CN107376897A - A kind of oxidation catalysis film containing three metals and preparation method and application - Google Patents
A kind of oxidation catalysis film containing three metals and preparation method and application Download PDFInfo
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- CN107376897A CN107376897A CN201710498033.7A CN201710498033A CN107376897A CN 107376897 A CN107376897 A CN 107376897A CN 201710498033 A CN201710498033 A CN 201710498033A CN 107376897 A CN107376897 A CN 107376897A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 239000002184 metal Substances 0.000 title claims abstract description 56
- 150000002739 metals Chemical class 0.000 title claims abstract description 50
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 41
- 230000003647 oxidation Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 58
- 230000003197 catalytic effect Effects 0.000 claims abstract description 39
- 239000011787 zinc oxide Substances 0.000 claims abstract description 37
- 239000003792 electrolyte Substances 0.000 claims abstract description 25
- 238000012545 processing Methods 0.000 claims abstract description 21
- 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 claims abstract description 19
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 19
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 14
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 13
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 13
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 239000000853 adhesive Substances 0.000 claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 4
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000011159 matrix material Substances 0.000 claims description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- 230000015556 catabolic process Effects 0.000 claims description 20
- 238000006731 degradation reaction Methods 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 244000137852 Petrea volubilis Species 0.000 claims description 11
- 238000011065 in-situ storage Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000000498 cooling water Substances 0.000 claims description 2
- 238000005498 polishing Methods 0.000 claims description 2
- 239000011229 interlayer Substances 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 31
- 239000010936 titanium Substances 0.000 abstract description 21
- 229910052719 titanium Inorganic materials 0.000 abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 20
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 238000002474 experimental method Methods 0.000 abstract description 4
- 230000007850 degeneration Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 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 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005238 degreasing Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/39—
-
- B01J35/59—
-
- B01J35/61—
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
-
- 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
Abstract
The invention discloses a kind of oxidation catalysis film containing three metals and its preparation method and application.This method comprises the following steps：（1）Surface preparation is carried out to Titanium base；（2）Alkaline sodium phosphate/phosphotungstic acid composite electrolyte is prepared, additive is nano granular of zinc oxide；（3）By step（1）In Titanium base as anode, be placed in equipped with step（2）In the double glazing reactor of electrolyte, plasma electrolytic oxidation processing is carried out, is made and contains TiO2‑WO3The metals of ZnO tri- aoxidize catalytic membrane.By obtained TiO2‑WO3The metals of ZnO tri- oxidation catalytic membrane, which is put into the photo catalysis reactor equipped with methylene blue solution, carries out catalysis degeneration experiment.Nano ZnO particles are contained on the catalytic membrane surface that the present invention obtains, and increase specific surface area, have the advantages that adhesive force is good, and photocatalytic activity is high.
Description
Technical field
The invention belongs to catalytic membrane field, and in particular to one kind contains three metals（TiO2-WO3-ZnO）Oxidation catalysis film
And preparation method and application.
Background technology
Methylene blue is common a kind of organic matter in printing and dyeing, be not added with any processing water body and environment can be caused it is very serious
Harm.Therefore, Many researchers are directed to finding suitable method to handle methylene blue waste water.
A kind of feasible method, it is to utilize photochemical catalyst catalytic degradation methylene blue in waste under illumination condition.At present
Most commonly used photochemical catalyst is powder titanium dioxide, achieves preferable effect.But the recovery of conventional powder titanium dioxide
Problem then increasingly highlights.
Plasma electrolytic oxidation is a kind of new metal surface treatment technology of comparison.The technical operation flow is simple, green
Colour circle is protected, can be in light metal（Al, Mg, Ti, Zr etc.）Surface in situ generates film layer.The film layer of generation combined with matrix it is strong, contain
There are excellent mechanics and mechanical performance, cause widely studied.Titanium alloy surface modification is used it for, Titanium base surface can be improved
Performance, prepare the film layer of difference in functionality.Although plasma electrolytic oxidation prepares catalyst, film layer has the advantages of uniqueness,
Its practical application is very limited --- and porosity and specific surface area are low, and microstructure is poor, and active component is low and is not easy richness
Collection etc., the actual catalytic effect of catalyst for causing it to prepare is poor.Therefore, the ratio table of plasma electrolytic oxidation film layer is improved
Area and active component content, to widening the technology in catalytic field research application containing being of great importance.In addition, conventional photocatalysis
In agent, zinc oxide is direct band-gap semicondictor material, and photoelectric efficiency is high, and its photocatalytic activity is even better than current in some aspects
Using most ripe titanium dioxide optical catalyst.And zinc oxide is cheap and easy to get, nontoxic pollution-free, New Generation Optical catalysis is expected to be used for
Agent.It is compound that tungsten oxide then can suppress photo-generate electron-hole to a certain extent.In consideration of it, invention describes one kind in titanium
Belong to matrix surface, the method for preparing three metals oxidation catalytic membrane in situ, the film layer prepared and matrix binding ability are strong, and catalysis is lived
Property it is high, the quick recovery of catalyst can be realized.
The content of the invention
The purpose of the present invention be for plasma electrolytic oxidation catalytic membrane catalytic efficiency it is low the shortcomings that, there is provided it is a kind of
Simple and reliable oxidation catalysis film containing three metals and preparation method and application.
The present invention, by the regulation of technological parameter, controls plasma electrolytic oxidation by selecting alkaline composite electrolyte
Course of reaction, three porous metal oxide film layers in situ are prepared, obtained film surface contains nano ZnO particles, increases
Specific surface area, there is the advantages that adhesive force is good, and photocatalytic activity is high.
The purpose of the present invention is realized by following scheme.
A kind of preparation method of the oxidation catalysis film containing three metals, comprises the following steps：
（1）Substrate pretreated：Matrix is polishing to sand paper step by step smooth；
（2）Matrix surface cleans：It is cleaned by ultrasonic step with ethanol, water successively（1）Pretreated matrix, and done in warm air
It is dry；
（3）Prepare alkaline composite electrolyte：Sodium phosphate, phosphotungstic acid is soluble in water, and additive nano granular of zinc oxide is added,
Mix, obtain alkaline composite electrolyte；
（4）Plasma electrolytic oxidation processing：By step（2）Dried matrix is connected to the anode of power supply, and stainless steel substrates are made
For negative electrode, anode, negative electrode are immersed in equipped with step（3）In the double glazing reactor of the alkaline composite electrolyte, to sun
Apply voltage response between pole, negative electrode, matrix surface growth in situ is gone out the oxidation catalysis film containing three metals.
Preferably, step（1）Described matrix is titanium alloy substrate.
Preferably, step（2）The cleaning of middle surface and oil contaminant and impurity, absolute ethyl alcohol and deionized water can be used, ultrasound is clearly
Wash 5 more than min.
Preferably, step（1）The sand paper is the sand paper of 220 to 4000 mesh.
Preferably, step（3）The sodium phosphate, phosphotungstic acid, the nano zine oxide concentration in alkaline composite electrolyte point
Wei not 12-18 g/L, 1-4 g/L, 1-3 g/L.
Preferably, step（4）In, the distance between anode, negative electrode are 2-5 cm.
Preferably, step（4）In power supply be dc source, the rate of rise of reaction is 20-40 V/10 s, terminal electricity
It is 5-30 min to press as 300-400 V, reaction time.
Preferably, step（4）In, the reactor used is double glazing reactor of the capacity for 500 mL, and reactor presss from both sides
The water temperature of recirculated cooling water is 33-36 DEG C in layer.
Preferably, a kind of electrolytic oxidation catalysis membrane preparation method for containing three metals, this method comprise the following steps：
（1）Polished step by step titanium alloy substrate surface using granularity 220-4000 mesh sand paper, remove surface oxide layer and greasy dirt etc.；
（2）Using absolute ethyl alcohol or acetone and other organic solvent, and deionized water, cleaning step（1）Treated is titanium alloy-based
Body surface face, except degreasing, impurity etc.；
（3）Sodium phosphate-phosphotungstic acid is used as electrolyte component, nano granular of zinc oxide is additive, and content is respectively 12-18
G/L, 1-4 g/L, 1-3 g/L.
（4）Using step（3）Middle electrolyte system, to by step（2）The titanium alloy substrate of processing carries out plasma
Electrolytic oxidation process, react and carried out in the double glazing reactor that a capacity is 500 mL, temperature is adjusted with recirculated water
Degree, circulating water temperature maintain 33-36 DEG C, and electrical parameter is：DC constant voltage operates, and negative and positive the two poles of the earth distance is 2-5 cm, control boosting
Speed is 20-40 V/10 s, and reaction time 5-30 min, end point voltage is 300-400 V, prepares porous TiO2、WO3、ZnO
The oxidation catalysis film of three metals.
A kind of oxidation catalysis film containing three metals as made from the process described above, the oxidation catalysis film mainly by
TiO2、WO3, ZnO compositions, adhesive force reaches 1 grade（GB/T9286-1998）, photocatalytic activity high the advantages that high containing adhesive force.
A kind of above-described application of the oxidation catalysis film in catalytic degradation methylene blue solution containing three metals, tool
Body applying step is as follows：
（1）Oxidation catalysis film containing three metals and methylene blue solution are together put into photo catalysis reactor, lucifuge stirring,
Make the oxidation catalysis film containing three metals and the thing that is degraded reaches adsorption equilibrium；
（2）Using high-pressure sodium lamp as light source, the oxidation catalysis film containing three metals is irradiated from top to bottom and carries out light-catalyzed reaction；
（3）Sampling and measuring is degraded liquid absorbance, is converted to concentration, calculates degradation rate.
Preferably, step（1）The dosage of the oxidation catalysis film containing three metals is accumulated with the effective illuminating surface received
Meter, is 4 cm2；The methylene blue dosage is 50 ml, and concentration is 15 mg/L.
Preferably, step（1）The lucifuge stir the time is 30 min.
Preferably, step（2）The power of the high-pressure sodium lamp is 100 W, light source and the oxidation catalysis film containing three metals
The distance on surface is 25 cm.
Preferably, step（3）In every 10 min sample, by Shimadzu UV-2450 determine solution absorbance, further according to
Standard curve is converted into concentration, calculates degradation rate.
The present invention has the following effects that compared with prior art：
（1）Catalysis film layer prepared by the present invention contains loose structure, is advantageous to the progress of catalytic reaction.
（2）Catalytic membrane prepared by the present invention has higher catalytic activity, and the ultraviolet catalytic of methylene blue solution is dropped
In solution experiment, from 4 cm2Oxidation catalysis film containing three metals, using 100 W high-pressure sodium lamps as light source, regulation light source and catalysis
Agent distance is 25 cm, to the mg/L of 50 ml concentration 15 min degradation rates of methylene blue degradation experiment 120 up to more than 80%, light
Catalytic activity is higher than common plasma electrolytic oxidation film.
（3）Film layer prepared by the present invention is growth in situ, can realize that catalyst is molten with being degraded after catalysis degeneration experiment
The recycling of the quick separating and catalyst of liquid, overcomes the shortcomings that traditional titania powder is not easily recycled separation.
Brief description of the drawings
Fig. 1 is TiO prepared by embodiment 12-WO3The metals of-ZnO three aoxidize the apparent form figure of catalytic membrane；
Fig. 2 is TiO prepared by embodiment 12-WO3The power spectrum and element composition figure of the metals of-ZnO three oxidation catalytic membrane；
Fig. 3 is TiO prepared by embodiment 1-42-WO3The metals of-ZnO three aoxidize degradation effect curve of the catalytic membrane to methylene blue
Figure.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Embodiment 1
A kind of preparation method of the oxidation catalysis film containing three metals, specifically includes following processing step：
（1）Titanium base pre-processes：Successively with 220 #, 400 #, 1000 #, 2000 #, 4000 # sand paper is polished titanium-based step by step
Body（Ti6Al4V）Surface, oxide layer, greasy dirt and the impurity on surface are removed, ensure the precision on processing surface；
（2）Matrix surface cleans：It is cleaned by ultrasonic step respectively with absolute ethyl alcohol, deionized water successively（1）Treated Titanium base
The min of surface 10, except degreasing, impurity, then dried in warm air；
（3）Electrolyte quota：By sodium phosphate and phosphotungstic acid deionized water dissolving, nano granular of zinc oxide is then added, is shaken up,
It is respectively 12 g/L, 2 g/L, 3 g/L electrolyte to obtain sodium phosphate, phosphotungstic acid, nano oxidized zinc concentration；
（4）Using step（3）Middle electrolyte system, to by step（2）The Titanium base of processing carries out plasma electrolytic oxidation
Processing, react and carried out in the double glazing reactor that a capacity is 500 mL, by step（2）Dried matrix is connected to
The anode of power supply, stainless steel substrates are as negative electrode, and negative and positive the two poles of the earth distance is 5 cm, and it is 30 V/10 s to control rate of pressure rise, and direct current is permanent
Press operation, reaction end voltage are 360 V, the min of reaction time 5, adjust temperature with recirculated water, circulating water temperature maintains
35 DEG C, prepare porous TiO2-WO3The metals of-ZnO three aoxidize catalytic membrane.
Application of the catalytic membrane of above-mentioned preparation in degradation of methylene blue solution, is comprised the following steps that：
Using 100 W high-pressure sodium lamps as ultraviolet source, illuminating area metered catalyst dosage is received so that catalyst is actual, by 4
cm2TiO2-WO3It is that 15 mg/L methylene blue solutions are together put into photocatalysis that the metals of-ZnO three, which aoxidize catalytic membrane and 50 ml concentration,
In reactor, light source and TiO2-WO3The metals of-ZnO three oxidation catalytic membrane distance is 25 cm, and lucifuge simultaneously stirs 30 min, every 10
Absorbance is measured by sampling in min, is converted to concentration, calculates degradation rate.
Three metal manufactured in the present embodiment aoxidizes catalytic membrane mainly by TiO2、WO3, ZnO composition（As shown in Figure 2）, adhesive force
Reach 1 grade（GB/T9286-1998）, film layer contains loose structure, is growth in situ（As shown in Figure 1）, 120 min degradation rates can
Up to 84.23%（As shown in Figure 3）.
Embodiment 2
A kind of preparation method of the oxidation catalysis film containing three metals, specifically includes following processing step：
（1）Titanium base pre-processes：Successively with 220 #, 400 #, 1000 #, 2000 #, 4000 # sand paper is polished titanium-based step by step
Body（Ti6Al4V）Surface, oxide layer, greasy dirt and the impurity on surface are removed, ensure the precision on processing surface；
（2）Matrix surface cleans：It is cleaned by ultrasonic step respectively with absolute ethyl alcohol, deionized water successively（1）Treated Titanium base
The min of surface 10, except degreasing, impurity, then dried in warm air；
（3）Electrolyte quota：By sodium phosphate and phosphotungstic acid deionized water dissolving, nano granular of zinc oxide is then added, is shaken up,
It is respectively 14 g/L, 4 g/L, 1 g/L electrolyte to obtain sodium phosphate, phosphotungstic acid, nano oxidized zinc concentration；
（4）Using step（3）Middle electrolyte system, to by step（2）The Titanium base of processing carries out plasma electrolytic oxidation
Processing, react and carried out in the double glazing reactor that a capacity is 500 mL, by step（2）Dried matrix is connected to
The anode of power supply, stainless steel substrates are as negative electrode, and negative and positive the two poles of the earth distance is 3 cm, and it is 20 V/10 s to control rate of pressure rise, and direct current is permanent
Press operation, reaction end voltage are 400 V, the min of reaction time 15, adjust temperature with recirculated water, circulating water temperature maintains
36 DEG C, prepare porous TiO2-WO3The metals of-ZnO three aoxidize catalytic membrane.
Application of the catalytic membrane of above-mentioned preparation in degradation of methylene blue solution, is comprised the following steps that：
Using 100 W high-pressure sodium lamps as ultraviolet source, illuminating area metered catalyst dosage is received so that catalyst is actual, by 4
cm2TiO2-WO3It is that 15 mg/L methylene blue solutions are together put into photocatalysis that the metals of-ZnO three, which aoxidize catalytic membrane and 50 ml concentration,
In reactor, light source and TiO2-WO3The metals of-ZnO three oxidation catalytic membrane distance is 25 cm, and lucifuge simultaneously stirs 30 min, every 10
Absorbance is measured by sampling in min, is converted to concentration, calculates degradation rate.
Three metal manufactured in the present embodiment aoxidizes catalytic membrane mainly by TiO2、WO3, ZnO compositions, adhesive force reaches 1 grade（GB/
T9286-1998）, film layer contains loose structure, is growth in situ, 120 min degradation rates are up to 84.74%（As shown in Figure 3）.
Embodiment 3
A kind of preparation method of the oxidation catalysis film containing three metals, specifically includes following processing step：
（1）Titanium base pre-processes：Successively with 220 #, 400 #, 1000 #, 2000 #, 4000 # sand paper is polished titanium-based step by step
Body（Ti6Al4V）Surface, oxide layer, greasy dirt and the impurity on surface are removed, ensure the precision on processing surface；
（2）Matrix surface cleans：It is cleaned by ultrasonic step respectively with absolute ethyl alcohol, deionized water successively（1）Treated Titanium base
The min of surface 10, except degreasing, impurity, then dried in warm air；
（3）Electrolyte quota：By sodium phosphate and phosphotungstic acid deionized water dissolving, nano granular of zinc oxide is then added, is shaken up,
It is respectively 18 g/L, 1g/L, 2 g/L electrolyte to obtain sodium phosphate, phosphotungstic acid, nano oxidized zinc concentration；
（4）Using step（3）Middle electrolyte system, to by step（2）The Titanium base of processing carries out plasma electrolytic oxidation
Processing, react and carried out in the double glazing reactor that a capacity is 500 mL, by step（2）Dried matrix is connected to
The anode of power supply, stainless steel substrates are as negative electrode, and negative and positive the two poles of the earth distance is 2 cm, and it is 40 V/10 s to control rate of pressure rise, and direct current is permanent
Press operation, reaction end voltage are 330 V, the min of reaction time 30, adjust temperature with recirculated water, circulating water temperature maintains
33 DEG C, prepare porous TiO2-WO3The metals of-ZnO three aoxidize catalytic membrane.
Application of the catalytic membrane of above-mentioned preparation in degradation of methylene blue solution, is comprised the following steps that：
Using 100 W high-pressure sodium lamps as ultraviolet source, illuminating area metered catalyst dosage is received so that catalyst is actual, by 4
cm2TiO2-WO3It is that 15 mg/L methylene blue solutions are together put into photocatalysis that the metals of-ZnO three, which aoxidize catalytic membrane and 50 ml concentration,
In reactor, light source and TiO2-WO3The metals of-ZnO three oxidation catalytic membrane distance is 25 cm, and lucifuge simultaneously stirs 30 min, every 10
Absorbance is measured by sampling in min, is converted to concentration, calculates degradation rate.
Three metal manufactured in the present embodiment aoxidizes catalytic membrane mainly by TiO2、WO3, ZnO compositions, adhesive force reaches 1 grade（GB/
T9286-1998）, film layer contains loose structure, is growth in situ, 120 min degradation rates are up to 76.34%（As shown in Figure 3）.
Embodiment 4
A kind of preparation method of the oxidation catalysis film containing three metals, specifically includes following processing step：
（1）Titanium base pre-processes：Successively with 220 #, 400 #, 1000 #, 2000 #, 4000 # sand paper is polished titanium-based step by step
Body（Ti6Al4V）Surface, oxide layer, greasy dirt and the impurity on surface are removed, ensure the precision on processing surface；
（2）Matrix surface cleans：It is cleaned by ultrasonic step respectively with absolute ethyl alcohol, deionized water successively（1）Treated Titanium base
The min of surface 10, except degreasing, impurity, then dried in warm air；
（3）Electrolyte quota：By sodium phosphate and phosphotungstic acid deionized water dissolving, nano granular of zinc oxide is then added, is shaken up,
It is respectively 16 g/L, 3 g/L, 1.5 g/L electrolyte to obtain sodium phosphate, phosphotungstic acid, nano oxidized zinc concentration；
（4）Using step（3）Middle electrolyte system, to by step（2）The Titanium base of processing carries out plasma electrolytic oxidation
Processing, react and carried out in the double glazing reactor that a capacity is 500 mL, by step（2）Dried matrix is connected to
The anode of power supply, stainless steel substrates are as negative electrode, and negative and positive the two poles of the earth distance is 4 cm, and it is 30 V/10 s to control rate of pressure rise, and direct current is permanent
Press operation, reaction end voltage are 300 V, the min of reaction time 20, adjust temperature with recirculated water, circulating water temperature maintains
34 DEG C, prepare porous TiO2-WO3The metals of-ZnO three aoxidize catalytic membrane.
Application of the catalytic membrane of above-mentioned preparation in degradation of methylene blue solution, is comprised the following steps that：
Using 500 W high-pressure sodium lamps as ultraviolet source, illuminating area metered catalyst dosage is received so that catalyst is actual, by 4
cm2TiO2-WO3It is that 15 mg/L methylene blue solutions are together put into photocatalysis that the metals of-ZnO three, which aoxidize catalytic membrane and 50 ml concentration,
In reactor, light source and TiO2-WO3The metals of-ZnO three oxidation catalytic membrane distance is 25 cm, and lucifuge simultaneously stirs 30 min, every 10
Absorbance is measured by sampling in min, is converted to concentration, calculates degradation rate.
Three metal manufactured in the present embodiment aoxidizes catalytic membrane mainly by TiO2、WO3, ZnO compositions, adhesive force reaches 1 grade（GB/
T9286-1998）, film layer contains loose structure, is growth in situ, 120 min degradation rates are up to 81.94%（As shown in Figure 3）.
Claims (10)
1. a kind of preparation method of the oxidation catalysis film containing three metals, it is characterised in that comprise the following steps：
（1）Substrate pretreated：Matrix is polishing to sand paper step by step smooth；
（2）Matrix surface cleans：It is cleaned by ultrasonic step with ethanol, water successively（1）Pretreated matrix, and done in warm air
It is dry；
（3）Prepare alkaline composite electrolyte：Sodium phosphate, phosphotungstic acid is soluble in water, additive nano granular of zinc oxide is added,
Mix, obtain alkaline composite electrolyte；
（4）Plasma electrolytic oxidation processing：By step（2）Dried matrix is connected to the anode of power supply, and stainless steel substrates are made
For negative electrode, anode, negative electrode are immersed in equipped with step（3）In the double glazing reactor of the alkaline composite electrolyte, to sun
Apply voltage response between pole, negative electrode, matrix surface growth in situ is gone out the oxidation catalysis film containing three metals.
2. a kind of preparation method of oxidation catalysis film containing three metals according to claim 1, it is characterized in that：Step
（1）Described matrix is titanium alloy substrate.
3. a kind of preparation method of oxidation catalysis film containing three metals according to claim 1, it is characterized in that：Step
（1）The sand paper is the sand paper of 220 to 4000 mesh.
4. a kind of preparation method of oxidation catalysis film containing three metals according to claim 1, it is characterized in that：Step
（3）The concentration of the sodium phosphate, phosphotungstic acid, nano zine oxide in alkaline composite electrolyte is respectively 12-18 g/L, 1-4 g/
L、1-3 g/L。
5. a kind of preparation method of oxidation catalysis film containing three metals according to claim 1, it is characterized in that：Step
（4）In, the distance between anode, negative electrode are 2-5 cm.
6. a kind of preparation method of oxidation catalysis film containing three metals according to claim 1, it is characterized in that：Step
（4）In power supply be dc source, the rate of rise of reaction is 20-40 V/10 s, and end point voltage is 300-400 V, during reaction
Between be 5-30 min.
7. a kind of preparation method of oxidation catalysis film containing three metals according to claim 1, it is characterized in that：Step
（4）In, the reactor of use is double glazing reactor, and the water temperature of recirculated cooling water is 33-36 DEG C in reactor interlayer.
A kind of 8. oxidation catalysis film containing three metals as made from the method described in claim any one of 1-7.
9. a kind of oxidation catalysis film containing three metals according to claim 8, it is characterized in that：The oxidation catalysis film is main
By TiO2、WO3, ZnO compositions, adhesive force reaches 1 grade.
A kind of 10. the answering in catalytic degradation methylene blue solution of oxidation catalysis film containing three metals described in claim 9
With.
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| CN113749982A (en) * | 2021-09-05 | 2021-12-07 | 梁莲芝 | Preparation method of antibacterial hand sanitizer |
| CN114057261A (en) * | 2021-08-19 | 2022-02-18 | 南京国兴环保产业研究院有限公司 | Continuous photocatalytic disinfection and purification natural water body equipment and application method thereof |
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| EP3816327A1 (en) | 2019-06-25 | 2021-05-05 | Politechnika Slaska | The formation method of porous antibacterial coatings on titanium and titanium alloys surface |
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| CN110965108A (en) * | 2019-12-27 | 2020-04-07 | 沈兰兰 | Zn-TiO2Method for producing a coating |
| CN113209981A (en) * | 2021-04-02 | 2021-08-06 | 华南理工大学 | FeOOH/Fe3O4/WO3/TiO2photo-Fenton catalytic membrane and preparation method and application thereof |
| CN114057261A (en) * | 2021-08-19 | 2022-02-18 | 南京国兴环保产业研究院有限公司 | Continuous photocatalytic disinfection and purification natural water body equipment and application method thereof |
| CN113749982A (en) * | 2021-09-05 | 2021-12-07 | 梁莲芝 | Preparation method of antibacterial hand sanitizer |
| CN113749982B (en) * | 2021-09-05 | 2024-01-12 | 江西展宏医疗器械有限公司 | Preparation method of antibacterial hand sanitizer |
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