CN107699901B - Preparation method of zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode for photoproduction cathodic protection - Google Patents
Preparation method of zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode for photoproduction cathodic protection Download PDFInfo
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- CN107699901B CN107699901B CN201710865494.3A CN201710865494A CN107699901B CN 107699901 B CN107699901 B CN 107699901B CN 201710865494 A CN201710865494 A CN 201710865494A CN 107699901 B CN107699901 B CN 107699901B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
- C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
- C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
- C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
- C23F13/12—Electrodes characterised by the material
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
Abstract
The invention discloses a preparation method of a zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode for photoproduction cathodic protection, and relates to a composite membrane photo-anode. The invention loads zinc-iron-aluminum hydrotalcite with a unique interlayer structure on a titanium dioxide nanotube to prepare the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode. The zinc-iron-aluminum-loaded hydrotalcite enhances the visible light absorption performance of titanium dioxide, and the unique interlayer structure of the hydrotalcite can improve the separation efficiency of photoproduction electrons and holes. Compared with pure titanium dioxide nanotubes, the composite film photoanode prepared by the invention has higher photocurrent density and potential drop, and can effectively slow down the corrosion of stainless steel.
Description
Technical Field
The invention relates to a composite film photo-anode, in particular to a preparation method of a zinc-iron-aluminum hydrotalcite/titanium dioxide composite film photo-anode for photoproduction cathode protection.
Background
Titanium dioxide (TiO)2) Has good photocatalysis and photosensitization characteristics, and is a photoelectric material with good prospect. At present, titanium dioxide is widely applied to the fields of conductive materials, sensors, photocatalytic materials and the like, and the titanium dioxide also draws wide attention of scholars at home and abroad for the photo-generated cathodic protection of stainless steel. However, TiO2Is aWide forbidden band (3.2eV) conductor which can only absorb ultraviolet light with wavelength less than 380nm, reducing the utilization efficiency of visible light, and TiO2The recombination rate of the photogenerated carriers is high, so that the photogenerated cathode protection has great defects.
Hydrotalcite is a layered multi-metal hydroxide, which has been widely used in the fields of catalysis, photochemistry, electrochemistry, etc. due to its special interlayer structure, ion exchange characteristics, etc., but has not been developed better due to development limitations.
Disclosure of Invention
The invention aims to provide a preparation method of a zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode for photoproduction cathodic protection.
In order to achieve the purpose, the invention adopts the technical scheme that:
a zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode for photoproduction cathode protection is characterized in that a hydrothermal method is adopted to load zinc-iron-aluminum hydrotalcite on a titanium dioxide nanotube to prepare the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode; wherein the loading amount of the zinc-iron-aluminum hydrotalcite is 2-8mmol (based on the total metal ion concentration).
The titanium dioxide nanotube is obtained by carrying out anodic oxidation and calcination on a titanium substrate.
The preparation method of the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode for photoproduction cathodic protection comprises the following steps:
1) TiO on the surface of the titanium substrate2Preparing the nanotube: dissolving ammonium fluoride in ultrapure water, adding ethylene glycol, uniformly mixing to prepare electrolyte, taking the treated titanium substrate as an anode and a platinum sheet as a counter electrode, carrying out anodic oxidation in the electrolyte, calcining in a muffle furnace, and cooling to room temperature to obtain TiO on the surface of the titanium substrate2A nanotube;
2) preparing a zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode: weighing zinc nitrate, ferric nitrate, aluminum nitrate and urea, uniformly mixing, adjusting the pH to 3-4 by using a sodium hydroxide solution, continuously stirring, transferring the uniformly stirred solution into a hydrothermal reaction kettle, and adding the prepared TiO2Nanotube and method of manufacturing the sameSealing the substrate, and carrying out hydrothermal reaction at 100-180 ℃ for 8-16 hours to obtain the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode for photo-generated cathodic protection.
The electrolyte in the step 1) is a glycol solution containing 0.3-0.6 wt.% of ammonium fluoride and 1-2 vol.% of ultrapure water;
anodizing in electrolyte at 20-30V for 0.5-2 hr;
the calcination is to place the titanium matrix after the anodic oxidation treatment in a muffle furnace to be calcined for 2-3 hours at the temperature rising rate of 5 ℃/min to 400-450 ℃.
The processed titanium substrate is cut from a titanium foil with the purity of more than 99.9 percent, the specification size is 40 x 10 x 0.2mm, the titanium substrate is cut and polished by polishing solution, and then the titanium substrate is sequentially ultrasonically cleaned by absolute ethyl alcohol and deionized water and dried for standby.
The polishing solution is a mixed solution of ammonium fluoride, ultrapure water and hydrogen peroxide and nitric acid, wherein the volume ratio of the ultrapure water to the hydrogen peroxide to the nitric acid is 5:12:12, and the mass percent of the ammonium fluoride is 3%.
The hydrothermal method loading refers to uniformly mixing zinc nitrate, ferric nitrate, aluminum nitrate and urea, then adjusting the pH to 3-4 by using 0.5-1mol/L sodium hydroxide solution, continuously stirring, transferring the uniformly stirred solution to a 100ml hydrothermal reaction kettle, and adding the prepared TiO2Sealing the nanotube substrate, and carrying out hydrothermal reaction at 100-180 ℃ for 8-16 hours.
The amounts of the zinc nitrate, the ferric nitrate and the aluminum nitrate are respectively 1-10mmol, 0.05-0.3mmol and 0.2-2mmol, and the amount of the urea is 5-40 mmol.
The prepared zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode is subjected to photo-induced cathodic protection effect test, and a double electrolytic cell system consisting of a photo-electrolytic cell and a corrosion electrolytic cell is specifically adopted. The zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode is arranged in a photo-electrolytic cell, wherein the electrolyte is a mixed solution of 0.1mol/L sodium sulfide and 0.1mol/L sodium thiosulfate. The corrosion electrolytic cell is a two-electrode system, the working electrode is 304 stainless steel, the reference electrode is a saturated calomel electrode, and NaCl solution with the mass concentration of 3.5% is used as a corrosion medium. The photoanode is connected with the protected 304 stainless steel through a lead to serve as a working electrode, and the photoelectrolysis cell is connected with the corrosion electrolysis cell through a salt bridge (agar containing saturated KCl). A300W high-pressure xenon lamp is used as a visible light source (an ultraviolet light filter is added, so that the wavelength of the light source is more than or equal to 400nm), the visible light source directly irradiates the surface of a composite film photo-anode in a photo-electrolytic cell, and an electrochemical workstation P4000 is used for testing the potential change of the stainless steel electrode potential before and after the irradiation.
And testing the photocurrent density of the prepared zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photoanode, wherein the system is a single-electrolytic cell three-electrode system, the Pt electrode is a counter electrode, the saturated calomel electrode is a reference electrode, the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photoanode is a working electrode, and the used solution is a mixed solution of 0.1mol/L of sodium sulfide and 0.1mol/L of sodium thiosulfate. During illumination, a 300W xenon lamp is used as a visible light source (an ultraviolet light filter is added to ensure that the wavelength of the light source is more than or equal to 400nm), and the visible light source directly irradiates the surface of a composite membrane photo-anode in a photo-electrolytic cell.
The basic principle of the invention is as follows: the photo-generated electrons and holes generated under the illumination of titanium dioxide can greatly reduce the recombination probability by virtue of the unique structure of hydrotalcite, and in addition, under the light absorption effect of zinc-iron-aluminum hydrotalcite, compared with pure titanium dioxide, the photo-anode of the composite film has more photo-generated electrons transferred to 304 stainless steel, so that the potential of a stainless steel electrode is shifted negatively, and the stainless steel electrode is in a cathode protection state to slow down corrosion.
The invention has the advantages that:
by means of the visible light absorption characteristic and the interlayer structure characteristic of the hydrotalcite, the invention can increase the light absorption range of the titanium dioxide, simultaneously reduce the recombination probability of photo-generated electrons and holes, greatly enhance the photo-generated cathodic protection characteristic of the titanium dioxide, and solve the problems of weak light absorption and low quantum yield of the existing titanium dioxide as a photo-anode.
1. The invention combines the zinc-iron-aluminum hydrotalcite with a layered structure and the titanium dioxide together, the photocurrent intensity under illumination is obviously enhanced, the potential of the stainless steel is reduced after the zinc-iron-aluminum hydrotalcite is coupled with 304 stainless steel, and the potential drop is far greater than that of the pure titanium dioxide coupled with the stainless steel.
2. The hydrotalcite prepared by the invention has high crystallinity, and the used raw materials are cheap and easy to obtain, thereby effectively saving the cost.
3. The unique interlayer structure of the zinc-iron-aluminum hydrotalcite can effectively reduce the recombination of photo-generated electrons and holes and improve the yield of photo-generated carriers.
4. When the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode prepared by the invention is irradiated by visible light, the potential of a 304 stainless steel electrode in a corrosion electrolytic cell connected with the photo-anode can be obviously reduced and is obviously lower than the self-corrosion potential, and obvious cathode polarization occurs.
5. The potential of the stainless steel electrode stops being raised by light, but is still obviously lower than the natural corrosion potential of the stainless steel, which shows that the composite membrane has good cathodic protection effect and good stability in a dark state.
Drawings
FIG. 1 is a view of TiO provided in example 1 of the present invention2The surface topography of the nanotubes (SEM image) is 2.0 μm with the scale on the top left.
Fig. 2 is a surface topography (SEM image) of the zinc-iron-aluminum hydrotalcite/titanium dioxide composite film provided in embodiment 1 of the present invention, with a scale of 5.0 μm and an enlarged view at the upper left corner.
FIG. 3 is a graph showing the change of electrode potential with time before and after illumination when 304 stainless steel provided in example 1 of the present invention is coupled with a zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photoanode in a 3.5% NaCl solution. Wherein the abscissa is time(s) and the ordinate is electrode potential (V).
FIG. 4 shows TiO provided in example 1 of the present invention2The photo-generated current density of the nanotube and zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane before and after illumination changes along with time, wherein the abscissa is time(s) and the ordinate is the photo-current density (mu A-cm)-2)。
FIG. 5 shows TiO provided in example 2 of the present invention2The surface topography of the nanotubes (SEM image) is 2.0 μm with the scale on the top left.
Fig. 6 is a surface topography (SEM image) of the zinc-iron-aluminum hydrotalcite/titanium dioxide composite film provided in example 2 of the present invention, with a scale of 5.0 μm and an enlarged view at the upper left corner.
FIG. 7 is a graph showing the change of electrode potential with time before and after illumination when 304 stainless steel provided in example 2 of the present invention is coupled with a zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photoanode in a 3.5% NaCl solution. Wherein the abscissa is time(s) and the ordinate is electrode potential (V).
FIG. 8 shows TiO provided in example 2 of the present invention2The photo-generated current density of the nanotube and zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane before and after illumination changes along with time, wherein the abscissa is time(s) and the ordinate is the photo-current density (mu A-cm)-2)。
Detailed Description
The invention is further explained below with reference to the figures and examples.
Example 1
A preparation method of a zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode for photoproduction cathodic protection comprises the following steps:
cutting a titanium sheet with the specification and size of 40 x 10 x 0.2mm from a titanium foil with the purity of more than 99.9 percent as a substrate, sequentially carrying out ultrasonic cleaning in absolute ethyl alcohol and deionized water, and airing for later use.
1.80g NH4F in 10.0mL H2Adding 24.0mL of H into the mixture2O2And 24.0mL HNO3Preparing polishing solution, polishing the cleaned titanium sheet in the polishing solution for 30 seconds, cleaning with a large amount of distilled water, and drying in the air for later use.
0.44g of NH are weighed4F is dissolved in 8mL of deionized water, and 80mL of ethylene glycol is added and uniformly stirred to serve as an electrolyte. And (3) at room temperature, anodizing for 1.5 hours at 20V voltage in electrolyte by using the treated titanium substrate as an anode and a platinum sheet as a cathode, and then washing with deionized water and absolute ethyl alcohol. Then placing the sample in a muffle furnace, raising the temperature to 450 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours, and then cooling to room temperature to obtain TiO on the surface of the titanium substrate2A nanotube.
In TiO2Nanotube surface modified zinc-iron-aluminum loaded hydrotalcite for preparing zinc-iron-aluminum waterTalc/titanium dioxide composite film photo-anode: weighing 1.5mmol of zinc nitrate, 0.05mmol of ferric nitrate, 0.45mmol of aluminum nitrate and 7mmol of urea, uniformly mixing, adjusting the pH to 3.5 by using 0.6mol/L sodium hydroxide solution, continuously stirring for 10 minutes, transferring the uniformly stirred solution to a 100ml hydrothermal reaction kettle, and adding the prepared TiO2Sealing the nanotube substrate, and placing the nanotube substrate in an oven for hydrothermal reaction at 120 ℃ for 8 hours. And obtaining the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode for photoproduction cathode protection.
And (3) carrying out photoproduction cathode protection test on the photo-anode of the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane obtained by the preparation: the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane is used as a photo-anode and is placed in a photo-electrolytic cell containing a mixed solution of 0.1mol/L sodium sulfide and 0.1mol/L sodium thiosulfate. The protected 304 stainless steel is used as a working electrode and is placed in a corrosion electrolytic cell, and 3.5% NaCl is used as a corrosion medium solution. The photo-anode is connected with the stainless steel electrode through a lead and is connected with a working electrode of the electrochemical workstation, and the photo-electrolytic cell is connected with the corrosion electrolytic cell through a salt bridge (containing saturated KCl agar). During illumination, a 300W xenon lamp is used as a visible light source (an ultraviolet light filter is added to ensure that the wavelength of the light source is more than or equal to 400nm), and the visible light source directly irradiates the surface of a composite membrane photo-anode in a photo-electrolytic cell.
And testing the photocurrent of the prepared zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode by using a three-electrode system, wherein a Pt electrode is a counter electrode, a saturated calomel electrode is a reference electrode, a zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane is a working electrode, and the used solution is a mixed solution of 0.1mol/L sodium sulfide and 0.1mol/L sodium thiosulfate. During illumination, a 300W xenon lamp is used as a visible light source (an ultraviolet light filter is added to ensure that the wavelength of the light source is more than or equal to 400nm), and the visible light source directly irradiates the surface of a composite membrane photo-anode in a photo-electrolytic cell.
FIG. 1 shows the TiO thus obtained2SEM image of nanotubes. It can be seen that the nanotubes are relatively uniform.
TiO can be seen from FIG. 22A large amount of zinc-iron-aluminum hydrotalcite is loaded on the surface of the nanotube, and the synthesized hydrotalcite is in a lamellar structure.
304 stainless steel can be seen from figure 33.5 percent NaCl solution and pure TiO in a photoelectrolysis cell respectively2The change curve of the electrode potential along with time after the film is coupled with the zinc-iron-aluminum hydrotalcite/titanium dioxide composite film photoanode, wherein the abscissa is time(s), and the ordinate is the electrode potential (V). The interval time for switching the light on and off was 200 s. Pure TiO in stainless steel and light2When the membrane electrode is coupled, the corrosion potential of the 304 stainless steel is reduced to about-0.38V, and a certain photoproduction cathode protection effect is achieved. When the composite film is coupled with the zinc-iron-aluminum hydrotalcite/titanium dioxide composite film, the potential of the 304 stainless steel can be reduced to about-0.65V, which is obviously lower than the self-corrosion potential. When the light source is switched off, the electrode potential of the stainless steel begins to rise, but at this time the electrode potential of the 304 stainless steel is still much lower than its self-corrosion potential. And (3) performing illumination again, wherein the electrode potential of the stainless steel connected with the composite film is rapidly reduced, which shows that the composite film has good photoproduction cathode protection effect.
As can be seen from FIG. 4, TiO was exposed to light2The maximum transient photocurrent value of the nanotube was 15 μ A cm-2When the zinc-iron-aluminum hydrotalcite is compounded, the maximum value of the transient photocurrent of the composite film is 115 mu A-cm-2The photocurrent density was significantly increased.
Example 2
A preparation method of a zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode for photoproduction cathodic protection comprises the following steps:
cutting a titanium sheet with the specification and size of 40 x 10 x 0.2mm from a titanium foil with the purity of more than 99.9 percent as a substrate, sequentially carrying out ultrasonic cleaning in absolute ethyl alcohol and deionized water, and airing for later use.
0.45g NH4F in 2.5mL H2Adding 6mL of H into the mixture2O2And 6mL HNO3Preparing polishing solution, polishing the cleaned titanium sheet in the polishing solution for 30 seconds, cleaning with a large amount of distilled water, and drying in the air for later use.
0.44g of NH are weighed4F is dissolved in 8mL of deionized water, and 80mL of ethylene glycol is added and uniformly stirred to serve as an electrolyte. At room temperature, the treated titanium matrix is used as an anode, a platinum sheet is used as a cathode, and after anodic oxidation is carried out for 1.5 hours under the voltage of 20V in electrolyte, deionized water is used forAnd washing with absolute ethyl alcohol. Then placing the sample in a muffle furnace, raising the temperature to 450 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 2 hours, and then cooling to room temperature to obtain TiO on the surface of the titanium substrate2A nanotube.
In TiO2Modifying the surface of the nanotube to load zinc-iron-aluminum hydrotalcite, and preparing a zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode: weighing 3mmol of zinc nitrate, 0.1mmol of ferric nitrate, 0.9mmol of aluminum nitrate and 14mmol of urea, uniformly mixing, adjusting the pH to 3.5 by using 0.6mol/L sodium hydroxide solution, continuously stirring for 10 minutes, transferring the uniformly stirred solution to a 100ml hydrothermal reaction kettle, and adding the prepared TiO2Sealing the nanotube substrate, and placing the nanotube substrate in an oven for hydrothermal reaction at 120 ℃ for 8 hours. And obtaining the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode for photoproduction cathode protection.
And (3) carrying out photoproduction cathode protection test on the photo-anode of the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane obtained by the preparation: the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane is used as a photo-anode and is placed in a photo-electrolytic cell containing a mixed solution of 0.1mol/L sodium sulfide and 0.1mol/L sodium thiosulfate. The protected 304 stainless steel is used as a working electrode and is placed in a corrosion electrolytic cell, and 3.5% NaCl is used as a corrosion medium solution. The photo-anode is connected with the stainless steel electrode through a lead and is connected with a working electrode of the electrochemical workstation, and the photo-electrolytic cell is connected with the corrosion electrolytic cell through a salt bridge (containing saturated KCl agar). During illumination, a 300W xenon lamp is used as a visible light source (an ultraviolet light filter is added to ensure that the wavelength of the light source is more than or equal to 400nm), and the visible light source directly irradiates the surface of a composite membrane photo-anode in a photo-electrolytic cell.
And testing the photocurrent of the prepared zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode by using a three-electrode system, wherein a Pt electrode is a counter electrode, a saturated calomel electrode is a reference electrode, a zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane is a working electrode, and the used solution is a mixed solution of 0.1mol/L sodium sulfide and 0.1mol/L sodium thiosulfate. During illumination, a 300W xenon lamp is used as a visible light source (an ultraviolet light filter is added to ensure that the wavelength of the light source is more than or equal to 400nm), and the visible light source directly irradiates the surface of a composite membrane photo-anode in a photo-electrolytic cell.
FIG. 5 shows the TiO produced2SEM image of nanotubes. It can be seen that the nanotubes are relatively uniform.
TiO can be seen from FIG. 62A large amount of zinc-iron-aluminum hydrotalcite is loaded on the surface of the nanotube, and the synthesized hydrotalcite is in a lamellar structure.
From FIG. 7, it can be seen that 304 stainless steel in 3.5% NaCl solution is separated from pure TiO in the photoelectrolysis cell2The change curve of the electrode potential along with time after the film is coupled with the zinc-iron-aluminum hydrotalcite/titanium dioxide composite film photoanode, wherein the abscissa is time(s), and the ordinate is the electrode potential (V). The interval time for switching the light on and off was 200 s. Pure TiO in stainless steel and light2When the membrane electrode is coupled, the corrosion potential of the 304 stainless steel is reduced to about-0.38V, and a certain photoproduction cathode protection effect is achieved. When the composite film is coupled with the zinc-iron-aluminum hydrotalcite/titanium dioxide composite film, the potential of the 304 stainless steel can be reduced to about-0.78V, which is obviously lower than the self-corrosion potential. When the light source is switched off, the electrode potential of the stainless steel begins to rise, but at this time the electrode potential of the 304 stainless steel is still much lower than its self-corrosion potential. And (3) performing illumination again, wherein the electrode potential of the stainless steel connected with the composite film is rapidly reduced, which shows that the composite film has good photoproduction cathode protection effect.
As can be seen from FIG. 8, TiO was irradiated with light2The maximum transient photocurrent value of the nanotube was 15 μ A cm-2When the zinc-iron-aluminum hydrotalcite is compounded, the maximum value of the transient photocurrent of the composite film is 129 muA-cm-2The photocurrent density was significantly increased.
Claims (7)
1. A zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode for photoproduction cathodic protection is characterized in that: 1) TiO on the surface of the titanium substrate2Preparing the nanotube: dissolving ammonium fluoride in ultrapure water, adding ethylene glycol, uniformly mixing to prepare electrolyte, taking the treated titanium substrate as an anode and a platinum sheet as a counter electrode, carrying out anodic oxidation in the electrolyte, calcining in a muffle furnace, and cooling to room temperature to obtain TiO on the surface of the titanium substrate2A nanotube;
2) preparing a zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode: weighing zinc nitrate, ferric nitrate and nitreMixing aluminum and urea uniformly, adjusting pH to 3-4 with sodium hydroxide solution, stirring, transferring the uniformly stirred solution to a hydrothermal reaction kettle, and adding the prepared TiO2Sealing the nanotube substrate, and carrying out hydrothermal reaction at 100-180 ℃ for 8-16 hours to obtain a zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode for photo-generated cathodic protection;
wherein the loading amount of the zinc-iron-aluminum hydrotalcite is 2-8 mmol.
2. A method for preparing the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode for photo-generated cathodic protection according to claim 1, which is characterized in that:
1) TiO on the surface of the titanium substrate2Preparing the nanotube: dissolving ammonium fluoride in ultrapure water, adding ethylene glycol, uniformly mixing to prepare electrolyte, taking the treated titanium substrate as an anode and a platinum sheet as a counter electrode, carrying out anodic oxidation in the electrolyte, calcining in a muffle furnace, and cooling to room temperature to obtain TiO on the surface of the titanium substrate2A nanotube;
2) preparing a zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode: weighing zinc nitrate, ferric nitrate, aluminum nitrate and urea, uniformly mixing, adjusting the pH to 3-4 by using a sodium hydroxide solution, continuously stirring, transferring the uniformly stirred solution into a hydrothermal reaction kettle, and adding the prepared TiO2Sealing the nanotube substrate, and carrying out hydrothermal reaction at 100-180 ℃ for 8-16 hours to obtain the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photo-anode for photo-generated cathodic protection.
3. The method for preparing the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photoanode for photoproduction cathodic protection according to claim 2, characterized in that:
the electrolyte in the step 1) is a glycol solution containing 0.3-0.6 wt.% of ammonium fluoride and 1-2 vol.% of ultrapure water;
anodizing in electrolyte at 20-30V for 0.5-2 hr;
the calcination is to place the titanium matrix after the anodic oxidation treatment in a muffle furnace to be calcined for 2-3 hours at the temperature rising rate of 5 ℃/min to 400-450 ℃.
4. The method for preparing the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photoanode for photoproduction cathodic protection according to claim 2, characterized in that: the processed titanium substrate is cut from a titanium foil with the purity of more than 99.9 percent, the specification size is 40 multiplied by 10 multiplied by 0.2mm, the titanium substrate is cut and polished by polishing solution, and then the titanium substrate is sequentially cleaned by absolute ethyl alcohol and deionized water in an ultrasonic mode and dried for standby.
5. The method for preparing the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photoanode for photoproduction cathodic protection according to claim 4, characterized in that: the polishing solution is a mixed solution of ammonium fluoride, ultrapure water and hydrogen peroxide and nitric acid, wherein the volume ratio of the ultrapure water to the hydrogen peroxide to the nitric acid is 5:12:12, and the mass percent of the ammonium fluoride is 3%.
6. The method for preparing the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photoanode for photoproduction cathodic protection according to claim 2, characterized in that: the hydrothermal method loading refers to uniformly mixing zinc nitrate, ferric nitrate, aluminum nitrate and urea, then adjusting the pH to 3-4 by using 0.5-1mol/L sodium hydroxide solution, continuously stirring, transferring the uniformly stirred solution to a 100ml hydrothermal reaction kettle, and adding the prepared TiO2Sealing the nanotube substrate, and carrying out hydrothermal reaction at 100-180 ℃ for 8-16 hours.
7. The method for preparing the zinc-iron-aluminum hydrotalcite/titanium dioxide composite membrane photoanode for photoproduction cathodic protection according to claim 6, characterized in that: the amounts of the zinc nitrate, the ferric nitrate and the aluminum nitrate are respectively 1-10mmol, 0.05-0.3mmol and 0.2-2mmol, and the amount of the urea is 5-40 mmol.
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