CN108714424A - A kind of preparation method of the three compound crystalline phase WO 3 film of oblique-six sides of Fe2O3 doping - Google Patents
A kind of preparation method of the three compound crystalline phase WO 3 film of oblique-six sides of Fe2O3 doping Download PDFInfo
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- CN108714424A CN108714424A CN201810456659.6A CN201810456659A CN108714424A CN 108714424 A CN108714424 A CN 108714424A CN 201810456659 A CN201810456659 A CN 201810456659A CN 108714424 A CN108714424 A CN 108714424A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title abstract description 8
- 150000001875 compounds Chemical class 0.000 title description 17
- 239000010408 film Substances 0.000 claims abstract description 51
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000010409 thin film Substances 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 238000010276 construction Methods 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 239000011521 glass Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000002791 soaking Methods 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
- 239000000758 substrate Substances 0.000 claims 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 5
- 230000008030 elimination Effects 0.000 abstract description 4
- 238000003379 elimination reaction Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000000356 contaminant Substances 0.000 abstract description 3
- 235000010344 sodium nitrate Nutrition 0.000 abstract description 3
- 239000004317 sodium nitrate Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000003403 water pollutant Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 34
- 239000003054 catalyst Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009643 growth defect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 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
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 230000004304 visual acuity Effects 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- 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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- 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)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the preparation methods of a kind of three oblique crystalline phases and the WO 3 film of hexagonal phase composite construction, belong to technical field of material.WO is made with hydro-thermal method using sodium nitrate and ferric nitrate as raw material in the method for the present invention3Thin-film material makes WO obtained using Fe2O3 doping as measure3Film has three oblique crystalline phase WO3With hexagonal phase WO3It constitutes, there is good elimination performance to heavy metal contaminants in water.This method has the advantages that equipment and simple for process, manufacturing cost are low etc..The film surface obtained is smooth, and particle size distribution is uniform, and thin film stability is good；This material has wide practical use in photocatalysis water pollutant elimination etc..
Description
Technical field
The present invention relates to a kind of WO 3 films with three oblique crystalline phases and hexagonal phase composite construction of Fe2O3 doping
Preparation method belongs to technical field of material.
Background technology
WO3Semiconductor light-catalyst is considered as one of ideal photocatalyst material, it has following features：Green nothing
Poison, preparation is simple, physicochemical properties are stable, sensitive to visible light, electronic transmission performance is good, raw material are cheap.In gas
Detection, photocatalysis, the fields such as light shutter device and electrochromic device have a wide range of applications.But WO3Middle light induced electron-sky
The Quick Casting in cave pair constrains its photocatalysis efficiency to a certain extent.Therefore, effectively inhibit WO3Middle photo-generate electron-hole
To it is compound be to further increase WO3The effective way of photochemical catalyst efficiency.
Currently, for improving WO3The effective way of photocatalysis film device efficiency is concentrated mainly on and improves its electron hole
Separative efficiency, in terms of promoting its electron transfer efficiency.The method mainly used have metal ion mixing, it is nonmetallic ion-doped,
Semi-conducting material meets.
Such as A.Hoel in 2004 is prepared for the WO of doping Al with high-frequency induction evaporation source vapour deposition method3Al is mixed in thick film, discovery
WO3Film is to H2The sensibility of S is than pure WO3Good, resolving power is pure WO33 times of film.Wang Xuan in 2010 etc. is with wolframic acid and the tetrabutyl
Ammonium hydroxide is raw material, and preparing C by sol-gal process adulterates WO3-x, the results showed that C doping changes WO to a certain extent3
Crystal structure, do not generate crystallography transformation under the premise of so that catalyst surface W5+Increase with Lacking oxygen content, these are arranged
It applies and all improves WO3-xAbsorbing properties and electronic transmission performance, to be conducive to the raising of photocatalytic activity.Ultraviolet and
Under radiation of visible light, C adulterates WO3Photocatalytic water hydrogen generation efficiency ratio WO3-xIt improves up to 91%.For another example Bi Dongqin in 2012 etc. uses machine
Tool mixed method, is prepared for WO3And Fe2O3Mixture, test result show when calcination temperature be 400 DEG C and Fe2O3Contain
Amount is when mass percentage is 1.0%, to the photocatalysis effect highest of organic dyestuff X3B.Cui Yu people in 2011 etc. are prepared for
Complex phase photochemical catalyst WO3/ ZnO, and the processing of the waste water containing acid black dye is studied, find complex phase photochemical catalyst
WO3/ ZnO is obvious to the percent of decolourization effect of acid black dye solution, up to 99.6%.White stamen in 2011 etc. uses colloidal sol-
Gel method is prepared for WO3-TiO2Nanocomposite works as WO3Mass percentage 3%, when calcination temperature is 550 DEG C,
The efficiency of photo-catalytic degradation of methyl-orange waste water from dyestuff, than pure WO3And TiO2Degradation efficiency be significantly improved.
WO at present3And its preparation method of film mainly has sol-gel method, electrochemical deposition method, magnetron sputtering method, change
Learn vapor phase deposition method, hydro-thermal and solvent-thermal method etc..The wherein low temperature of hydro-thermal method, high-pressure solution condition, be conducive to growth defect it is few,
It is orientated, the crystal of perfect structure, and the product crystallinity synthesized is high, thermal stress is small, uniformity and purity are higher, granularity is easily-controllable
And process costs it is cheap the advantages that.WO is made with hydro-thermal method using sodium nitrate and ferric nitrate as raw material in the present invention3Thin-film material, and
For the first time using Fe2O3 doping as measure, make WO obtained3Film has three oblique crystalline phase WO3With hexagonal phase WO3The compound crystalline phase knot of composition
Structure.The three compound crystalline phase WO 3 films of oblique-six sides prepared have good disappear to organic and heavy metal contaminants in water
Except performance.
Invention content
It is an object of the invention to propose a kind of preparation method of the compound crystalline phase WO 3 film of three oblique-six sides；The party
WO is made with hydro-thermal method using sodium nitrate and ferric nitrate as raw material in method3Thin-film material, this method make to be made using Fe2O3 doping as measure
WO3Film has three oblique crystalline phase WO3With hexagonal phase WO3The compound crystal phase structure of composition, has heavy metal contaminants in water
There is good elimination performance.
The preparation method of the three compound crystalline phase WO 3 films of oblique-six sides, which is characterized in that the method passes through sodium tungstate
Hydrolysis and ferric nitrate doping be made, include the following steps：
(1) a certain amount of sodium tungstate and ferric nitrate are dissolved in distilled water, are stirred evenly；
(2) it is slowly added to a certain amount of hydrochloric acid solution in above-mentioned solution, be vigorously stirred；
(3) FTO electro-conductive glass is added in above-mentioned solution, carries out hydro-thermal reaction, then natural cooling；
(4) after a certain period of time by the cleaning of above-mentioned FTO electro-conductive glass, dry, calcining, being made has three oblique crystalline phase-hexagonal crystals
Phase WO 3 film.
In the above preparation method, the raw material in the step (1) is from tungstates and nitre such as sodium tungstate, ammonium tungstates
The molysite such as sour iron, iron chloride.
In the above preparation method, the step (1) and (2) middle operation carry out under stirring.
In the above preparation method, the temperature of hydro-thermal reaction is 80-200 DEG C in the step (3).
In the above preparation method, the soaking time in the step (3) under hydrothermal temperature is 12-48 hours.
In the above preparation method, cleaning is rinsed using deionized water in the step (4).
In the above preparation method, drying mode is dried in vacuo using 50-100 DEG C in the step (4).
In the above preparation method, the calcination temperature in the step (4) is 300-800 DEG C.
In the above preparation method, soaking time is 1-6 hours at calcination temperatures in the step (4).
In the above preparation method, the iron content of the middle gained WO 3 film of the step (4) is 0.3% to 5.0%
Between.
In the above preparation method, three oblique crystalline phases and hexagonal phase in gained WO 3 film in the step (4)
Ratio is 1:4 to 3:Between 5.
Using the WO 3 film of the three oblique compound crystalline phases of-six sides prepared by this technology, there is equipment and simple for process, system
The features such as standby condition is stringent controllable, of low cost, the film surface uniform ground of preparation, firmness is high, can Reusability, and light
Catalysis efficiency is notable.
Description of the drawings
Fig. 1 is the three compound crystalline phase WO 3 films of oblique-six sides prepared by the embodiment of the present invention 1 in photo catalytic reduction sexavalence
Pattern before and after chromium
Fig. 2 is the stereoscan photograph of the three compound crystalline phase WO 3 films of oblique-six sides prepared by the embodiment of the present invention 1
Fig. 3 a are the XRD spectrum of the three compound crystalline phase WO 3 films of oblique-six sides prepared by the embodiment of the present invention 1, Fig. 3 b
It is the XRD spectrum for not adding the oblique crystalline phase WO 3 film of single three prepared when ferric nitrate
Specific implementation mode
Technical solution of the present invention is described further with reference to embodiment.
The present invention proposes a kind of preparation method of the compound crystalline phase WO 3 film of three oblique-six sides, which is characterized in that described
Method sodium tungstate and ferric nitrate are raw material, WO 3 film obtained by three oblique crystalline phases WO3With the WO of hexagonal phase3Composition,
And include the following steps and content：
(1) raw material used by is commercially available sodium tungstate and ferric nitrate.
(2) preparation manipulation carries out under stirring.
(3) in preparation process, first a certain amount of sodium tungstate and ferric nitrate is dissolved in distilled water, stirred evenly, it then will be upper
It states and is slowly added to a certain amount of hydrochloric acid solution in solution, be vigorously stirred.
(4) FTO electro-conductive glass is added in above-mentioned solution, carries out hydro-thermal reaction, hydrothermal temperature is 80-200 DEG C, is protected
The warm time is 12-48 hours.
(5) after taking out the cleaning of FTO electro-conductive glass deionized waters, 50-100 DEG C of vacuum drying.
(6) by above-mentioned FTO electro-conductive glass in 300-800 DEG C of temperature lower calcination 1-6 hours.
The obtained three compound crystalline phase WO 3 film appearances of oblique-six sides are the uniform film in light yellow surface.
Under a scanning electron microscope, it may be observed that a large amount of nano particles, particle are about 1-2 microns.XRD test displays should
Film is collectively constituted by three oblique crystalline phase tungstic acids and hexagonal phase tungstic acid.The spectrophotometric to be developed the color by sulfosalicylic acid
Between the content that method measures iron in WO 3 film is 0.3% to 5.0%.WO 3 film is obtained by XRD test analysis
In the ratio of three oblique crystalline phases and hexagonal phase 1:4 to 3:Between 5.
In short, the three compound crystalline phase WO 3 films of oblique-six sides can be made using this technology.
Embodiment：The sodium tungstate of 23.1g is slowly dissolved in 300mL distilled water under stirring, continues to stir
30min, be added while stirring 1% to 50% different quality relative to sodium tungstate than ferric nitrate, FTO is added in the solution and leads
After electric glass, hydro-thermal reaction is carried out at 80-200 DEG C 12-48 hours, after taking out the cleaning of FTO electro-conductive glass deionized waters, 50-
100 DEG C of vacuum drying, in 300-800 DEG C of temperature lower calcination 1-6 hours.
The compound crystalline phase WO 3 film of oblique-six sides of prepared three is light yellow, and to containing the heavy metal water body property eliminated
Pattern is basically unchanged (see Fig. 1) before and after energy test reaction, under scanning electron microscope, it may be observed that a large amount of sample particles, particle
About 1-2 microns (see Fig. 2), the film is by three oblique crystalline phase tungstic acids and hexagonal phase tungstic acid is compound forms (see Fig. 3
(a) it is film XRD test charts, Fig. 3 (b) is film XRD test charts when undoping iron), there is excellent elimination to heavy metal in water
Performance reached 96.1% within 120 minutes time to 10mg/L hexavalent chromium solution photo catalytic reduction rates.
Claims (8)
1. a kind of WO 3 film, which is characterized in that the WO 3 film has doped with iron, the WO 3 film
Three oblique crystalline phases-hexagonal phase composite construction.
2. WO 3 film as described in claim 1, wherein in the WO 3 film content of iron be 0.3% to
Between 5.0%.
3. WO 3 film as described in claim 1, wherein three oblique crystalline phases and hexagonal phase in the WO 3 film
Ratio be 1:4 to 3:Between 5.
4. WO 3 film as described in any one of claims 1-3, wherein the WO 3 film has 1-2 microns
Particle.
5. a kind of preparation method of WO 3 film, the WO 3 film is that tungstic acid described in claim 1 is thin
Film, which is characterized in that the described method comprises the following steps：
(1) sodium tungstate and ferric nitrate are dissolved in distilled water, are stirred evenly；
(2) glass substrate is added in above-mentioned solution, carries out hydro-thermal reaction；
(3) aforesaid substrate is taken out, calcines, forms the WO 3 film on the substrate.
6. the preparation method of WO 3 film as claimed in claim 5, wherein in the step (1), wolframic acid is first added
Sodium adds the ferric nitrate for accounting for that the mass ratio of sodium tungstate is 1% to 50%.
7. the preparation method of WO 3 film as claimed in claim 5, wherein in the step (2), the temperature of hydro-thermal reaction
Degree is 80-200 DEG C, and soaking time is 12-48 hours.
8. the preparation method of WO 3 film as claimed in claim 5, wherein in the step (3), the temperature model of calcining
It is 300-800 DEG C to enclose, and calcination time is 1-6 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810456659.6A CN108714424A (en) | 2018-05-14 | 2018-05-14 | A kind of preparation method of the three compound crystalline phase WO 3 film of oblique-six sides of Fe2O3 doping |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810456659.6A CN108714424A (en) | 2018-05-14 | 2018-05-14 | A kind of preparation method of the three compound crystalline phase WO 3 film of oblique-six sides of Fe2O3 doping |
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| CN108714424A true CN108714424A (en) | 2018-10-30 |
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| CN111235600A (en) * | 2020-01-13 | 2020-06-05 | 中国计量大学 | Iron ion doped tungsten oxide hydrate covered foam nickel catalytic electrode and preparation method thereof |
| CN116282174A (en) * | 2023-04-11 | 2023-06-23 | 北京化工大学 | Preparation method of tungsten oxide nano-micro material in metal ion auxiliary and acid and alkaline environments |
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| CN106222685A (en) * | 2016-08-22 | 2016-12-14 | 南京航空航天大学 | A kind of WO of photoelectrocatalysis water decomposition3the preparation method of LDH laminated film |
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| CN106399979A (en) * | 2016-10-17 | 2017-02-15 | 天津城建大学 | Preparation method of inflorescence type WO3 thin film for electrochromism |
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| CN111235600A (en) * | 2020-01-13 | 2020-06-05 | 中国计量大学 | Iron ion doped tungsten oxide hydrate covered foam nickel catalytic electrode and preparation method thereof |
| CN111235600B (en) * | 2020-01-13 | 2020-12-15 | 中国计量大学 | Preparation method of iron ion doped tungsten oxide hydrate covered foam nickel catalytic electrode |
| CN116282174A (en) * | 2023-04-11 | 2023-06-23 | 北京化工大学 | Preparation method of tungsten oxide nano-micro material in metal ion auxiliary and acid and alkaline environments |
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