CN111172545B - Photo-anode of ionic liquid modified semiconductor composite film and preparation method thereof - Google Patents
Photo-anode of ionic liquid modified semiconductor composite film and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 239000004065 semiconductor Substances 0.000 title claims abstract description 17
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 42
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 239000010963 304 stainless steel Substances 0.000 abstract description 22
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 abstract description 22
- 239000012528 membrane Substances 0.000 abstract description 4
- 229910010413 TiO 2 Inorganic materials 0.000 abstract 3
- 230000008021 deposition Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 238000005260 corrosion Methods 0.000 description 9
- 239000002071 nanotube Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000007598 dipping method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000007743 anodising Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000005286 illumination Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000004210 cathodic protection Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 tetramethyl lactate Chemical compound 0.000 description 1
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
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Abstract
本发明涉及改性的半导体复合膜，尤其是涉及一种离子液体改性的半导体复合膜(针对304不锈钢)的光阳极及其制备方法。具体为以清洗后基材作为阳极在氟化铵溶液中反复进行氧化处理，获得TiO2纳米阵列管，而后将TiO2纳米阵列管于TMGL溶液中浸渍2‑3h，进而获得沉积TMGL@TiO2膜光阳极。本发明所得光阳极采用离子液体改性的半导体复合膜针对304不锈钢进行光生阴极保护，使其具有良好的热力学稳定性、可设计性和可操作性。The invention relates to a modified semiconductor composite film, in particular to a photoanode of an ionic liquid modified semiconductor composite film (for 304 stainless steel) and a preparation method thereof. Specifically, the cleaned substrate is used as the anode for repeated oxidation treatment in ammonium fluoride solution to obtain TiO 2 nano-array tubes, and then the TiO 2 nano-array tubes are immersed in TMGL solution for 2-3 h to obtain deposition of TMGL@TiO 2 . Membrane photoanode. The photoanode obtained by the invention adopts the semiconductor composite film modified by ionic liquid to carry out photocathode protection for 304 stainless steel, so that it has good thermodynamic stability, designability and operability.
Description
Technical Field
The invention relates to a modified semiconductor composite film, in particular to a photoanode of an ionic liquid modified semiconductor composite film (aiming at 304 stainless steel) and a preparation method thereof.
Background
Titanium dioxide belongs to an n-type semiconductor, the surface of the titanium dioxide is enriched with electrons when the titanium dioxide is illuminated, and if the electrons can be transferred to the surface of 304 stainless steel, a cathode protection effect is generated on 304. The titanium dioxide semiconductor material has the advantages of good chemical and thermodynamic stability, environmental protection, no electric energy consumption and the like, is one of the most developed green, economic and environment-friendly photocatalysts, and is widely applied to the fields of photocatalytic degradation of organic matters, photocatalytic hydrogen cracking, cathode protection of light and the like. Some of the present methods for preparing TiO2The methods of (2) all have certain disadvantages, such as: the inner diameter of the prepared nano material is generally larger by a template method, and the appearance is limited by the appearance of the template. The preparation process is also relatively complex, and mass production of samples is not easy to realize; the hydrothermal synthesis method has high requirements on equipment, needs a lining resistant to high temperature and high pressure corrosion, needs to be carried out in a closed container, is not favorable for observing the growth process of the material, has poor safety performance, is sensitive to external conditions such as temperature and the like, and ensures that the prepared TiO is2The nanotube array is disordered and irregular, and the structure is disordered.
Disclosure of Invention
The invention aims to provide a photoanode of an ionic liquid modified semiconductor composite film (aiming at 304 stainless steel) and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing ionic liquid modified photo-anode of semiconductor composite film includes using cleaned substrate as anode to carry out oxidation treatment in ammonium fluoride solution repeatedly to obtain TiO2Nano array tube and then TiO2Soaking the nano array tube in TMGL tetramethyl lactate (TMGL solution) solution for 2-3h to obtain deposit TMGL @ TiO2And (6) film photo-anode.
The repeated oxidation treatment is to repeatedly perform anodic oxidation on the matrix in an ammonium fluoride solution, and then calcine the matrix to obtain the substrate with the TiO2 nanotube array film attached to the surface; wherein, hydrochloric acid is adopted to clean the matrix between two times of anodic oxidation.
Further, the cleaned base material is used as an anode to be subjected to oxidation treatment in an ammonium fluoride solution, the surface of the cleaned base material is subjected to ultrasonic treatment by using a hydrochloric acid solution after the oxidation treatment, and then the cleaned base material is subjected to oxidation treatment in the ammonium fluoride solution to obtain TiO2Oxidizing the nano array tube to obtain TiO2Dipping the nano array tube in a TMGL solution for 2-3h to obtain a deposit TMGL @ TiO2And (6) film photo-anode.
Dipping TMGL on the surface of the substrate with the TiO2 nanotube array film attached to the surface by adopting a dipping method, and then calcining to obtain the TMGL modified TiO2 nanotube array film.
The base material is a pure titanium sheet which is washed by acetone, absolute ethyl alcohol and distilled water in sequence through ultrasonic washing.
Taking the cleaned substrate as an anode, carrying out oxidation treatment for 1-2h in ammonium fluoride solution at a voltage of 60-75V for the anode, cleaning after oxidation, carrying out ultrasonic treatment under the condition of hydrochloric acid, airing, carrying out oxidation treatment for 1-2h in the ammonium fluoride solution at a voltage of 60-75V for the dried substrate, cleaning after oxidation, raising the temperature to 550 ℃ at a heating rate of 5-10 ℃/min in a muffle furnace for calcining for 2-3h, and cooling to room temperature along with the furnace after calcining to obtain the TiO2And (4) nano array tubes.
The ammonium fluoride solution is prepared by dissolving ammonium fluoride in water, adding ethylene glycol, and stirring for 3-4 h; wherein the volume ratio of the deionized water to the ethylene glycol is 1: 9-1:10, and the mass fraction of ammonium fluoride is 0.3% -0.4%.
Said to obtain TiO2Immersing the nano array tube in a TMGL solution, soaking for 2-3h at room temperature, and then calcining for 2-3h at the temperature of 150-; the concentration of TMGL is 5.0-10 g/L.
The photoanode of the ionic liquid modified semiconductor composite film is prepared according to the method.
The invention has the advantages that:
the photo-anode adopts the ionic liquid modified semiconductor composite film to carry out photo-cathode protection on 304 stainless steel, so that the photo-anode has good thermodynamic stability, designability and operability. As can be seen from FIGS. 2 and 3, the TiO2 nanotube photoanode without TMGL modification under the irradiation of visible light causes the self-corrosion potential of 304 stainless steel to be reduced by 91mV, and the current density transmitted to 304 stainless steel is 1X 10-5mA/cm2The self-corrosion potential of the 304 stainless steel is reduced by 164mV under the irradiation of visible light by the TMGL-modified TiO2 nanotube photo-anode, and the current density transmitted to the 304 stainless steel is 3.5X 10-5mA/cm2The photo-generated cathodic protection effect of the photo-anode on the 304 stainless steel is greatly improved.
Drawings
Fig. 1 is an SEM image of a TiO2 nanotube array film prepared according to an embodiment of the present invention.
FIG. 2 is a diagram illustrating the effect of the composite membrane prepared according to the embodiment of the present invention.
FIG. 3 is a diagram illustrating the effect of the composite membrane prepared according to the embodiment of the present invention.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
Example 1
1. A flat and smooth rectangular pure titanium foil sample with the thickness of 0.3mm is taken and sequentially subjected to ultrasonic cleaning for 10min by acetone, absolute ethyl alcohol and distilled water respectively.
2. 1.72g of ammonium fluoride is weighed into 50g of distilled water, the mixture is stirred evenly, 450mL of ethylene glycol is added, and the mixture is stirred for 3 hours to prepare ammonium fluoride solution. And (3) anodizing the titanium foil substrate cleaned in the step (1) at room temperature for 1h at a voltage of 60V in the ammonium fluoride solution by using a platinum sheet as an anode. And (3) washing the titanium foil substrate by using distilled water, carrying out ultrasonic treatment in a 0.1M hydrochloric acid solution for 30min until the surface is smooth and bright, and airing the titanium foil substrate to obtain the primarily oxidized titanium foil substrate for later use.
3. And (3) anodizing the titanium foil substrate subjected to primary oxidation at room temperature for 1h at a voltage of 60V in the ammonium fluoride solution by using a platinum sheet as a cathode. Washing with distilled water. Then placing the sample in a muffle furnace to be calcined for 2h at the temperature of 450 ℃, and then cooling the sample to room temperature along with the furnace to obtain TiO2The nano array tube (see fig. 1).
4. Dipping the obtained TiO2 nano array tube in 5.0g/L TMGL solution for 2h, and calcining at 150 ℃ for 3h to obtain TMGL @ TiO for 304 stainless steel photo-generated cathode protection2A photoanode of the film.
As can be seen from FIG. 1, the TiO we prepared2The inner diameter of the nano-array tube is about 150nm, and the nano-array tube is uniformly and orderly arranged.
Example 2
1. A flat and smooth rectangular pure titanium foil sample with the thickness of 0.3mm is taken and is sequentially subjected to ultrasonic cleaning for 5min by acetone, absolute ethyl alcohol and distilled water respectively.
2. 0.172g of ammonium fluoride is weighed into 5g of distilled water, the mixture is stirred evenly, 45mL of ethylene glycol is added, and the mixture is stirred for 3 hours to prepare ammonium fluoride solution. And (3) anodizing the titanium foil substrate cleaned in the step (1) at room temperature for 2h at a voltage of 75V in the ammonium fluoride solution by taking the titanium foil substrate as an anode and a platinum sheet as a cathode. And (3) washing the titanium foil substrate by using distilled water, carrying out ultrasonic treatment in a 0.1M hydrochloric acid solution for 45min until the surface is smooth and bright, and airing the titanium foil substrate to obtain the primarily oxidized titanium foil substrate for later use.
3. And (3) anodizing the titanium foil substrate subjected to primary oxidation at room temperature for 1h at a voltage of 60V in the ammonium fluoride solution by using a platinum sheet as a cathode. Washing with distilled water. Then the sample is placed in a muffle furnace to be calcined at 550 ℃ for 2h, and thenCooling to room temperature along with the furnace to obtain TiO2And (4) nano array tubes.
4. Dipping the obtained TiO2 nano array tube in 10.0g/L TMGL solution for 3h, and calcining at 150 ℃ for 3h to obtain TMGL @ TiO for 304 stainless steel photo-generated cathode protection2A photoanode of the film.
Application example 1
Characterization of open circuit potential under switching light:
1. TMGL @ TiO obtained in the above example2Photo-anode sheet of film was cut to 1x1cm2The back sides of the squares were connected with enameled wires and sealed with 704 silicone rubber, leaving one side exposed.
2. The electrodes obtained by the step 1) are respectively arranged in an H-shaped electrolytic cell and are divided into a photoelectrolysis cell or a corrosion cell for measuring open-circuit potential (see figure 2). The electrolyte solution of the photoelectrolysis cell is 0.25M NaS2+0.35M Na2SO3The solution, the corrosion cell, is 3.5% wt NaCl solution.
3. The 304 stainless steel electrode and the saturated calomel electrode are placed in an etching cell, and the photo anode is placed in a photo-electrolysis cell. The 304 stainless steel electrode and the photoanode are in short circuit to serve as working electrodes, and the saturated calomel electrode serves as a reference electrode.
The 4 experiments were tested with Chenhua C660e, and the procedure was chosen such that the distance between the Open Circuit Potential-Time photoelectrolysis cell and the Xe lamp light source was 15 cm. The test was to switch the light once every 100 s.
It can be seen from fig. 2 that the potential of the coupling electrode rapidly drops under the irradiation of the visible light, since the electrons on the photo-anode surface are transferred to the surface of the 304 stainless steel electrode, thereby generating the cathode protection effect on the 304 stainless steel electrode. The open-circuit potential under visible light illumination is reduced to 98mv and 164mv respectively relative to the open-circuit potential without visible light illumination. Has good corrosion resistance. Pure titanium dioxide causes a potential drop of 98mv for 304 stainless steel, and the TMGL @ TiO2 membrane causes a potential drop of about 164mv for 304 stainless steel. It can be concluded that the presence of TMGL makes TiO2The photo-cathode protection performance of the nanotube array film is greatly improved.
Application example 2
Under intermittent visible light illumination, TMGL @ TiO2、TiO2Detection of photo-induced current density generated by photo-anode pair 304 stainless steel electrodes:
1. TMGL @ TiO obtained in the above example2Photo-anode sheet of film was cut to 1x1cm2The back sides of the squares were connected with enameled wires and sealed with 704 silicone rubber, leaving one side exposed.
2. The electrodes obtained by the step 1) are respectively arranged in an H-shaped electrolytic cell and are divided into a photoelectrolysis cell or a corrosion cell for measuring open-circuit potential (see figure 3). Wherein the electrolyte solution of the photoelectrolysis cell is 0.25M NaS2+0.35M Na2SO3The solution, the corrosion cell, is 3.5% wt NaCl solution.
3. The 304 stainless steel electrode was placed in the corrosion cell and the photoanode in the photoelectrolysis cell. The 304 stainless steel electrode is connected with the ground wire, the photo-anode is used as a working electrode, and the reference electrode wire and the counter electrode wire are in short circuit.
4. The experiment was tested with Chenghua C660e, the procedure chosen was Amperometrici-t Curve photoelectrolysis cell at a distance of 15cm from the Xe lamp source. The test was to switch the light once every 50 s.
From FIG. 3 it can be seen that TMGL @ TiO is exposed to intermittent visible light2,TiO2The photo-induced current density generated by the electrodes. About 3.5X 10-5mA/cm2，1X 10-5mA/cm2，TMGL@TiO2And the more excellent photo-induced cathodic protection performance is embodied.
Claims (4)
1. A preparation method of a photo-anode of an ionic liquid modified semiconductor composite film is characterized by comprising the following steps: taking the cleaned substrate as an anode, carrying out oxidation treatment for 1-2h in ammonium fluoride solution at a voltage of 60-75V for the anode, cleaning after oxidation, carrying out ultrasonic treatment under the condition of hydrochloric acid, airing, carrying out oxidation treatment for 1-2h in the ammonium fluoride solution at a voltage of 60-75V for the dried substrate, cleaning after oxidation, raising the temperature to 550 ℃ at a heating rate of 5-10 ℃/min in a muffle furnace for calcining for 2-3h, and cooling to room temperature along with the furnace after calcining to obtain the TiO2A nano array tube;
then, TiO will be obtained2Immersing the nano array tube in the TMGL solution for 2-3h at room temperature,then calcining at 150 ℃ and 200 ℃ for 2-3h, wherein the concentration of TMGL is 5.0-10 g/L.
2. The method for preparing the photoanode of the ionic liquid modified semiconductor composite film according to claim 1, wherein the method comprises the following steps: the base material is a pure titanium sheet which is washed by acetone, absolute ethyl alcohol and distilled water in sequence through ultrasonic washing.
3. The method for preparing the photoanode of the ionic liquid modified semiconductor composite film according to claim 1, wherein the method comprises the following steps: the ammonium fluoride solution is prepared by dissolving ammonium fluoride in water, adding ethylene glycol, and stirring for 3-4 h; wherein the volume ratio of the deionized water to the ethylene glycol is 1: 9-1:10, and the mass fraction of ammonium fluoride is 0.3% -0.4%.
4. A photoanode of an ionic liquid modified semiconductor composite film prepared by the method of claim 1.
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| CN103346016A (en) * | 2013-07-10 | 2013-10-09 | 四川农业大学 | Composite material filled with polyethylenedioxythiophene in inner and outer space of TiO2 nanotube array tube and its preparation method and application |
| CN107723712A (en) * | 2017-09-30 | 2018-02-23 | 青岛大学 | ZnIn for photoproduction cathodic protection2S4/TiO2The preparation method of nanometer tube composite film light anode |
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| CN103346016A (en) * | 2013-07-10 | 2013-10-09 | 四川农业大学 | Composite material filled with polyethylenedioxythiophene in inner and outer space of TiO2 nanotube array tube and its preparation method and application |
| CN107723712A (en) * | 2017-09-30 | 2018-02-23 | 青岛大学 | ZnIn for photoproduction cathodic protection2S4/TiO2The preparation method of nanometer tube composite film light anode |
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