CN109126794A - Fe, Si co-doped nano TiO2The preparation method and application of composite powder and composite coating - Google Patents
Fe, Si co-doped nano TiO2The preparation method and application of composite powder and composite coating Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 99
- 239000002131 composite material Substances 0.000 title claims abstract description 97
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 97
- 238000000576 coating method Methods 0.000 title claims abstract description 80
- 239000011248 coating agent Substances 0.000 title claims abstract description 79
- 239000000843 powder Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 80
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000007750 plasma spraying Methods 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 96
- 239000011159 matrix material Substances 0.000 claims description 26
- 238000005507 spraying Methods 0.000 claims description 24
- 239000007921 spray Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 238000005422 blasting Methods 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000010431 corundum Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 238000007788 roughening Methods 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- 238000005488 sandblasting Methods 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000010865 sewage Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 239000002957 persistent organic pollutant Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000007751 thermal spraying Methods 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 abstract description 16
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000007769 metal material Substances 0.000 abstract description 2
- 238000007747 plating Methods 0.000 abstract description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 14
- 229960000907 methylthioninium chloride Drugs 0.000 description 14
- 238000007789 sealing Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 230000001699 photocatalysis Effects 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000005286 illumination Methods 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 239000010963 304 stainless steel Substances 0.000 description 3
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 2
- -1 TiO2 compound Chemical class 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- 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
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The preparation method and application of Fe, Si co-doped nano TiO2 composite powder and composite coating of the present invention belong to the plating field to metal material, and reusable Fe, Si co-doped nano TiO is prepared more particularly to a kind of plasma spraying2The method of composite coating.Its purpose is to provide the preparation method and application of a kind of reusable Fe, Si co-doped nano TiO2 composite powder and composite coating.Fe, Si co-doped nano TiO of the present invention2The molar ratio of Fe, Si and Ti are respectively 1:4 and 1:10 in composite powder.The nano-TiO of Fe, Si codope produced by the present invention2Photocatalysis performance of the composite coating under natural light is good, high recycling rate；The nano-TiO of Fe, Si codope prepared by the present invention2Composite coating is secured, stablizes, and can be used for being mass produced.
Description
Technical field
The invention belongs to the plating fields to metal material, prepare more particularly to a kind of plasma spraying reusable
Fe, Si co-doped nano TiO2The method of composite coating.
Background technique
Nano-TiO2It is a kind of photochemical catalyst being widely studied in recent years, it has photocatalytic activity height, photoelectric properties
The advantages that excellent, chemical stability is good and hypotoxicity, is widely used in solar battery assembling, sewage treatment, and air is net
Change, the fields such as organic matter degradation, is a kind of photochemical catalyst for most having application potential at present.But due to TiO2Excitation is illuminated by the light to produce
The recombination rate again of raw photo-generate electron-hole pair is high, and light quantum utilization rate is relatively low；Forbidden bandwidth (3.2eV) is wider, spectral response
Narrow range, light absorption are confined to ultra-violet (UV) band, lead to nano-TiO2There is also some limitations in practical applications for photocatalysis technology.
It is answered currently, people mainly pass through nonmetal doping, metal ion mixing, surface noble metal loading, surface sensitization and semiconductor
Close the methods of modified, raising nano-TiO2Photocatalysis performance under natural light.Y Lin et al. reports [Electronic
and optical performances of Si and Fe-codoped TiO2,nanoparticles:A
photocatalyst for the degradation of methylene blue,2013,s 142–143(10):38-44]
Fe, Si co-doped nano TiO are prepared using sol-gel method2Composite powder, the results showed that collaboration effect when Fe, Si codope
It should make nano-TiO2Composite powder is than single doping and pure TiO2Photocatalysis performance it is more preferable.
But nano-TiO2Powder diameter is tiny, carries out being easy to be lost when photocatalysis in liquid phase or gas phase, be not easily recycled, makes
At the wasting of resources, and it is easy to cause secondary pollution.By nano-TiO2It is supported on certain carrier, can solve the separation of catalyst
This problem is recycled, TiO is improved2Utilization rate.Chinese patent (publication number CN1230572C) discloses one kind shape on substrate
At the preparation method of miscellaneous nitrogen photo-catalytic activity of nano titanium dioxide agent coating, with the inert gases such as nitrogen, argon gas or Krypton or it
Mixed gas be powder feeding gas, using plasma spray coating process by TiO2It is sprayed on matrix surface, is obtained by heat treatment miscellaneous
Nitrogen nanometer titanium dioxide coating.Chinese patent (publication number CN103409715A) discloses a kind of porous TiO2/SiO2Composite coating
Preparation method, with TiO2、SiO2Mixed powder is raw material, prepares TiO using plasma spray coating process2/SiO2Composite coating.Deng
Plasma spray is a kind of method that high efficiency, low cost prepare Large area coatings, and the coating as made from the technique is fine and close, in conjunction with strong
Degree is high, property is stablized.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of reusable Fe, Si co-doped nano TiO2 composite powders
The preparation method and application of end and composite coating, it is based on TiO2Photocatalysis characteristic propose, utilize plasma spraying skill
Art, by Fe, Si codope TiO2Composite powder partial melting is deposited on stainless steel base, makes have excellent photocatalysis performance
Fe, Si co-doped nano TiO2It is reused, avoids the wasting of resources.
The present invention relates to a kind of Fe, Si co-doped nano TiO2Composite powder, Fe, Si co-doped nano TiO2It is compound
The molar ratio of Fe, Si and Ti are respectively 1:4 and 1:10 in powder；That is n (Fe)/n (Ti)=1:4, n (Si)/n (Ti)=1:10.
The invention further relates to a kind of Fe, Si co-doped nano TiO2The preparation method of composite powder, the method includes with
Lower step:
Using tetra-n-butyl titanate as titanium source, Fe (NO3)3·9H2O is source of iron, and ethyl orthosilicate is silicon source, solidifying using colloidal sol-
Glue method obtains Fe, Si co-doped nano TiO2Colloidal sol, colloidal sol room temperature are aged after 3d in 100 DEG C of drying 10h, grind 30min, then
600 DEG C of roasting 3h, furnace cooling in Muffle furnace, obtain Fe, Si co-doped nano TiO of the invention2Composite powder；Powder
Crystal phase is Detitanium-ore-type, average grain diameter 80nm.
The invention further relates to a kind of Fe, Si co-doped nano TiO2The preparation method of composite coating, the method includes with
Lower step:
(1) Fe, Si co-doped nano TiO2The preparation of composite powder: its above-mentioned method is prepared；
(2) preparation of dusty spray: by Fe, Si codope TiO obtained in step (1)2Composite powder by doing by spraying
Dry technology is prepared into micron order Fe, Si co-doped nano TiO suitable for thermal spraying2Composite powder；
(3) matrix surface cleaning, blasting treatment；
(4) plasma spraying: using plasma spraying equipment in the repeatable benefit of matrix surface preparation handled through step (3)
Fe, Si co-doped nano TiO2Composite coating；
Substrate preheating is to 150~200 DEG C before spraying, parameter in spraying process: main gas Ar 80L/min, auxiliary gas H2
10L/min, spray voltage 60V, spraying current 450A, 80~100mm of spray distance, powder feeding rate 15g/min, spraying are with powder
Micron order Fe, Si co-doped nano TiO that step (2) is prepared2Composite powder, partial size are 41-96 μm.
Preferably, the concrete operations of the step (2) are as follows:
With Fe, Si co-doped nano TiO2Composite powder is raw material, and polyvinyl alcohol is binder, mixed using V-type batch mixer
It closes uniformly, is then spray-dried, reuse stainless steel mesh sieving, take the fine powder between 160-350 mesh, as micron order Fe,
Si co-doped nano TiO2Composite powder.
Preferably, the concrete operations of the step (3) are as follows:
Using the flaky matrix of 15mm × 20mm, it is cleaned by ultrasonic respectively with dehydrated alcohol and deionized water, drying；Using grain
The corundum sand that diameter is 200-700 μm carries out sandblasting roughening treatment to matrix surface, improves the roughness of matrix surface.
The substrate includes but is not limited to 304 stainless steels, can be various forms of metal plates, glass plate, ceramic wafer,
Metal mesh, bead.
The matrix can preheat, and can not also preheat direct spraying, and preheating can be improved the bond strength of coating, subtract
Small stress is concentrated.
Preferably, the flaky matrix is 304 stainless steels.
Preferably, to Fe, Si co-doped nano TiO after the step (4)2Composite coating carries out sealing pores.
Preferably, Fe, Si co-doped nano TiO made from the step (4)2Composite coating applies with a thickness of 200-300 μm
TiO in layer2Crystal phase be Detitanium-ore-type and rutile-type, Detitanium-ore-type TiO2The mass percent for accounting for coating is 6.25%.
The invention further relates to a kind of Fe, Si co-doped nano TiO2Composite coating, the coating are to make according to the method described above
For what is obtained.
The invention further relates to a kind of Fe, Si co-doped nano TiO2The application of composite coating, the coating are used for photocatalysis
Organic pollutant in degradation air or sewage.
The preparation method and application and the prior art of Fe, Si co-doped nano TiO2 composite powder and composite coating of the present invention
The difference is that:
1, Fe, Si co-doped nano TiO produced by the present invention2Composite powder, forbidden bandwidth reduce, photo-generate electron-hole
Recombination probability reduce, nano-TiO2Photocatalysis performance under natural light is improved.
2, Fe, Si co-doped nano TiO that the present invention is obtained using plasma spraying technology2Composite coating surface is by melting
Melt, partial melting and on a small quantity do not melt molten drop composition, form rough pattern, with micron-sized roughness, have
Conducive to increase and by the contact area of photocatalysis object.
3, the nano-TiO of Fe, Si codope produced by the present invention2Photocatalysis performance of the composite coating under natural light is good
It is good, high recycling rate.
4, the nano-TiO of Fe, Si codope prepared by the present invention2Composite coating is secured, stablizes, and can be used for extensive life
It produces.
Detailed description of the invention
Fig. 1 is embodiment 1Fe, Si co-doped nano TiO2Composite coating surface topography SEM photograph；
Fig. 2 is embodiment 1Fe, Si co-doped nano TiO2Composite coating Cross Section Morphology SEM photograph；
Fig. 3 is embodiment 1Fe, Si co-doped nano TiO2Composite coating XRD spectrum；
Fig. 4 is embodiment 1Fe, Si co-doped nano TiO2The result of composite coating photocatalytic degradation methylene blue；
Fig. 5 is Fe, Si co-doped nano TiO of 2 sealing pores of embodiment2Composite coating surface topography SEM photograph；
Fig. 6 is Fe, Si co-doped nano TiO of 2 sealing pores of embodiment2Composite coating photocatalytic degradation methylene blue
As a result；
Fig. 7 is embodiment 3Fe, Si co-doped nano TiO2The recycling rate of waterused of composite coating.
Specific embodiment
By following embodiment and verification test to Fe, Si co-doped nano TiO2 composite powder of the invention and compound painting
The preparation method and application of layer are further described.
Embodiment 1
Fe, Si co-doped nano TiO of the present embodiment2Composite coating is prepared according to the following steps:
(1) Fe, Si co-doped nano TiO2The preparation of composite powder: with tetra-n-butyl titanate, Fe (NO3)3·9H2O, just
Silester is raw material, prepares Fe, Si co-doped nano TiO using sol-gel method2Composite powder.Wherein, n (Fe)/n
(Ti)=0.25%, n (Si)/n (Ti)=10.00%, TiO2For Detitanium-ore-type, average grain diameter 80nm
(2) preparation of spray powders: with Fe, Si co-doped nano TiO2Composite powder is raw material, and polyvinyl alcohol is viscous
Agent is tied, spray-dried, grinding is sieved using stainless steel mesh, takes the fine powder between -350 mesh of 160 mesh, spare.
(3) matrix cleaning, blasting treatment: 304 stainless steel base of sheet of 15mm × 20mm is used, uses dehydrated alcohol respectively
It is cleaned by ultrasonic with deionized water, drying；Sandblasting roughening treatment is carried out to matrix using 200-700 μm of partial size of corundum sand, is mentioned
The roughness of high matrix surface.
(4) plasma spraying: using air plasma spraying equipment in the matrix surface preparation by step (3) processing
Fe, Si co-doped nano TiO2Composite coating, spraying process are realized by controlling following parameter: main gas Ar 80L/min, auxiliary
Gas H2 10L/min, spray voltage 60V, spraying current 450A, 80~100mm of spray distance, powder feeding rate 15g/min, spraying
It is micron order Fe, Si co-doped nano TiO2 compound spraying powder that step (2) is prepared with powder, partial size is 41~96 μm；
To Fe, Si co-doped nano TiO2The photocatalysisization that composite coating carries out degradation of methylene blue under natural lighting is real
It tests.Experiment used coating size is 15mm × 20mm × 2mm, and xenon lamp simulates natural lighting, and 50mL concentration is the methylene of 10mg/L
Base is blue；Coating is put into solution, and 1h is stirred under dark condition, starts illumination after balance to be adsorbed, takes 5mL methylene blue every 1h
Solution measures its absorbance at 664nm, calculates the degradation rate of methylene blue, stops illumination after 3h.
Fe, Si co-doped nano TiO obtained by 1 process of embodiment2Composite coating surface topography SEM photograph is as schemed
Shown in 1.As seen from the figure, coating has typical plasma spraying coating pattern, does not on a small quantity melt by melting, partial melting and
Molten drop composition.
Fig. 2 is Fe, Si co-doped nano TiO being prepared by real 1 process of case2The Cross Section Morphology of composite coating
SEM photograph.As seen from the figure, the thickness of coating is uniform, and porosity is higher.
Fig. 3 is Fe, Si co-doped nano TiO being prepared by real 1 process of case2The XRD spectrum of composite coating,
It can be seen that coating is by Detitanium-ore-type and rutile TiO2Composition.
Fig. 4 is Fe, Si co-doped nano TiO being prepared by real 1 process of case2Composite coating photocatalytic degradation
The experimental result of methylene blue.It can be seen that Fe, Si co-doped nano TiO2Composite coating is under natural light to methylene blue
Photocatalytic degradation effect is obvious.
Embodiment 2
Fe, Si co-doped nano TiO of the present embodiment2Composite coating is prepared according to the following steps:
(1) Fe, Si co-doped nano TiO2The preparation of composite powder: with tetra-n-butyl titanate, Fe (NO3)3·9H2O, just
Silester is raw material, prepares Fe, Si co-doped nano TiO using sol-gel method2Composite powder.Wherein, n (Fe)/n
(Ti)=0.25%, n (Si)/n (Ti)=10.00%, TiO2For Detitanium-ore-type, average grain diameter 80nm
(2) preparation of spray powders: with Fe, Si co-doped nano TiO2Composite powder is raw material, and polyvinyl alcohol is viscous
Agent is tied, spray-dried, grinding is sieved using stainless steel mesh, takes the fine powder between -350 mesh of 160 mesh, spare.
(3) matrix cleaning, blasting treatment: 304 stainless steel base of sheet of 15mm × 20mm is used, uses dehydrated alcohol respectively
It is cleaned by ultrasonic with deionized water, drying；Sandblasting roughening treatment is carried out to matrix using 200-700 μm of partial size of corundum sand, is mentioned
The roughness of high matrix surface.
(4) plasma spraying: using air plasma spraying equipment in the matrix surface preparation by step (3) processing
Fe, Si co-doped nano TiO2Composite coating, spraying process are realized by controlling following parameter: main gas Ar 80L/min, auxiliary
Gas H2 10L/min, spray voltage 60V, spraying current 450A, 80~100mm of spray distance, powder feeding rate 15g/min, spraying
It is micron order Fe, Si co-doped nano TiO2 compound spraying powder that step (2) is prepared with powder, partial size is 41~96 μm；
(5) sealing pores: Fe, Si co-doped nano TiO that will be obtained by step (4)2Composite coating is through dehydrated alcohol
After deionized water ultrasonic cleaning, with Fe, Si co-doped nano TiO2Colloidal sol carries out sealing pores, reduces composite coating surface holes
Gap rate.The process of sealing pores is as follows: at room temperature, sample impregnates 20min in colloidal sol, and then 90 DEG C of dry 30min are slowly cold
But it to room temperature, is repeated 3 times.
To Fe, Si co-doped nano TiO of sealing of hole2Composite coating carries out the photocatalysis of degradation of methylene blue under natural lighting
Change experiment.Experiment used coating size is 15mm × 20mm × 2mm, and xenon lamp simulates natural lighting, and 50mL concentration is 10mg/L's
Methylene blue；Coating is put into solution, and 1h is stirred under dark condition, starts illumination after balance to be adsorbed, takes 5mL methylene every 1h
Base indigo plant solution measures its absorbance at 664nm, calculates the degradation rate of methylene blue, stops illumination after 3h
Fe, Si co-doped nano TiO of sealing pores are obtained by 2 process of embodiment2Composite coating surface topography SEM
Photo is as shown in Figure 5.As seen from the figure, the hole of the coating surface after sealing pores reduces.
Fig. 6 is Fe, Si co-doped nano TiO of the sealing pores prepared by real 2 process of case2Composite coating light is urged
Change the experimental result of degradation of methylene blue.As can be seen that Fe, Si co-doped nano TiO of sealing pores2Composite coating is in nature
It is obvious to the photocatalytic degradation effect of methylene blue under light, but than Fe, Si co-doped nano TiO of non-sealing pores2Compound painting
The photocatalysis performance of layer decreases, this is because sealing pores lead to the reduction of the contact area of coating surface and methylene blue
's.
Embodiment 3
Fe, Si co-doped nano TiO of the present embodiment2Composite coating is prepared according to the following steps:
(1) Fe, Si co-doped nano TiO2The preparation of composite powder: with tetra-n-butyl titanate, Fe (NO3)3·9H2O, just
Silester is raw material, prepares Fe, Si co-doped nano TiO using sol-gel method2Composite powder.Wherein, n (Fe)/n
(Ti)=0.25%, n (Si)/n (Ti)=10.00%, TiO2For Detitanium-ore-type, average grain diameter 80nm
(2) preparation of spray powders: with Fe, Si co-doped nano TiO2Composite powder is raw material, and polyvinyl alcohol is viscous
Agent is tied, spray-dried, grinding is sieved using stainless steel mesh, takes the fine powder between -350 mesh of 160 mesh, spare.
(3) matrix cleaning, blasting treatment: 304 stainless steel base of sheet of 15mm × 20mm is used, uses dehydrated alcohol respectively
It is cleaned by ultrasonic with deionized water, drying；Sandblasting roughening treatment is carried out to matrix using 200-700 μm of partial size of corundum sand, is mentioned
The roughness of high matrix surface.
(4) plasma spraying: using air plasma spraying equipment in the matrix surface preparation by step (3) processing
Fe, Si co-doped nano TiO2Composite coating, spraying process are realized by controlling following parameter: main gas Ar 80L/min, auxiliary
Gas H2 10L/min, spray voltage 60V, spraying current 450A, 80~100mm of spray distance, powder feeding rate 15g/min, spraying
It is micron order Fe, Si co-doped nano TiO that step (2) is prepared with powder2Compound spraying powder, partial size are 41~96 μm；
(5) by Fe, Si co-doped nano TiO after 1 photocatalysis of embodiment experiment2Composite coating deionized water and anhydrous
EtOH Sonicate cleaning, drying, then detect it in the photocatalysis performance of natural light.
Fig. 7 is Fe, Si co-doped nano TiO prepared by 3 process of embodiment2Composite coating photocatalytic degradation methylene
The experimental result of base indigo plant.It can be seen that Fe, Si co-doped nano TiO2The photocatalysis performance of composite coating is good, recycling rate of waterused
It is high.
Although specific embodiments of the present invention have been described above, it will be appreciated by those of skill in the art that these
It is merely illustrative of, protection scope of the present invention is defined by the appended claims.Those skilled in the art is not carrying on the back
Under the premise of from the principle and substance of the present invention, various changes or modifications can be made to these embodiments, but these are changed
Protection scope of the present invention is each fallen with modification.
Claims (9)
1. a kind of Fe, Si co-doped nano TiO2Composite powder, it is characterised in that: Fe, Si co-doped nano TiO2Composite powder
The molar ratio of Fe, Si and Ti are respectively 1:4 and 1:10 in end.
2. a kind of Fe, Si co-doped nano TiO described in claim 12The preparation method of composite powder, it is characterised in that: described
Method the following steps are included:
Using tetra-n-butyl titanate as titanium source, Fe (NO3)3·9H2O is source of iron, and ethyl orthosilicate is silicon source, using sol-gel method
Obtain Fe, Si co-doped nano TiO2Colloidal sol, colloidal sol room temperature are aged after 3d in 100 DEG C of drying 10h, 30min are ground, then in horse
Not 600 DEG C of roasting 3h, furnace cooling in furnace, obtains Fe, Si co-doped nano TiO of the invention2Composite powder.
3. a kind of Fe, Si co-doped nano TiO2The preparation method of composite coating, it is characterised in that: the method includes following steps
It is rapid:
(1) Fe, Si co-doped nano TiO2The preparation of composite powder: it is prepared according to method as stated in claim 2；
(2) preparation of dusty spray: by Fe, Si codope TiO obtained in step (1)2Composite powder passes through spray drying technology
It is prepared into micron order Fe, Si co-doped nano TiO suitable for thermal spraying2Composite powder；
(3) matrix surface cleaning, blasting treatment；
(4) Fe, Si codope plasma spraying: are prepared in the matrix surface handled through step (3) using plasma spraying equipment
Nano-TiO2Composite coating；
Substrate preheating is to 150~200 DEG C before spraying, parameter in spraying process: main gas Ar 80L/min, auxiliary gas H210L/min,
Spray voltage 60V, spraying current 450A, 80~100mm of spray distance, powder feeding rate 15g/min, spraying are step (2) with powder
Micron order Fe, Si co-doped nano TiO being prepared2Composite powder, partial size are 41-96 μm.
4. Fe, Si co-doped nano TiO according to claim 32The preparation method of composite coating, it is characterised in that: described
The concrete operations of step (2) are as follows:
With Fe, Si co-doped nano TiO2Composite powder is raw material, and polyvinyl alcohol is binder, is mixed using V-type batch mixer equal
It is even, it is then spray-dried, re-sieving, takes the fine powder between 160-350 mesh, as micron order Fe, Si co-doped nano TiO2It is multiple
Close powder.
5. Fe, Si co-doped nano TiO according to claim 32The preparation method of composite coating, it is characterised in that: described
The concrete operations of step (3) are as follows:
Using the flaky matrix of 15mm × 20mm, it is cleaned by ultrasonic respectively with dehydrated alcohol and deionized water, drying；Use partial size for
200-700 μm of corundum sand carries out sandblasting roughening treatment to matrix surface, improves the roughness of matrix surface.
6. Fe, Si co-doped nano TiO according to claim 52The preparation method of composite coating, it is characterised in that: described
Flaky matrix is 304 stainless steels.
7. Fe, Si co-doped nano TiO according to claim 32The preparation method of composite coating, it is characterised in that: the step
Suddenly Fe, Si co-doped nano TiO made from (4)2Composite coating is with a thickness of 200-300 μm, TiO in coating2Crystal phase be anatase
Type and rutile-type, Detitanium-ore-type TiO2The mass percent for accounting for coating is 6.25%.
8. a kind of Fe, Si co-doped nano TiO2Composite coating, it is characterised in that: the coating is according to described in claim 3
What method was prepared.
9. Fe, Si co-doped nano TiO described in a kind of claim 82The application of composite coating, it is characterised in that: the coating
For the organic pollutant in photocatalytic degradation air or sewage.
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