CN109468674B - TiO2/WO3Preparation method of nano composite film - Google Patents
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Abstract
The invention provides a TiO2/WO3A method of preparing a nanocomposite film, comprising: ultrasonically cleaning a titanium foil to obtain a titanium substrate sample; preparing a first electrolyte solution by using ammonium fluoride, glycerol and water; taking a titanium substrate sample as an anode and a platinum sheet as a cathode, and carrying out anodic oxidation reaction in a first electrolyte solution; after the anodic oxidation reaction is finished, a sample prepared on the anode is washed by deionized water, dried and calcined in a muffle furnace, and TiO is prepared on the surface of a titanium substrate sample2A nanotube array film; with a surface coated with TiO2Preparing TiO by constant potential deposition with a titanium matrix sample of the nanotube array film as a cathode and a platinum sheet as an anode2/WO3A nanocomposite film. Through the technical scheme of the invention, the prepared TiO2/WO3The nano composite film has good photoelectric effect and energy storage performance, and shows good photoproduction cathodic protection effect on metal, especially stainless steel under illumination and dark state.
Description
Technical Field
The invention relates to the technical field of metal corrosion and protection, in particular to TiO2/WO3A method for preparing a nano composite film.
Background
The metal corrosion causes huge losses of several trillion yuan each year to national economy of China, which accounts for about 3.34% of the total production value (GDP) in China in the current year, and also relates to important economic and social problems of personal safety, resource waste, environmental pollution and the like. To date, a large number of anti-corrosion technologies are widely applied, and play a great role in national economic construction. Cathodic protection is one of electrochemical protection technologies, and the principle of cathodic protection is that a current is applied to a metal to be protected by an external means or an anode is added to the metal to be protected so that the metal becomes a cathode to be protected. But conventional cathodic protection requires sacrificial anodes or consumes electrical energy.
For corrosion prevention, the photoproduction cathode protection technology fundamentally solves the energy and environmental problems caused by metal corrosion, and the technology is worthy of deep research, popularization and application. However, pure TiO is affected by natural conditions such as day and night, season, climate and the like, and solar radiation has discontinuity and intermittency2The film has the following technical defects when applied to the corrosion prevention of metal materials:
(1)TiO2the film can only absorb ultraviolet light with the wavelength less than 387nm, the ultraviolet light only accounts for 4 to 5 percent of sunlight, the film does not absorb visible light, and the solar energy cannot be fully utilized。
(2)TiO2The semiconductor has high recombination rate of photo-generated electrons and holes and low photoelectric conversion efficiency.
(3) When the light is converted into the dark state, no electrons are transferred, continuous cathode current cannot be provided for the protected metal, and the cathode protection is difficult to maintain.
Therefore, how to solve the problem of energy storage is to store solar energy in sunny day as much as possible for use at night or in rainy days, so as to realize continuous protection of metal under a dark condition, and the technical problem to be solved is urgently needed.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art or the related art.
Therefore, the invention aims to provide TiO2/WO3Preparation method of nano composite film, TiO prepared on titanium foil surface by anode oxidation method2The nanotube array film is based on the electrodeposition technology on TiO2WO with electronic storage function coated on surface of nanowire3Nano particles to obtain energy-storage TiO2/WO3The nano composite film has good photoelectric conversion effect, can be used as a composite light anode to provide photoproduction cathodic protection for metal, and can release electrons in a dark state to continuously perform cathodic protection on the metal.
In order to achieve the purpose, the technical scheme of the invention provides TiO2/WO3A method of preparing a nanocomposite film, comprising: ultrasonically cleaning a titanium foil in acetone, absolute ethyl alcohol and deionized water in sequence to obtain a titanium matrix sample; preparing a first electrolyte solution from ammonium fluoride, glycerol and water, wherein the volume ratio of the glycerol to the water in the first electrolyte solution is 3: 3-3: 1, and the mass fraction of the ammonium fluoride is 0.45-0.55%; taking a titanium substrate sample as an anode and a platinum sheet as a cathode, and carrying out anodic oxidation reaction for 0.5-1.5 h in a first electrolyte solution at room temperature and 15-25V; after the anodic oxidation reaction is finished, a sample prepared on the anode is washed by deionized water, dried and calcined in a muffle furnace, and TiO is prepared on the surface of a titanium substrate sample2A nanotube array film; coating TiO on the surface by adopting a constant potential deposition technology2The titanium matrix sample of the nanotube array film is used as a cathode, a platinum sheet is used as an anode, and Na is used2WO4、H2O2Preparing a second electrolyte solution from ethanol and water, adjusting the pH value, depositing at a specified deposition potential to prepare TiO2/WO3A nanocomposite film.
Preferably, the thickness of the titanium foil is 0.05 mm-0.15 mm, and the purity of the titanium foil is not less than 99.7%.
Preferably, the titanium foil has a length of 1.0cm to 2.0cm and a width of 0.5cm to 1.5 cm.
Preferably, the titanium foil is ultrasonically cleaned in acetone, absolute ethyl alcohol and deionized water for 25-40 min.
Preferably, in the second electrolyte solution, the volume ratio of ethanol to water is 1:1, and Na is2WO4Has a concentration of 0.001mol/L to 0.005mol/L, H2O2The mass fraction of the second electrolyte solution is 0.05-0.08%, and the pH value of the second electrolyte solution is 1-2.
Preferably, the calcining temperature in the muffle furnace is 420-470 ℃, and the calcining time is 100-150 min.
Preferably, the specified deposition potential is 0.5V to 1.0V, and the deposition time is 5min to 15 min.
Through the technical scheme, the TiO is prepared2/WO3The nano composite film has strong repeatability and stability, WO3The nano particles are uniformly distributed in the TiO2The nano tube can be used as photo anode inside and outside, can greatly reduce the electrode potential of the connected protected metal in photo-generated cathodic protection, and can still provide continuous cathodic protection for the metal in a dark state2/WO3Nanocomposite film of Na in electrolyte2SO4And CH3In the OH mixed solution, when white light is irradiated, the potential of a metal electrode to be protected, such as a stainless steel electrode, connected with the OH mixed solution and positioned in the NaCl solution is reduced to be lower than the natural corrosion potential of the metal to be protected relative to a reference electrode, the cathodic protection effect is remarkable, and after illumination is stopped，WO3The electrons stored in the electron storage device are transferred to the surface of the protected metal, and certain cathodic protection is provided for the protected metal. In summary, TiO prepared by the invention2/WO3The nano composite film has good photoelectric effect and energy storage performance, and shows good photoproduction cathodic protection effect on metal, especially stainless steel under illumination and dark state.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 shows TiO prepared according to an embodiment of the invention2/WO3Surface topography of the nanocomposite film;
FIG. 2 shows TiO prepared according to an embodiment of the invention2Nanotube array film and TiO2/WO3A photo-electric flow spectrum of the nano composite film;
FIG. 3 shows a stainless steel electrode and TiO according to an embodiment of the invention2/WO3The electrode potential change curve with time before and after the nano composite membrane is connected with illumination in 0.5mol/L NaCl solution, a stainless steel electrode and TiO2And (3) comparing the electrode potential change curve with time in 0.5mol/L NaCl solution before and after the connection of the nanotube array membrane and illumination.
Detailed Description
The invention discloses a TiO 22/WO3The preparation method of the nano composite film can be realized by appropriately improving the process parameters by the persons skilled in the art with reference to the contents. It is expressly intended that all such similar substitutes and modifications which would be obvious to one skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The invention is further illustrated by the following examples:
example 1
Taking a rectangular pure titanium foil with the thickness of 0.1mm, wherein the purity of the titanium foil is more than 99.7%, the length of the titanium foil is 1.5cm, and the width of the titanium foil is 1.0cm, and sequentially carrying out ultrasonic cleaning in acetone, absolute ethyl alcohol and deionized water for 30min to obtain a titanium substrate sample;
preparation of TiO by anodic oxidation2Preparing a first electrolyte solution by using ammonium fluoride, glycerol and water, wherein the volume ratio of the glycerol to the water in the first electrolyte solution is 3:2, anodizing the titanium substrate sample obtained after treatment at the voltage of 20V for 1.0h at room temperature by using a treated titanium substrate sample as an anode and a treated platinum sheet as a cathode, after the reaction is finished, cleaning the prepared sample by using a large amount of deionized water, drying and calcining the sample in a muffle furnace at the temperature of 450 ℃ for 120 min;
covering the surface with TiO by constant potential deposition technology2The titanium matrix sample of the nanotube array film is used as a cathode, a platinum sheet is used as an anode, and Na is used2WO4、H2O2Preparing a second electrolyte solution from ethanol and water, wherein the volume ratio of the ethanol to the water in the second electrolyte solution is 1:1, and Na2WO4Has a concentration of 0.005mol/L, H2O2The mass fraction of the titanium dioxide is 0.075 percent, the pH value is 1.4, the cathode deposition potential is 0.7V (vs. SCE), and the TiO can be prepared after 5min of deposition2/WO3A nanocomposite film.
TiO2/WO3The surface topography of the nanocomposite film is shown in FIG. 1, TiO2Both the interior and the exterior of nanotubes have been treated by WO3The nano-particles are uniformly covered, and the particle dispersibility is good, wherein (a) is a plan view, and (b) is a cross-sectional view.
TiO2Nanotube array film and TiO2/WO3The photo-electric flow spectrum of the nano composite film is shown in FIG. 2, wherein (a) is for TiO2Nanotube array films with very low photocurrent values, and TiO in (b)2/WO3The photocurrent value of the nano composite film is greatly improved, and visible TiO2/WO3The nano composite film has low probability of photo-generated electron-hole recombination, expanded light absorption range and obviously improved photoelectric conversion efficiency.
Testing of TiO2/WO3The nano composite film has photoproduction cathode protection effect on stainless steel: TiO 22/WO3The nano composite film is used as a photo-anode and is placed at a position containing 0.5mol/LNa2SO4And 1.0mol/LCH3In a photoelectrolysis cell of an OH solution, stainless steel is placed in a corrosion electrolysis cell containing 0.5mol/L NaCl solution, a photoanode is connected with the stainless steel through a lead, the photoelectrolysis cell is connected with the corrosion electrolysis cell through a salt bridge, a three-electrode system is adopted for electrochemical testing of the stainless steel in the corrosion electrolysis cell, a working electrode is a stainless steel electrode, a reference electrode is a Saturated Calomel Electrode (SCE), a counter electrode is a platinum electrode, and a 500W xenon lamp is used as a white light source during illumination and directly irradiates the surface of the photoanode in the electrolysis cell. And after the light is irradiated for a certain time, the light source is turned off, and the potential change of the stainless steel electrode in different states is tested. At the same time, with TiO2The nanotube array film is used as a photo-anode to form a control group, a stainless steel electrode and TiO2/WO3The electrode potential change curve with time before and after the nano composite membrane is connected with illumination in 0.5mol/L NaCl solution, a stainless steel electrode and TiO2Comparing the electrode potential change curve with time in 0.5mol/L NaCl solution before and after the connection of the nanotube array film and the illumination, as shown in FIG. 3, after the illumination, the electrode potential change curve is compared with the electrode potential change curve of the TiO solution2The electrode potential of the stainless steel electrode connected to the nanotube array film rapidly dropped by about 175mV, as shown in (a), compared to TiO2/WO3The electrode potential of the nanocomposite film-bonded stainless steel electrode was reduced by about 325mV relative to TiO as shown in (b)2The drop amplitude of the nanotube array membrane is increased by 150 mV. After switching off the light source, i.e. in the dark state, with TiO2/WO3The electrode potential of the stainless steel connected with the nano composite film rises, but the electrode potential of the stainless steel is still lower than that of the stainless steel connected with the TiO2The potential of the stainless steel electrode connected with the nanotube array film can be seen from the TiO prepared by the method2/WO3The nano composite film has excellent photoproduction cathode protection performance.
Example 2
Taking a rectangular pure titanium foil with the thickness of 0.05mm, wherein the purity of the titanium foil is more than 99.7%, the length of the titanium foil is 1.0cm, and the width of the titanium foil is 0.5cm, and sequentially carrying out ultrasonic cleaning in acetone, absolute ethyl alcohol and deionized water for 25min to obtain a titanium substrate sample;
preparation of TiO by anodic oxidation2Preparing a first electrolyte solution by using ammonium fluoride, glycerol and water, wherein the volume ratio of the glycerol to the water in the first electrolyte solution is 3:1, performing anodic oxidation for 0.5h at the room temperature under the voltage of 15V by using a titanium matrix sample obtained after treatment as an anode and a platinum sheet as a cathode, after the reaction is finished, cleaning the prepared sample by using a large amount of deionized water, drying, and calcining for 100min at the temperature of 420 ℃ in a muffle furnace;
covering the surface with TiO by constant potential deposition technology2The titanium matrix sample of the nanotube array film is used as a cathode, a platinum sheet is used as an anode, and Na is used2WO4、H2O2Preparing a second electrolyte solution from ethanol and water, wherein the volume ratio of the ethanol to the water in the second electrolyte solution is 1:1, and Na2WO4Has a concentration of 0.001mol/L, H2O2The mass fraction of the titanium dioxide is 0.05 percent, the pH value is 1, the cathode deposition potential is 0.5V (vs. SCE), and the TiO can be prepared after 10min of deposition2/WO3A nanocomposite film.
Testing and preparing the TiO2/WO3The nano composite film has excellent photoproduction cathode protection performance.
Example 3
Taking a rectangular pure titanium foil with the thickness of 0.15mm, wherein the purity of the titanium foil is more than 99.7%, the length of the titanium foil is 2.0cm, the width of the titanium foil is 1.5cm, and sequentially carrying out ultrasonic cleaning in acetone, absolute ethyl alcohol and deionized water for 40min to obtain a titanium substrate sample;
preparation of TiO by anodic oxidation2Preparing a first electrolyte solution by using ammonium fluoride, glycerol and water, wherein the volume ratio of the glycerol to the water in the first electrolyte solution is 3:3, anodizing at 25V for 1.5h at room temperature by using the treated titanium matrix sample as an anode and a platinum sheet as a cathode, washing the prepared sample by using a large amount of deionized water after the reaction is finished, drying, and calcining for 150min at 470 ℃ in a muffle furnace;
covering the surface with TiO by constant potential deposition technology2Titanium matrix test sample of nanotube array film asCathode, platinum sheet as anode and Na2WO4、H2O2Preparing a second electrolyte solution from ethanol and water, wherein the volume ratio of the ethanol to the water in the second electrolyte solution is 1:1, and Na2WO4Has a concentration of 0.003mol/L, H2O2The mass fraction of the titanium dioxide is 0.08 percent, the pH value is 2, the cathode deposition potential is 1.0V (vs. SCE), and the TiO can be prepared after 15min of deposition2/WO3A nanocomposite film.
Testing and preparing the TiO2/WO3The nano composite film has excellent photoproduction cathode protection performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (4)
1. TiO 22/WO3The preparation method of the nano composite film is characterized by comprising the following steps:
ultrasonically cleaning a titanium foil in acetone, absolute ethyl alcohol and deionized water in sequence to obtain a titanium matrix sample, and ultrasonically cleaning the titanium foil in acetone, absolute ethyl alcohol and deionized water in sequence for 25-40 min;
preparing a first electrolyte solution from ammonium fluoride, glycerol and water, wherein the volume ratio of the glycerol to the water in the first electrolyte solution is 3: 3-3: 1, and the mass fraction of the ammonium fluoride is 0.45-0.55%;
taking the titanium substrate sample as an anode and a platinum sheet as a cathode, and carrying out anodic oxidation reaction for 0.5-1.5 h in the first electrolyte solution at room temperature and 15-25V;
after the anodic oxidation reaction is finished, cleaning a sample prepared on the anode with deionized water, drying, calcining in a muffle furnace, and preparing TiO on the surface of the titanium substrate sample2A nanotube array film;
coating the surface with the TiO by constant potential deposition technology2Titanium of nanotube array filmThe matrix sample is a cathode, the platinum sheet is an anode, and Na is used2WO4、H2O2Preparing a second electrolyte solution from ethanol and water, adjusting the pH value, depositing at a specified deposition potential to prepare TiO2/WO3The volume ratio of ethanol to water in the second electrolyte solution is 1:1, and Na is added to the second electrolyte solution2WO4Has a concentration of 0.001mol/L to 0.005mol/L, H2O2The mass fraction of the second electrolyte solution is 0.05-0.08%, the pH value of the second electrolyte solution is 1-2, the specified deposition potential is 0.5-1.0V, and the deposition time is 5-15 min.
2. The TiO of claim 12/WO3A method for preparing a nano composite film is characterized in that,
the thickness of the titanium foil is 0.05 mm-0.15 mm, and the purity of the titanium foil is not less than 99.7%.
3. The TiO of claim 12/WO3A method for preparing a nano composite film is characterized in that,
the length of the titanium foil is 1.0 cm-2.0 cm, and the width of the titanium foil is 0.5 cm-1.5 cm.
4. The TiO of claim 12/WO3A method for preparing a nano composite film is characterized in that,
the calcining temperature in the muffle furnace is 420-470 ℃, and the calcining time is 100-150 min.
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