CN105771963A - Wool ball shaped tungsten trioxide (WO3) photocatalyst and green synthetic method thereof - Google Patents
Wool ball shaped tungsten trioxide (WO3) photocatalyst and green synthetic method thereof Download PDFInfo
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- CN105771963A CN105771963A CN201610202708.4A CN201610202708A CN105771963A CN 105771963 A CN105771963 A CN 105771963A CN 201610202708 A CN201610202708 A CN 201610202708A CN 105771963 A CN105771963 A CN 105771963A
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- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 210000002268 wool Anatomy 0.000 title claims abstract description 24
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 13
- 238000010189 synthetic method Methods 0.000 title claims abstract 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000011780 sodium chloride Substances 0.000 claims abstract description 13
- 239000002135 nanosheet Substances 0.000 claims abstract description 5
- 238000009940 knitting Methods 0.000 claims description 20
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001308 synthesis method Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 230000001788 irregular Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229960004756 ethanol Drugs 0.000 description 4
- 239000000975 dye Substances 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000002060 nanoflake Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000002063 nanoring Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0207—Water
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a wool ball shaped tungsten trioxide (WO3) photocatalyst and a green synthetic method thereof. The catalyst is of a wool ball shape integrally, and in the catalyst, a number of nanosheets are stacked layer by layer and then are folded and assembled; sodium chloride and absolute ethyl alcohol, which are non-toxic, cheap and easily-available, are used as green additives, and the catalyst is prepared by a solvothermal method. Results show that the nanosheets can be directionally assembled into a wool ball shaped structure due to the addition of an appropriate amount of sodium chloride and a little amount of absolute ethyl alcohol, and more active sites are provided; therefore, wastewater degradation and high-efficiency oxygen production can be effectively realized. The successful development of the preparation method of the catalyst has certain theoretical and practical meanings on environment protection, reduction of WO3 catalyst synthesis cost, and solution of energy crisis via visible light catalytic degradation of wastewater and photocatalytic water splitting.
Description
Technical field
The present invention relates to photocatalysis field, more particularly, it relates to a kind of knitting wool bulk tungsten trioxide photocatalyst and green synthesis method thereof, this catalyst can be used to carry out the photocatalysis field researchs such as light degradation Organic substance, photochemical catalyzing and application.
Background technology
Photocatalysis, semiconducting external layer electronics is subject to extraneous photon energy radiation and is excited, and transits to conduction band from valence band, produces hole, and hole has stronger catalytic oxidation ability on conduction band.
Tungstic anhydride. has photocatalysis degradation organic contaminant activity height, environmental pollution is little, toxicity is low, stability high.According to WO3Band structure, its energy gap is narrower, about 2.7eV, it is possible to responding to visible light effectively, it is possible to effectively absorb visible ray.Although WO3Photo-catalysis capability cause the great interest of people, and it is successfully applied to multiple photochemical catalyzing reaction system, but building-up process is selected mostly the noble metal loading of some costlinesses reduce gap, forbidden band, adding organic formwork agent and obtain desirable catalyst pattern, addition Fluohydric acid. class corrosive liquids exposes the methods such as certain particular crystal plane and prepares highly active photocatalyst.Therefore, a kind of WO is sought3The green synthesis method of catalyst, makes this catalyst not only have high catalytic activity, and synthesizes with low cost, low in the pollution of the environment, easy and simple to handle, one of study hotspot becoming photocatalysis field.
Come at most recent two decades, about in the research that Tungstic anhydride. is constantly incremented by, different structure, pattern nano tungsten trioxide be successfully synthesized, as monocrystalline, cube, hexagonal structure；The medicine ball of zero dimension, hollow ball, nuclear shell ball, one-dimensional nano line, nanotube, nano belt, nano-rings, three-dimensional manometer cube, octahedron, wedge structure etc. all had been reported that.It is known that two-dimensional nano sheet is least easily-synthesized in these structures.Because flake structure means that nanocrystal grows only along certain specific direction, slightly impurity mixes, and namely can grow into block, octahedron etc. and expose the structure that crystal face is numerous.But, if in crystal growing process, if only nano flake occurs, crystal accumulation will certainly be caused to reunite serious, pore passage structure is less, causes avtive spot substantially to reduce.Spherical or flower-shaped, bulk structure, because of the specific surface area that it is bigger, is more beneficial for strengthening the crystal absorbability to reactant.
Therefore, the Tungstic anhydride. of the knitting wool bulk (possessing many Active site structure) that preparation is assembled by nano flake, take into account in building-up process green synthesis methods such as using additive nontoxic, cheap and easy to get simultaneously, be then particularly important.
Summary of the invention
Technical problem: in order to improve in catalyst synthesis to add noxious substance for cost to improve the present situation of visible light catalytic efficiency, the present invention proposes a kind of knitting wool bulk tungsten trioxide photocatalyst and green synthesis method thereof.This knitting wool bulk catalyst, for hexagonal structure WO3·1/3H2O, inside is a large amount of irregular tungstic oxide nano-sheets (these nanometer sheet are first piled up refolding layer by layer and assembled formation knitting wool bulk structure)；Synthesize with sodium chloride nontoxic, cheap and easy to get, dehydrated alcohol for green additive qualitative, quantitative.Because catalyst surface is coarse, have substantial amounts of loose duct, showing good catalysis activity in visible region, quantum efficiency is significantly improved.
Technical scheme: the knitting wool bulk tungsten trioxide photocatalyst of the present invention, with the mixed liquor of dehydrated alcohol and water be solvent, sodium chloride for fixed brilliant agent, its concrete preparation method is as follows:
Under room temperature, being added drop-wise in sodium tungstate solution by hydrochloric acid solution, first produce white precipitate postprecipitation and disappear, then regulate pH value of solution=0.5～1, be subsequently added alcohol solvent, wherein dehydrated alcohol volume fraction in reaction solution is 2～50%, it is preferable that 5%；Being subsequently added into fixed brilliant agent sodium chloride, wherein sodium tungstate is 4:1～1:8 with the mol ratio of sodium chloride, it is preferable that 1:1；After stirring, move into hydrothermal reaction kettle, continuously stirred lower 100～180 DEG C of thermostatic crystallization 3～24h, naturally cool to room temperature；Through ultrasonic vibration, centrifuge washing, lyophilization, obtain knitting wool bulk tungsten trioxide photocatalyst.
Just under the effect that anhydrous ethanol solvent, sodium chloride are fixed brilliant agent, Tungstic anhydride. precursor solution thermostatic crystallization in the reactor with agitating function, the nanoparticle obtained uniformly assembles, it does not have substantially cohesion and be piled into nano powder.Under follow-up lyophilization, the effect of caving in of nano-particle internal gutter structure falls below minimum, and the nanoparticle activated position obtained is more.This catalyst can be used for photocatalytic degradation industrial wastewater, waste gas dyestuff and the reaction of photodissociation Aquatic product oxygen.
Beneficial effect: first, sodium chloride, ethanol itself are common inorganic salt, basic organic solvent, cheap and easy to get, nontoxic.Secondly, after sodium chloride introduces, oriented adsorption is on tungstic trioxide nano-slice；And the hydrophilic of hydroxyl in dehydrated alcohol so that closely fold between the axial nanometer sheet in this crystal zone.The anisotropy of nanocrystal, causes that nanometer sheet is assembled into knitting wool bulk.Additionally, owing to bulk nanometer sheet surface is rougher, irregular duct is also more, contribute to providing more active sites, and light excites the electronic energy of generation to transmit along nanometer sheet rapidly, while being effectively improved the catalyst absorbability to visible ray, promotion photo-excited electron separates with hole, thus improving quantum efficiency.
Accompanying drawing explanation
Fig. 1, for knitting wool bulk nanometer WO in case study on implementation 13·1/3H2The XRD figure of O photocatalyst.
Fig. 2, for knitting wool bulk nanometer WO in case study on implementation 13·1/3H2The scanning electron microscope (SEM) photograph of O.
Fig. 3, for knitting wool bulk nanometer WO in case study on implementation 13·1/3H2The UV-Vis diffuse-reflectance figure of O.
Fig. 4, under different visible light light application time in case study on implementation 1, the UV-vis absorption of rhodamine B solution is schemed.
Detailed description of the invention
Embodiment 1 knitting wool bulk Tungstic anhydride. visible light photocatalytic degradation organic dyestuff
(1) catalyst of dehydrated alcohol volume fraction about 5% is prepared
Weigh 6.6032g sodium tungstate (Na2WO4·2H2O), it is dissolved under room temperature in 100mL deionized water, is stirred vigorously down and dropwise drips the dense HCl of 4mL37.0%, obtain precursor solution.Measure 8mL dehydrated alcohol, 44mL deionized water simultaneously, pour into after mix homogeneously in precursor solution, pH=0.5～1.Adding 1.1713g sodium chloride (NaCl), stirring 0.5h, to pistac, moves in hydrothermal reaction kettle, and continuously stirred lower 120 DEG C of constant temperature maintain 12h, naturally cool to room temperature；Through each centrifuge washing of the ultrasonic 10min of room temperature, water and ethanol three times, lyophilization, grind to obtain visible light catalyst.
(2) photocatalytically degradating organic dye test
The rhodamine B solution 400mL of preparation 20mg/L, adds 0.4g catalyst, after the ultrasonic 0.5h of lucifuge, with 500W high pressure xenon lamp (the following wavelength of elimination 400nm) simulated solar irradiation, carries out photocatalytic degradation test in 500mL photo catalysis reactor.
Sample every 0.5h, high speed centrifugation, take the supernatant and survey its absorbance at 556nm place, and calculate degradation rate.It is shown that major part rhodamine B solution is degraded after 4h, degradation rate reaches 92%, hence it is evident that higher than commercial WO3。
Embodiment 2 knitting wool bulk Tungstic anhydride. visible light photocatalytic degradation industry phenolic waste water
(1) catalyst of dehydrated alcohol volume fraction about 2.5% is prepared
Weigh 6.5934gNa2WO4·2H2O, is dissolved under room temperature in 100mL deionized water, is stirred vigorously the lower dropping dense HCl of 4mL37.0%, obtains precursor solution.Measure 4mL dehydrated alcohol, 50mL deionized water simultaneously, pour into after mix homogeneously in precursor solution, pH=0.5～1.Adding 0.5862gNaCl, stirring 0.5h to pistac, move in hydrothermal reaction kettle, continuously stirred lower 150 DEG C of constant temperature maintain 6h, naturally cool to room temperature；Through each centrifuge washing of the ultrasonic 10min of room temperature, water and ethanol three times, lyophilization, grind to obtain visible light catalyst.
(2) Photocatalytic Degradation of Phenol test
The phenol solution 400mL of preparation 0.02g/L, adds 0.4g catalyst, after the ultrasonic 0.5h of lucifuge, with 500W high pressure xenon lamp (the following wavelength of elimination 400nm) simulated solar irradiation, carries out photocatalytic degradation reaction in 500mL photo catalysis reactor.Measure the concentration of phenol solution by bromate method every 0.5h, and calculate its degradation rate.It is shown that phenol degrading rate reaches 80% after 4h.
Embodiment 3 knitting wool bulk Tungstic anhydride. visible light catalytic decomposes Aquatic product oxygen
(1) catalyst of dehydrated alcohol volume fraction about 50% is prepared:
Weigh 6.5956gNa2WO4·2H2O, is dissolved under room temperature in 60mL deionized water, is stirred vigorously down and dropwise drips the dense HCl of 4mL37.0%, obtains precursor solution.Measure 80mL dehydrated alcohol, 16mL deionized water simultaneously, pour into after mix homogeneously in precursor solution, pH=0.5～1.Adding 0.2930gNaCl, stirring 0.5h to pistac, move in hydrothermal reaction kettle, continuously stirred lower 100 DEG C of constant temperature maintain 24h, naturally cool to room temperature；Through each centrifuge washing of the ultrasonic 10min of room temperature, water and ethanol three times, lyophilization, grind to obtain visible light catalyst.
(2) photochemical catalyzing oxygen test
500mL photo catalysis reactor adds 0.4g visible light catalyst, 400mL deionized water, adds a certain amount of KIO3(0.4mol/L) as electron acceptor, the ultrasonic 0.5h of lucifuge, with 500W high pressure xenon lamp (the following wavelength of elimination 400nm) simulated solar irradiation, carry out light-catalyzed reaction, the collection and confinement of gases that reaction is produced, and use gas chromatographic detection.The productivity of oxygen is 0.25mmol/h.
Claims (3)
1. a knitting wool bulk tungsten trioxide photocatalyst, it is characterised in that this catalyst is hexagonal structure WO3·1/3H2O, presents knitting wool bulk, and inside is made up of a large amount of irregular tungstic oxide nano-sheets；These nanometer sheet are first piled up layer by layer, and refolding assembles and forms knitting wool bulk structure.
2. the green synthesis method of a knitting wool bulk tungsten trioxide photocatalyst as claimed in claim 1, it is characterised in that concrete building-up process is as follows:
Under room temperature, hydrochloric acid solution is added drop-wise in sodium tungstate solution, and regulates pH value of solution to 0.5～1.0, be subsequently added dehydrated alcohol and solid sodium chloride；After stirring, move in hydrothermal reaction kettle, continuously stirred lower 100～180 DEG C of crystallization 3～24h, naturally cool to room temperature, through ultrasonic vibration, centrifuge washing, lyophilization, obtain knitting wool bulk tungsten trioxide photocatalyst.
3. a kind of photocatalyst synthetic method according to claim 2, it is characterised in that described dehydrated alcohol volume fraction in reaction solution is 2～50%, and the mol ratio of sodium tungstate and sodium chloride is 4:1～1:8.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106622383A (en) * | 2016-09-27 | 2017-05-10 | 天津师范大学 | Prussian blue/tungsten trioxide composite photocatalyst and preparation method and application thereof |
| CN106807359A (en) * | 2017-03-01 | 2017-06-09 | 南京信息工程大学 | A kind of simple method for preparing of the hexapetalous flower shape tungsten trioxide photocatalyst containing heterojunction structure |
| CN107739054A (en) * | 2017-11-08 | 2018-02-27 | 东北大学 | A kind of tungsten trioxide powder and preparation method thereof |
| CN108855047A (en) * | 2018-08-29 | 2018-11-23 | 河南师范大学 | A kind of flower-shaped tungstic acid/graphene composite photocatalyst and preparation method thereof |
| CN109364871A (en) * | 2018-11-05 | 2019-02-22 | 江苏大学 | A kind of oxygen defect type tungstic trioxide nano-slice adsorbent and preparation method thereof |
| CN112121830A (en) * | 2020-09-18 | 2020-12-25 | 江苏大学 | Preparation method and application of silver phosphate/tungsten trioxide core-shell nano photocatalytic composite material |
| CN112458791A (en) * | 2020-12-08 | 2021-03-09 | 马鞍山市康辉纸箱纸品有限公司 | Corrugated paper processing technology for improving easy glue opening of corrugated paper surface sizing agent |
| CN114602486A (en) * | 2022-03-25 | 2022-06-10 | 中南大学 | Method for preparing nickel ion-doped tungsten trioxide photocatalyst, product and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009056395A (en) * | 2007-08-31 | 2009-03-19 | Toshiba Lighting & Technology Corp | Visible light responsive photocatalyst |
| CN101774643A (en) * | 2010-01-12 | 2010-07-14 | 中南大学 | Process for preparing tungstic oxide hydrate from sodium tungstate solution |
| CN102068981A (en) * | 2010-12-31 | 2011-05-25 | 同济大学 | Hydrothermal preparation method and product of film nano material with photocatalysis property |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009056395A (en) * | 2007-08-31 | 2009-03-19 | Toshiba Lighting & Technology Corp | Visible light responsive photocatalyst |
| CN101774643A (en) * | 2010-01-12 | 2010-07-14 | 中南大学 | Process for preparing tungstic oxide hydrate from sodium tungstate solution |
| CN102068981A (en) * | 2010-12-31 | 2011-05-25 | 同济大学 | Hydrothermal preparation method and product of film nano material with photocatalysis property |
Non-Patent Citations (1)
| Title |
|---|
| YI ZHENG等: "Template and surfactant free synthesis of hierarchical WO3•0.33H2O via a facile solvothermal route for photocatalytic RhB degradation", 《CRYSTENGCOMM》 * |
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| CN106622383B (en) * | 2016-09-27 | 2019-06-11 | 天津师范大学 | Prussian blue/tungstic acid composite photo-catalyst of one kind and the preparation method and application thereof |
| CN106807359A (en) * | 2017-03-01 | 2017-06-09 | 南京信息工程大学 | A kind of simple method for preparing of the hexapetalous flower shape tungsten trioxide photocatalyst containing heterojunction structure |
| CN107739054A (en) * | 2017-11-08 | 2018-02-27 | 东北大学 | A kind of tungsten trioxide powder and preparation method thereof |
| CN108855047A (en) * | 2018-08-29 | 2018-11-23 | 河南师范大学 | A kind of flower-shaped tungstic acid/graphene composite photocatalyst and preparation method thereof |
| CN109364871A (en) * | 2018-11-05 | 2019-02-22 | 江苏大学 | A kind of oxygen defect type tungstic trioxide nano-slice adsorbent and preparation method thereof |
| CN109364871B (en) * | 2018-11-05 | 2021-08-03 | 江苏大学 | Oxygen-deficient tungsten trioxide nanosheet adsorbent and preparation method thereof |
| CN112121830A (en) * | 2020-09-18 | 2020-12-25 | 江苏大学 | Preparation method and application of silver phosphate/tungsten trioxide core-shell nano photocatalytic composite material |
| CN112458791A (en) * | 2020-12-08 | 2021-03-09 | 马鞍山市康辉纸箱纸品有限公司 | Corrugated paper processing technology for improving easy glue opening of corrugated paper surface sizing agent |
| CN114602486A (en) * | 2022-03-25 | 2022-06-10 | 中南大学 | Method for preparing nickel ion-doped tungsten trioxide photocatalyst, product and application thereof |
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| CN105771963B (en) | 2018-07-17 |
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