution after magnetic agitation for some time respectively, by A, B solution mixing, continue to stir for some time. The mixing solutions obtained being placed in 80 DEG C of baking ovens dry 12 hours, after naturally cooling to room temperature, take out presoma, carry out calcination processing in the air atmosphere of 1000 DEG C, calcination time is 10 hours, and after being cooled to room temperature, grinding obtains photocatalyst wolframic acid caesium Cs2W3O10Powder.
Its main structure and morphology, diffuse reflection spectrum, SEM collection of illustrative plates, TEM collection of illustrative plates, the degradation rate of methylene blue is similar to embodiment 5 with the kinetic curve of degradation of methylene blue.
Embodiment 8:
According to chemical formula Cs2W3O10, take wolframic acid H respectively2WO4: 1.500 grams, cesium hydroxide CsOH:0.600 gram, adds in dilute nitric acid solution respectively, stir until dissolve completely, then add appropriate citric acid and make complexing agent, after magnetic agitation for some time, obtain A, B solution respectively, by A, B solution mixing, continue to stir for some time.The mixing solutions obtained being placed in 80 DEG C of baking ovens dry 12 hours, after naturally cooling to room temperature, take out presoma, carry out calcination processing in the air atmosphere of 1100 DEG C, calcination time is 12 hours, grinds and namely obtain photocatalyst wolframic acid caesium Cs after being cooled to room temperature2W3O10Powder.
Its main structure and morphology, diffuse reflection spectrum, SEM collection of illustrative plates, TEM collection of illustrative plates, the degradation rate of methylene blue is similar to embodiment 5 with the kinetic curve of degradation of methylene blue.
Claims (8)
1. a wolframic acid caesium powder, it is characterised in that: its chemical formula is Cs2W3O10。
2. the preparation method of a wolframic acid caesium powder as claimed in claim 1, it is characterised in that adopt high temperature solid-state method, comprise the steps:
(1) by general formula Cs2W3O10The stoichiometric ratio of middle corresponding element weighs a kind of containing tungsten ion W respectively6+Compound with a kind of containing cesium ion Cs+Compound, grind, mix;
(2) mixture that step (1) obtains being carried out precalcining process in air atmosphere, precalcining temperature is 400～800 DEG C, and calcination time is 4～15 hours, after naturally cooling to room temperature, grinds, mixes;
(3) mixture that step (2) obtains being carried out calcination processing in air atmosphere, calcining temperature is 800～1200 DEG C, and calcination time is 4～15 hours, and after naturally cooling to room temperature, grinding evenly, obtains a kind of wolframic acid caesium Cs2W3O10Powder body material.
3. the preparation method of a kind of wolframic acid caesium powder according to claim 3, it is characterised in that: described contains tungsten ion W6+Compound be Tungsten oxide 99.999 WO3, wolframic acid H2WO4, ammonium tungstate (NH4)10W12O41, ammonium metawolframate 3 (NH4)2O·7WO3·6H2O and ammonium paratungstate (NH4)2WO4In one; Described contains cesium ion Cs+Compound oxidation caesium Cs2O, cesium nitrate CsNO3, cesium carbonate Cs2CO3, cesium hydroxide CsOH and cesium chloride CsCl one.
4. the preparation method of a kind of wolframic acid caesium powder according to claim 3, it is characterised in that: the calcining temperature described in step (2) is 450～750 DEG C, and calcination time is 5～14 hours; Calcining temperature described in step (3) is 850～1150 DEG C, and calcination time is 5～14 hours.
5. the preparation method of a wolframic acid caesium powder as claimed in claim 1, it is characterised in that adopt chemical solution method, comprise the steps:
(1) by chemical formula Cs2W3O10In the stoichiometric ratio of each element, first take a kind of containing tungsten ion W6+Compound be dissolved in appropriate dilute nitric acid solution, heating, under agitation condition to dissolving completely, then add appropriate complexing agent and stir after evenly, obtain solution A; Take a kind of containing cesium ion Cs again+Compound be dissolved in appropriate dilute nitric acid solution, heating, under agitation condition to dissolving completely, then add appropriate complexing agent and stir after evenly, obtain solution B; By solution A, solution B mixing, stir process 1～5 hour when temperature is 70～100 DEG C, obtains wolframic acid caesium Cs2W3O10Precursor solution;
(2) by wolframic acid caesium Cs2W3O10Precursor solution when temperature is 50～100 DEG C ageing and dry;
(3) after naturally cooling, taking out presoma, carry out calcination processing in air atmosphere, calcining temperature is 750～1150 DEG C, and calcination time is 5～13 hours, and after naturally cooling, grinding evenly, namely obtains a kind of wolframic acid caesium Cs2W3O10Powdered material.
6. the preparation method of a kind of wolframic acid caesium powder according to claim 5, it is characterised in that: described contains tungsten ion W6+Compound be Tungsten oxide 99.999 WO3, wolframic acid H2WO4, ammonium tungstate (NH4)10W12O41, ammonium metawolframate 3 (NH4)2O·7WO3·6H2O and ammonium paratungstate (NH4)2WO4In one;Described contains cesium ion Cs+Compound be Cs2O Cs2O, cesium nitrate CsNO3, cesium carbonate Cs2CO3, cesium hydroxide CsOH and cesium chloride CsCl one; Described complexing agent is citric acid or oxalic acid.
7. the preparation method of a kind of wolframic acid caesium powder according to claim 5, it is characterised in that: the calcining temperature described in step (3) is 800～1100 DEG C, and calcination time is 6～12 hours.
8. the application of wolframic acid caesium powder as claimed in claim 1, it is characterised in that: as the photocatalyst of ultraviolet light response.
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