CN108772059B - Preparation of Ag by EDTA disodium-assisted ion exchange2O-TiO2Method for compounding film layer - Google Patents
Preparation of Ag by EDTA disodium-assisted ion exchange2O-TiO2Method for compounding film layer Download PDFInfo
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- 238000013329 compounding Methods 0.000 title claims abstract description 15
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 150000002500 ions Chemical class 0.000 claims abstract description 60
- 239000002243 precursor Substances 0.000 claims abstract description 43
- 238000005342 ion exchange Methods 0.000 claims abstract description 38
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- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
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- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
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- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B01J35/39—
-
- B01J35/393—
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- B01J35/40—
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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
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—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 an Ag preparation method by EDTA disodium auxiliary ion exchange2O‑TiO2A method for compounding a film layer, which belongs to the technical field of nano material preparation; aiming at Ag in the current preparation method2Ag with too low deposition rate of O, difficult process control and deposition2The invention firstly utilizes micro-arc oxidation technology in electrolyte containing precursor ions to prepare TiO containing the precursor ions on a titanium sheet substrate2The precursor ions are ions with EDTA (ethylene diamine tetraacetic acid) complexing stability constant larger than that of Ag ions; then soaking the prepared film layer into an Ag ion exchange solution to exchange the precursor ions in the film layer with the Ag ions in the exchange solution and deposit the Ag ions in situ on the TiO2Forming Ag on the surface of the film2O nano-particles to obtain nano-Ag2O-modified TiO2A heterojunction photocatalytic film layer; the method has the advantages of simple and easily-controlled preparation process, convenient operation, low cost and high and medium photocatalytic activity of the film layer.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to nano Ag2O modified TiO2A heterojunction photocatalytic film layer material and a preparation method thereof.
Background
TiO2The research on the photocatalytic performance began in 1972 and is the most deeply studied photocatalyst. By using TiO2The photocatalyst has the advantages of strong catalytic activity, high stability, no toxicity, high environmental safety and high TiO content2Is a conventional industrial raw material, has low price, is convenient and easy to obtain, and is convenient for industrialization. At present TiO2Has been widely used in the fields of wastewater treatment, environmental protection, antifouling, antibiosis and the like. However, the powder catalyst has many inconveniences in practical application, is difficult to separate and recover, and needs additional processes. The catalyst is therefore preferably provided with a support structure, which is most often coated and attached to the support surface.
The micro-arc oxidation technology can directly prepare TiO on the surface of titanium and titanium alloy2The coating has a complex porous structure and large specific surface area. In addition, micro-arc oxidationThe coating has good mechanical property, wear resistance and corrosion resistance. Thus preparing TiO by micro-arc oxidation technology2Photocatalytic coatings have natural advantages. However, TiO2Coating materials, like powdered materials, still have a number of disadvantages. First, TiO2The forbidden band width is large (3.2 ev), only absorbs ultraviolet light, the sunlight utilization rate is only 4 percent, and the TiO is2The biggest problem faced by the material. On the other hand, TiO2The photoproduction electron-hole pair is easy to recombine and lose efficacy in the photocatalysis process, and the photocatalysis efficiency is greatly reduced. Research shows that the TiO is2The semiconductor heterojunction structure is compounded with other materials to effectively solve the problems.
In TiO2Among the various heterogeneous materials, silver and silver-based compounds show great advantages due to the characteristics of high efficiency, low cost, easy preparation, suitability for industrialization and the like. Wherein Ag is2O is an excellent representative thereof. Ag2O is a narrow bandgap p-type semiconductor with a forbidden band width of only 1.2 eV. By using Ag2O to TiO2Sensitizing to form p-n heterojunction photocatalyst, and optionally adding TiO2The absorption spectrum of the solar cell is expanded to be within the visible light range, and the utilization rate of sunlight is improved. And utilizes Ag2O and TiO2The p-n junction effect between the two can force the photogenerated electrons in the system to the n-type TiO2And transferring the photo-generated holes to the valence band of the p-type Ag2O, realizing the high-efficiency separation of photo-generated electrons and holes of the photocatalyst, reducing the charge recombination probability and further improving the catalytic efficiency of the photocatalyst. Inspired by the above, researchers added Ag into the micro-arc oxidation electrolyte of titanium alloy2O particles to prepare Ag2O particle modified TiO2Micro-arc oxidation coating, and the result shows that the photocatalytic degradation capability of the coating is obviously improved. However, this method Ag2The utilization rate of O particles is extremely low, most of O particles are remained in electrolyte, a large amount of waste is caused, and the cost is increased while the environment is polluted. Therefore, it is necessary to develop an efficient and low-cost silver oxide composite technology for producing Ag with excellent properties and low price2O-modified TiO2And (3) micro-arc oxidation composite coating. Impregnation with silver ion-containing solutionThe deposition can also modify Ag on the surface of the coating2O, this method is convenient and rapid, but the problem is Ag2The deposition rate of O is too low, which is greatly influenced by the surface factors of the coating, the process is difficult to control, and the deposited Ag2The uniformity of O particles is poor and the adhesive force is low. However, if the manner of the impregnation deposition is modified, Ag can be obtained2The O deposition is changed into an in-situ growth process on the surface of the coating, so that the deposition position has selectivity, and the deposition amount can be quantitatively controlled, thereby solving the problems.
Therefore, the solution dipping deposition is a solid-liquid interface reaction, and the adsorption effect of the coating surface on silver ions is utilized, so that an ion exchange mechanism can be introduced, the silver ions are forced to carry out in-situ deposition on the coating surface, and the problems of deposition selectivity and quantitative control are solved by regulating and controlling the doping amount of precursor ions.
Disclosure of Invention
In order to solve the problems, the invention discloses an Ag preparation method by EDTA disodium auxiliary ion exchange2O-TiO2A method for compounding a film layer. Firstly, TiO doped with precursor ions (ions with EDTA complexing stability constant larger than that of Ag ions, such as common metal ions of Ca, Cu, Fe, Ni, Mn, Co, Ce and the like) is prepared by utilizing micro-arc oxidation technology2And (3) a film layer, and then immersing the film layer into an Ag ion exchange solution. Ag ions, EDTA ions and OH in the Ag ion exchange solution-Once the micro-arc oxidation film layer is immersed into the micro-arc oxidation film layer, the precursor ions in the film layer can replace the Ag ions complexed by the EDTA, and the replaced Ag ions are immediately mixed with OH-Reaction to form Ag2O is precipitated and deposited in situ on TiO2Forming Ag on the surface of the film2O-TiO2And (5) compounding the film layer. The method integrates all the advantages of micro-arc oxidation technology and ion exchange technology, can conveniently and rapidly prepare large-area coatings, and Ag2The O nano particles are uniformly distributed in the TiO2The surface of the film layer forms a micron-nanometer multilevel structure, thereby greatly improving the specific surface area, providing more reaction active sites for the photocatalytic reaction and obviously improving the Ag content2O-TiO2The photocatalytic performance of the composite film layer provides the possibility. The hair is usedThe method provides an effective way for preparing the nano composite membrane material, and the heterojunction photocatalytic membrane material prepared by the method has wide application prospect in the fields of sewage treatment, environmental protection and the like.
In addition, the invention can be used for preparing other oxide heterojunction compounds based on the principle, and is applied to the fields of photocatalysis, electrocatalysis, photo-electric conversion and the like.
Preparation of Ag by EDTA disodium-assisted ion exchange2O-TiO2The method for compounding the film layer comprises the following specific steps:
1) preparing precursor ion-doped TiO on a titanium sheet substrate by using a micro-arc oxidation technology by taking a titanium sheet substrate material as an anode, a stainless steel electrolytic tank as a cathode and a mixed solution containing precursor ions and phosphate ions as an electrolyte2A film layer; the titanium sheet base material may use pure titanium or a titanium alloy.
2) TiO doped with precursor ions2The film layer is immersed in the Ag ion exchange solution, the precursor ions in the film layer are used for replacing the Ag ions in the Ag ion exchange solution, and nano Ag is formed in situ on the surface of the film layer2O particles to finally obtain the nano Ag2O modified TiO2A heterojunction photocatalytic film layer material;
the precursor ions in the step 1) are ions with a complexing stability constant with EDTA (ethylene diamine tetraacetic acid) larger than that of Ag ions and EDTA, and comprise metal ions of Ca, Cu, Fe, Ni, Mn, Co, Ce and other elements.
The preparation method of the electrolyte containing the precursor ions used in the micro-arc oxidation process in the step 1) comprises the following steps: adding 8-16g/L trisodium phosphate, 2-6g/L disodium ethylene diamine tetraacetate and 6-10g/L nitrate or acetate of precursor ions into 1L of pure water, and stirring by using a magnetic stirrer until the salts are completely dissolved, namely the electrolyte required in the experimental process.
The preparation method of the Ag ion exchange solution in the step 2) comprises the following steps:
a. respectively preparing a solution A and a solution B:
solution A: 1-10g/L silver nitrate solution.
Solution B: 1-4g/L of disodium ethylene diamine tetraacetate and 0.5-4g/L of potassium hydroxide mixed solution;
b. and (3) slowly adding the solution A into the solution B drop by drop, centrifuging after precipitates appear, and taking supernate, namely the solution for ion exchange.
Step 1) the power supply parameters in the micro-arc oxidation process are set as follows:
the power supply adopts a biphase pulse mode, the frequency is 50-1200 Hz, the duty ratio is 45-80%, and the electrical parameters of the power supply input mode under the constant voltage mode and the constant current mode are set as follows:
under a constant voltage mode, applying a forward voltage of 350V-450V, and keeping the treatment time for 20-60 min;
in the constant current mode, the forward voltage is regulated to make the current density be 0.01A/cm2-1A/cm2Keeping the treatment time for 20-60 min.
Preferably, the ion replacement process parameters in step 2) are as follows: heating the Ag ion exchange solution in water bath at 0-100 deg.C for 2-6 hr.
The nano Ag obtained by the method2O modified TiO2The heterojunction photocatalytic film material has a porous structure and an inner layer of TiO2The thickness of the layer and the film layer is 5-100 mu m, and the surface layer is uniformly modified with nano Ag2O particles, Ag2The grain diameter of the O particles is between 5 and 70 nm.
The invention has the beneficial effects that:
1. the equipment is micro arc oxidation equipment, the auxiliary equipment is a simple solution tank, the method is simple, the cost is low, and the continuous preparation of large-area film materials can be realized.
2. Nano Ag2O and TiO2The formed heterojunction structure can reduce the recombination probability of photo-generated electron-hole pairs and broaden TiO2The photoresponse range of the film further improves the absorption of the film to light in a visible light range, effectively improves the photocatalytic degradation efficiency of the film to organic pollutants, and has high practical value and application prospect.
Drawings
FIG. 1 shows a schematic view of aFormation of precursor ion-containing Ca for inventive example 12+Of TiO22Scanning electron microscope photo of the film;
FIG. 2 shows the ion-exchanged Ag nanoparticles of example 1 of the present invention2O modified TiO2Scanning electron microscope photo of the heterojunction photocatalysis film layer;
FIG. 3 shows Ca containing precursor ion formed in example 1 of the present invention2+Of TiO22Film layer, nano Ag2O modified TiO2Heterojunction photocatalytic film layer and pure TiO2X-ray diffraction spectrum of the film layer;
FIG. 4 shows the formation of nano Ag according to example 1 of the present invention2O modified TiO2A spectrum of the heterojunction photocatalytic film layer;
FIG. 5 shows the nano Ag prepared in example 1 of the present invention2O modified TiO2An X-ray photoelectron energy spectrum of the heterojunction photocatalytic film layer;
FIG. 6 shows the nano Ag prepared in example 1 of the present invention2O modified TiO2Heterojunction photocatalytic film layer and TiO containing precursor ion Ca2Film and pure TiO2Ultraviolet-visible absorption spectrum of the film layer;
FIG. 7 shows the prepared nano Ag formed in example 1 of the present invention2O modified TiO2Heterojunction photocatalytic film layer and TiO containing precursor ion Ca2Film and pure TiO2The degradation effect of the film layer on methyl blue under ultraviolet light;
FIG. 8 shows the prepared nano Ag formed in example 1 of the present invention2O modified TiO2Heterojunction photocatalytic film layer and TiO containing precursor ion Ca2Film and pure TiO2The degradation effect of the film layer on methyl blue under visible light;
Detailed Description
The technical solution of the present invention is further explained and illustrated below with reference to the examples and the accompanying drawings.
Example 1
In this embodiment, EDTA disodium salt assisted ion exchange method for preparing Ag2O-TiO2A method of compounding a film comprising the steps of:
s1, mixing the mixture by 1cm2The pure titanium sample is subjected to degreasing and descaling treatment by acid liquor, and then is cleaned by ultrasonic waves in ethanol and deionized water for 5 minutes respectively; using a bidirectional pulse power supply, taking a pure titanium sample as an anode, a stainless steel electrolytic tank as a cathode, and a solution containing trisodium phosphate, ethylene diamine tetraacetic acid disodium salt and calcium acetate as an electrolyte, and carrying out micro-arc oxidation treatment under the stirring condition;
the electrolyte is prepared by dissolving 8g of trisodium phosphate, 2g of disodium ethylenediamine tetraacetic acid and 6g of calcium acetate in 1L of deionized water. The power supply mode adopts a constant voltage mode, and the processing time is 30min under a constant forward voltage of 400V. After the reaction is finished, taking out the titanium sheet, cleaning the titanium sheet by using deionized water, and naturally drying to obtain Ca containing precursor ions2+Of TiO22And (5) film layer.
S2, adding precursor ion Ca2+Of TiO22The membrane layer is immersed into 50mL of Ag ion exchange solution for ion exchange;
the preparation method of the Ag ion exchange solution comprises the following steps: firstly, preparing enough 10g/L silver nitrate solution (namely solution A), then preparing mixed solution (namely solution B) of ethylenediaminetetraacetic acid disodium salt and 2g/L potassium hydroxide, dropwise and slowly adding the solution A into the solution B until precipitates appear, centrifuging, and taking supernatant fluid, namely the solution for ion exchange. In the ion exchange process, the sample is taken out after the water bath heating is needed and the temperature is kept at 50 ℃ for 4 hours, and the sample is cleaned by deionized water and naturally dried to obtain the nano Ag2O modified TiO2And (4) storing the heterojunction photocatalytic film material in dark.
As shown in FIG. 1, the precursor ion Ca prepared by micro-arc oxidation2+Of TiO22The film layer is in a porous structure, and the hole wall is smooth. After ion exchange is carried out by comparing with the figure 2, a layer of uniform nano Ag is generated on the surface2O particles, which shows that the nano Ag is successfully prepared2O modified TiO2A heterojunction photocatalytic film layer. FIG. 3 is the X-ray diffraction spectrum of the film before and after ion exchange, and there is no obvious difference between the two spectra, and the main crystal phase is anatase type TiO2Description of ion exchangeThe replacing step can not damage TiO in the film layer2And (4) phase(s). In addition, because of Ag2Too small amount of O particles in the nano Ag2O modified TiO2Ag is not found in the spectrum of the heterojunction photocatalytic film layer2And the diffraction peak of O, so that the film layer is further subjected to energy spectrum analysis and surface photoelectron spectrum analysis. Ag is found in the spectrum result of FIG. 3, and the surface photoelectron spectrum result of FIG. 4 demonstrates that Ag is the same as Ag2The form of O exists. To show nano Ag3PO4Modified TiO2The degradation capability of the heterojunction photocatalytic film material is superior to that of the traditional micro-arc oxidation pure TiO2The film was compared to a TiO2 film containing only the precursor ion Ca. The ultraviolet-visible spectrum result of fig. 5 shows that the absorption capacity of the nano-Ag 2O modified TiO2 heterojunction film layer for visible light is obviously enhanced. The methyl blue degradation experiment of fig. 6 shows that the degradation capability is obviously improved under both ultraviolet light and visible light conditions.
The micro-arc oxidation process in the above step S1 is to prepare TiO containing precursor ions2The film layer, therefore, the content and the type of the precursor ions in the prepared film layer can be controlled by adjusting the components of the electrolyte. Therefore, in other embodiments, the electrolyte used for the micro-arc oxidation treatment is: adding 8-16g/L trisodium phosphate, 2-6g/L disodium ethylenediamine tetraacetic acid and 6-10g/L nitrate or acetate of precursor ions into 1L of pure water, and obtaining the required electrolyte after complete dissolution.
In addition, the power supply parameters and the micro-arc oxidation time in the micro-arc oxidation process are controlled, and the thickness of the film layer, the pore diameter of micropores on the surface of the film layer, the porosity, the mechanical strength of the film layer and the content of precursor ions can be regulated and controlled. Thus in other examples the micro arc oxidation power supply parameters are set as:
the power supply adopts a biphase pulse mode, the frequency is 50-1200 Hz, the duty ratio is 45-80%, and the output mode of the power supply can be selected from a constant voltage mode and a constant current mode.
Under a constant voltage mode, applying a forward voltage of 350V-450V, and keeping the treatment time for 20-60 min;
or in the constant-current mode, the voltage is controlled,applying a forward voltage to a current density of 0.01A/cm2-1A/cm2Keeping the treatment time for 20-60 min.
Therefore, the electrolyte, the power supply parameter and the micro-arc oxidation time used in the micro-arc oxidation process are controlled, so that the TiO rich in precursor ions can be effectively controlled2The thickness, the composition (including the types of the contained precursor ions), the internal microcrystalline structure form and the surface appearance of the film layer are optimized, so that the mechanical properties (including hardness, bonding strength and the like), the surface characteristics (including porosity, pore size distribution, specific surface area and the like) and the like of the film layer are optimized, and the TiO rich in the precursor ions2The quality of the film layer is obviously improved.
The purpose of the above step S2 is to make the TiO prepared in the step S12Exchanging the precursor ions contained in the film layer with Ag ions in the Ag ion exchange solution, and depositing the Ag ions on TiO in situ2Forming Ag on the surface of the film2O nano-particles to obtain nano-Ag2O-modified TiO2A heterojunction photocatalytic film layer.
Therefore, in other embodiments, the preparation method of the middle Ag ion exchange liquid is as follows:
a. respectively preparing a solution A and a solution B:
solution A: 1-10g/L silver nitrate solution.
Solution B: 1-4g/L of disodium ethylene diamine tetraacetate and 0.5-4g/L of potassium hydroxide mixed solution;
b. and (3) slowly adding the solution A into the solution B drop by drop, centrifuging after precipitates appear, and taking supernate, namely the solution for ion exchange.
The pH value and the contained Ag ion concentration of the Ag ion exchange solution directly determine the nano Ag2The degree of uniformity of distribution of O particles, the size of the particle diameter and the amount of deposition.
In addition, Ag2The degree of uniformity of the distribution of the O particles, the size of the particles, and the deposition amount are also influenced by the temperature and the soaking time, so in other embodiments, the ion replacement process parameters are specifically as follows: heating the Ag ion exchange solution in water bath at 0-100 deg.C for 2-6 hr.
Nano Ag2The formation of the O particles enables the film layer to utilize an expanded visible region for light, thereby improving the light utilization rate of the film layer material. Regulating nano Ag2The particle size and distribution of the O particles can more effectively inhibit the recombination of photo-generated electron-hole pairs, provide more reactive active sites and integrally improve the capability of the film layer of degrading pollutants by photocatalysis.
After the above steps of S1 and S2 processes and the control of the process conditions, in the above examples, the prepared nano Ag2O particle modified TiO2A heterojunction photocatalytic film layer composed of TiO2Base layer and nano Ag on surface thereof2And an O-modification layer. Wherein the TiO is2The layer presents the porous appearance of the micro-arc oxidation film layer, the thickness of the film layer is 5-100 μm, and the aperture is 0.1-10 μm. Ag2The grain diameter of the O particles is between 5 and 70 nm.
Claims (9)
1. Preparation of Ag by EDTA disodium-assisted ion exchange2O-TiO2The method for compounding the film layer comprises the following specific steps:
1) preparing precursor ion-containing TiO on a titanium sheet substrate by using a micro-arc oxidation method by taking a titanium sheet substrate material as an anode, a stainless steel electrolytic tank as a cathode and a solution containing precursor ions as an electrolyte2A film layer; the titanium sheet base material is pure titanium or titanium alloy;
2) TiO doped with precursor ions2The film layer is immersed in the Ag ion exchange solution, the precursor ions in the film layer are used for replacing the Ag ions in the Ag ion exchange solution, and nano Ag is formed in situ on the surface of the film layer2O particles to finally obtain the nano Ag2O modified TiO2A heterojunction photocatalytic film layer material;
the electrolyte containing the precursor ions in the step 1) is an aqueous solution containing the precursor ions, phosphate ions and ethylenediaminetetraacetic acid ions; the precursor ions refer to ions with the EDTA complex stability constant larger than that of the Ag ions and the EDTA;
the electrolyte containing the precursor ions in the step 1) is prepared by adding 8-16g/L trisodium phosphate, 2-6g/L disodium ethylenediamine tetraacetic acid and 6-10g/L nitrate or acetate of the precursor ions into 1L pure water and stirring until the precursor ions are completely dissolved;
the preparation method of the Ag ion exchange solution in the step 2) comprises the following steps:
a. respectively preparing a solution A and a solution B:
solution A: 1-10g/L silver nitrate solution;
solution B: 1-4g/L of disodium ethylene diamine tetraacetate and 0.5-4g/L of potassium hydroxide mixed solution;
b. and (3) slowly adding the solution A into the solution B drop by drop, centrifuging after precipitates appear, and taking supernate, namely the solution for ion exchange.
2. Preparation of Ag by disodium EDTA-assisted ion exchange according to claim 12O-TiO2A method for compounding a film layer, characterized in that,
in the step 1), when the micro-arc oxidation method is used, the power supply parameters are set as follows:
the power supply adopts a biphase pulse mode, the frequency is 50-1200 Hz, the duty ratio is 45-80%, and the electrical parameters of the power supply input mode under the constant voltage mode and the constant current mode are set as follows:
under a constant voltage mode, applying a forward voltage of 350V-450V, and keeping the treatment time for 20-60 min;
in the constant current mode, the forward voltage is regulated to make the current density be 0.01A/cm2-1A/cm2Keeping the treatment time for 20-60 min.
3. Preparation of Ag by disodium EDTA-assisted ion exchange according to claim 12O-TiO2The method for compounding the film layer is characterized in that the electrolyte containing precursor ions is prepared by adding 8g/L trisodium phosphate, 2g/L disodium ethylene diamine tetraacetate and 6g/L calcium acetate into 1L pure water and stirring until the trisodium phosphate, the disodium ethylene diamine tetraacetate and the calcium acetate are completely dissolved.
4. Preparation of Ag by disodium EDTA-assisted ion exchange according to claim 22O-TiO2The method for compounding the film layer is characterized in that the micro-arc oxidation treatment parameters in the step 1) are set as follows: power supplyThe mode adopts constant voltage mode, and the processing time is 30min under the constant forward voltage of 450V.
5. Preparation of Ag by disodium EDTA-assisted ion exchange according to claim 12O-TiO2A method of compounding a film, characterized in that solution a: 3g/L silver nitrate solution; solution B: 2g/L of ethylenediamine tetraacetic acid disodium salt and 1g/L of potassium hydroxide mixed solution.
6. Preparation of Ag by disodium EDTA-assisted ion exchange according to claim 12O-TiO2The method for compounding the film layer is characterized in that the precursor ions are metal ions of Ca, Cu, Fe, Ni, Mn, Co or Ce elements.
7. Preparation of Ag by disodium EDTA-assisted ion exchange according to claim 12O-TiO2The method for compounding the film layer is characterized in that the ion replacement process parameters in the step 2) are as follows: heating the Ag ion exchange solution in water bath at 0-100 deg.C for 2-6 hr.
8. Ag prepared by the preparation method of any one of claims 1-72O-TiO2And (4) compounding the membrane material.
9. Ag according to claim 82O-TiO2The composite membrane layer material is characterized in that the structure is porous, and the surface layer is modified with nano Ag2O particles, Ag2The grain diameter of O particles is 5-70nm, and the inner layer is TiO2The thickness of the film layer is 5-100 μm.
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