CN116180091A - CoO and Ag modified TiO 2 Composite nano tube array photo-anode and preparation method thereof - Google Patents
CoO and Ag modified TiO 2 Composite nano tube array photo-anode and preparation method thereof Download PDFInfo
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to the technical field of nano materials, in particular to CoO and Ag modified TiO 2 A composite nanotube array photo-anode and a preparation method thereof. The method is used for TiO 2 Modifying Ag nano particles by the nano tube array film to obtain Ag modified TiO 2 Nanotube array film, and Ag modified TiO 2 Modifying CoO nano particles by the nanotube array film to obtain CoO and Ag modified TiO 2 Composite nanotube array photo-anode. The method adopts CoO nano particles to modify, and can lead holes to be formed by TiO 2 Unidirectional transfer to CoO, reduce TiO 2 Surface water oxidation reaction overpotential effectively improves TiO 2 Hole consumption rate, promote TiO 2 Photo-generated cathode protection performance; coO and Ag modified TiO of the invention 2 The composite nanotube array photo-anode has excellent photoelectric performance and can effectively prevent corrosion of stainless steel in sodium chloride solution.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to CoO and Ag modified TiO 2 A composite nano tube array photo-anode and a preparation method thereof.
Background
With the rapid development of the industrialization process in China, the metal corrosion problem is more serious. The metal corrosion causes huge economic loss and resource waste, and also causes serious industrial accidents, pollutes the environment and endangers the health and safety of human beings. In recent years, researchers have developed a number of methods for preventing the problem of metal corrosion, including anticorrosive coatings, corrosion inhibitors, cathodic protection methods, and the like. Among these cathodic protection techniques are sacrificial anodic protection, which sacrifices the anode material, and impressed current protection, which requires additional impressed current.
The photo-generated cathode protection technology is a novel green anti-corrosion technology combining semiconductor photoelectric conversion characteristics and cathode protection mechanism, and has the advantages of being capable of utilizing solar energyTo inhibit corrosion of the metal and not release metal ions to the environment. The basic principle is as follows: under the irradiation of sunlight, electrons in the valence band of the semiconductor are transited to a conduction band, and holes are formed at the valence band; electrons are transferred to the surface of the protected metal to achieve the effect of cathodic protection, and holes are consumed by water oxidation reaction on the surface of the semiconductor. Various semiconductor photoelectrodes are currently investigated by researchers, in which TiO 2 The material has the characteristics of stable physical and chemical properties, no toxicity, low price and the like, and is often used as a photo-anode material for photo-generated cathode protection. However, tiO 2 The surface water oxidation reaction has higher overpotential, and the hole consumption rate is too slow, so that the overall photo-generated cathode protection effect is limited.
Disclosure of Invention
The technical problem to be solved by the invention is to provide CoO and Ag modified TiO 2 A composite nanotube array photo-anode and a preparation method thereof.
The technical scheme for solving the technical problems is as follows:
the invention provides a TiO modified by CoO and Ag 2 Preparation method of composite nanotube array photo-anode for TiO 2 Modifying Ag nano particles by the nano tube array film to obtain Ag modified TiO 2 Nanotube array film, and then modifying the Ag with TiO 2 Modifying CoO nano particles by the nanotube array film to obtain the CoO and Ag modified TiO 2 Composite nanotube array photo-anode.
Further, the method for modifying the CoO nano particles is a hydrothermal synthesis reaction, and comprises the following steps:
modifying the Ag-modified TiO 2 Soaking the nanotube array film in the mixed alcohol solution for 3-6 hr, and adding Co (CH) in 0.5-2 wt% in the weight ratio 3 COO) 2 ·H 2 The total volume of the O solution is 30-40 mL, the temperature is raised to 65-70 ℃, the temperature is kept for 5-7 h, and finally the mixed solution is transferred into a 50mL reaction kettle to react at 230-250 ℃ for 4-6 h; removing the CoO and Ag modified TiO of the solid after the reaction 2 Composite nanotube array photo-anode.
Further, the mixed alcohol solution is a mixed solution of ethanol and n-octanol, and the volume ratio of the ethanol to the n-octanol is 2: 7-10.
Further, the temperature of the mixed alcohol solution is 30-60 ℃.
Further, the TiO 2 The preparation method of the nanotube array film is a two-step anodic oxidation method, and the two-step anodic oxidation method comprises the following steps:
immersing Ti sheets serving as anodes and Pt sheets serving as cathodes in an electrolyte solution, and electrifying to perform first oxidation; after the first oxidation is finished, removing TiO on the surface of the Ti sheet 2 The nanotube is oxidized for the second time, and the conditions of the second oxidation are the same as those of the first oxidation; after the second oxidation is finished, washing the Ti sheet, drying, calcining the Ti sheet at 450-550 ℃ for 2h after drying to obtain the TiO 2 Nanotube array films.
Further, in the Ti sheet, the purity of Ti is 99.99% or more.
Further, the electrolyte solution contains NH 4 F and H 2 Glycol solution of O, in the electrolyte solution, NH 4 F concentration is 3-7 g/L, H 2 The volume percentage of O is 5-15%.
Further, in both the first oxidation and the second oxidation, a constant voltage is applied at the time of energization, the voltage is 20 to 40V, and the energization time per oxidation is 1 to 3 hours.
Further, the pair of TiO 2 The Ag nano particle modification of the nanotube array film comprises the following steps:
the TiO is treated with 2 AgNO with the immersion concentration of 0.04-0.08 mo1/L for nanotube array film 3 In the solution, ultraviolet light irradiation is carried out for 1 to 5 hours, thus obtaining the Ag modified TiO 2 Nanotube array films.
The invention also provides a TiO modified by CoO and Ag 2 The composite nanotube array photo-anode is prepared by adopting the method.
The beneficial effects of the invention are as follows:
(1) The invention is characterized in thatCoO and Ag modified TiO 2 The preparation method of the composite nanotube array photoanode adopts CoO nano particles to modify on the basis of Ag modification, so that holes can be formed by TiO 2 Unidirectional transfer to CoO, reduce TiO 2 The surface water oxidation reaction overpotential is used to effectively promote TiO 2 Hole consumption rate, in turn, increases TiO 2 Photo-generated cathode protection performance;
(2) CoO and Ag modified TiO of the invention 2 The preparation method of the composite nanotube array photo-anode also specifically limits TiO 2 Preparation method of nanotube array film and Ag nano particle modification method, so that Ag nano particles can be uniformly deposited on TiO 2 The surface is free from agglomeration and has uniform appearance.
(3) CoO and Ag modified TiO of the invention 2 Preparation method of composite nanotube array photo-anode, which is prepared by modifying TiO (titanium dioxide) with Ag 2 When the nanotube array film is continuously subjected to CoO modification, a CoO promoter can be rapidly and accurately deposited on the surface of the Ag nano particle, but is rarely deposited on TiO 2 A surface;
(4) CoO and Ag modified TiO of the invention 2 Composite nanotube array photoanode, and pure TiO 2 Compared with a nanotube array, the nanotube array has better light absorption performance, conductivity and photocarrier separation performance;
(5) CoO and Ag modified TiO of the invention 2 The composite nanotube array photoanode has excellent photoelectric performance, can provide a large amount of electrons for 304 stainless steel under a larger photoinduced current density, and can effectively prevent the 304 stainless steel from corroding in sodium chloride solution.
Drawings
FIG. 1 is a CoO and Ag modified TiO of the present invention 2 In the preparation method of the composite nanotube array photoanode, the TiO-coated material in example 1 2 Ti sheet physical photo of the nanotube array;
FIG. 2 is a CoO and Ag modified TiO of the present invention 2 In the preparation method of the composite nanotube array photoanode, coO and Ag modified TiO in example 1 2 Ti sheet physical photo of composite nanotube array film.
Detailed Description
The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
CoO and Ag modified TiO of the invention 2 Preparation method of composite nanotube array photo-anode for TiO 2 Modifying Ag nano particles by the nano tube array film to obtain Ag modified TiO 2 Nanotube array film, and Ag modified TiO 2 Modifying CoO nano particles by the nanotube array film to obtain CoO and Ag modified TiO 2 Composite nanotube array photo-anode.
The preparation method of the invention sequentially adopts Ag and CoO for modification, and the CoO has higher water oxidation reaction activity and can construct a Z-type heterojunction, thus, the CoO is utilized to carry out the reaction on TiO 2 Modified to enable holes to be formed from TiO 2 Unidirectional transfer to CoO, reduce TiO 2 The surface water oxidation reaction overpotential is used to effectively promote TiO 2 Hole consumption rate, in turn, increases TiO 2 Photo-generated cathodic protection performance.
Preferably, the method for modifying the CoO nano-particles is a hydrothermal synthesis reaction, which comprises the following steps: ag modified TiO 2 Soaking the nanotube array film in the mixed alcohol solution for 3-6 hr, and adding Co (CH) in 0.5-2 wt% in the weight ratio 3 COO) 2 ·H 2 And (3) O solution, wherein the total volume of the solution is 30-40 mL, heating to 65-70 ℃, maintaining for 5-7 h, and finally transferring the mixed solution into a 50mL reaction kettle for reaction at 230-250 ℃.
Preferably, the mixed alcohol solution is a mixed solution of ethanol and n-octanol, and the volume ratio of the ethanol to the n-octanol is 2: 7-10.
Preferably, the temperature of the mixed alcohol solution is 30 to 60 ℃.
Preferably, tiO 2 The preparation method of the nanotube array film comprises the following steps: immersing Ti sheets serving as anodes and Pt sheets serving as cathodes in an electrolyte solution, and electrifying to perform first oxidation; after the first oxidation is finished, tiO on the surface of the Ti sheet is removed 2 The nanotube is oxidized for the second time, and the second oxidation condition is the same as the first oxidation condition; after the second oxidation is finished, washing the Ti sheet, drying, calcining the Ti sheet at 450-550 ℃ for 2h after drying to obtain TiO 2 Nanotube array films.
Preferably, in the Ti sheet, the purity of Ti is 99.99% or more.
Preferably, the electrolyte solution is an electrolyte solution containing NH 4 F and H 2 Glycol solution of O, NH in electrolyte solution 4 F concentration is 3-7 g/L, H 2 The volume percentage of O is 5-15%.
Preferably, in both the first oxidation and the second oxidation, a constant voltage is applied at the time of energization, the voltage is 20 to 40V, and the energization time for each oxidation is 1 to 3 hours.
Preferably, for TiO 2 The Ag nano particle modification of the nanotube array film comprises the following steps: tiO is mixed with 2 AgNO with the immersion concentration of 0.04-0.08 mo1/L for nanotube array film 3 In the solution, ultraviolet light irradiation is carried out for 1 to 5 hours, and Ag modified TiO is obtained 2 Nanotube array films.
The specific TiO is adopted 2 Preparation method of nanotube array film and Ag modified TiO (titanium dioxide) obtained by Ag nanoparticle modification method 2 The nano tube array film can uniformly deposit Ag nano particles on TiO 2 The surface is free from agglomeration and has uniform appearance. Meanwhile, in the Ag modified TiO 2 When the nanotube array film is continuously subjected to CoO modification, a CoO promoter can be rapidly and accurately deposited on the surface of the Ag nano particle, but is rarely deposited on TiO 2 A surface.
CoO and Ag modified TiO of the invention 2 The composite nanotube array photo-anode is prepared by adopting the method. And pure TiO 2 Compared with the nanotube array, the nanotube array has better light absorption performance, conductivity and photocarrier separation performance. The excellent photoelectric property can provide a large amount of electrons for the 304 stainless steel under a larger photoelectric current density, which effectively prevents the 304 stainless steel from corroding in sodium chloride solution.
The effects of the present invention are specifically illustrated by the following specific examples and comparative examples:
example 1
This example uses the method of the present invention to prepare CoO and Ag modified TiO 2 The preparation method of the composite nanotube array photo-anode comprises the following specific steps:
1)TiO 2 preparation of nanotube array films
Ti sheet with purity of 99.99% is used as anode, pt sheet is used as cathode, NH with purity of 3.5g/L 4 F and 10vol.% H 2 Applying 120mA constant current to an ethylene glycol solution composed of O as an electrolyte, oxidizing for 3h, ultrasonically cleaning the oxidized Ti sheet with 0.1M hydrochloric acid for 30min, and removing TiO formed on the surface 2 Nanotube, obtaining smooth Ti sheet, oxidizing under the same condition for the second time, thoroughly washing the surface of the Ti sheet with deionized water, drying in air, transferring into a resistance furnace, calcining at 450 ℃ for 2h to obtain TiO on the Ti sheet 2 Nanotube array films.
2) Ag modified TiO 2 Preparation of nanotube array films
TiO obtained in the step 1) is prepared 2 Nanotube array film immersed in AgNO at a concentration of 0.07mo1/L 3 Obtaining Ag modified TiO by ultraviolet irradiation for 4h in the solution 2 Nanotube array films.
3) CoO and Ag modified TiO 2 Preparation of composite nanotube array photo-anode
Ag modified TiO 2 The volume ratio of the immersed ethanol to the n-octanol of the nanotube array film is 2:9, the temperature of the mixed solution is 50 ℃, and after the mixed solution is kept for 5 hours, co (CH) with the mass fraction of 1.2wt.% is added 3 COO) 2 ·H 2 O is further heated to 65 ℃ and kept for 6 hours, then transferred to an autoclave and kept at 240 ℃ for 6 hours, cooled, washed and dried to obtain CoO and Ag modified TiO 2 Composite nanotube array photo-anode.
FIG. 1 is a TiO-coated 2 FIG. 2 is a photograph of a Ti sheet of a nanotube array, showing CoO and Ag-modified TiO obtained in this example 2 Ti sheet physical photo of composite nanotube array film can be seenTiO after CoO and Ag modification 2 The nanotube array changes from blue to brown-black.
Example 2
Preparation of TiO according to the three procedures in example 1 2 Ag modified TiO 2 (Ag/TiO 2 ) CoO and Ag modified TiO 2 Nanotube array film (CoO/Ag/TiO) 2 ) Step 2) is skipped and the TiO is prepared 2 Directly carrying out the operation of the step 3) on the nanotube array film to prepare the CoO modified TiO 2 (CoO/TiO 2 ) Composite nanotube array photoanode material.
TiO to be obtained 2 、Ag/TiO 2 、CoO/TiO 2 And CoO/Ag/TiO 2 The following photoelectrochemical property tests were performed on the anode material coupled with 304 stainless steel, respectively, and these results were used to evaluate the electrochemical properties of the photoanode material, and the protective effect that may be achieved on 304 stainless steel, and the results are shown in table 1.
The specific equipment and method for performance test are as follows:
the device comprises an electrochemical workstation and a xenon lamp light source H-type electrolytic cell. Wherein the photoelectric cell part of the H-type electrolytic cell is provided with a quartz glass sealing window with the diameter of 30.0mm, and the electrolyte is 0.25M Na 2 S+0.35M Na 2 SO 3 The corrosion cell part comprises 304 electrodes as working electrodes, saturated calomel electrodes as reference electrodes, pt sheets as counter electrodes, 3.5wt.% NaCl as electrolyte, and Nafion film as salt bridge connected with two electrolytic cells.
The electrochemical workstation, the xenon lamp light source and the H-type electrolytic cell are used for testing the cathodic protection potential, the photo-induced cathodic protection current and the oxygen evolution overpotential of the 304 electrode of the coupling electrode of the nanocomposite electrode and the 304 electrode under intermittent visible light irradiation.
TABLE 1TiO 2 、Ag/TiO 2 、CoO/TiO 2 And CoO/Ag/TiO 2 Photo-electrochemical performance of anode material and 304 stainless steel coupling
As can be seen from Table 1, the potential drop of the anode material after coupling with 304 electrode has a remarkable effect, which not only shows that CoO can generate a large amount of photo-generated electrons as a narrow bandgap semiconductor, but also shows that Ag-loaded TiO 2 Can effectively promote the separation of photogenerated carriers and increase the amount of effective photogenerated electrons. Wherein CoO/Ag/TiO 2 The potential drop is maximally 539mV, and the photoinduced current density is 45 mu A/cm 2 Exhibits the best photocathode protection performance.
Comparative example 1
1) Preparation of TiO on Ti sheets according to the procedure described in example 1 2 Nanotube array films.
2) TiO is mixed with 2 Nanotube arrays immersed in AgNO at a concentration of 0.04mo1/L 3 The Ag/TiO is obtained by ultraviolet irradiation for 4 hours in the solution 2 Nanotube array films.
3) Ag/TiO 2 The volume ratio of the nano rod array composite film to the immersed ethanol to the n-octanol is 2:9, the temperature of the mixed solution is 50 ℃, and after the mixed solution is kept for 5 hours, co (CH) with the mass fraction of 0.5wt.% is added 3 COO) 2 ·H 2 O was further warmed to 65℃for 5 hours, then transferred to an autoclave and kept at 240℃for 6 hours, cooled, and then washed and dried to finally obtain CoO/Ag/TiO of comparative example 1 2 Composite nanotube array photoanode material.
Comparative example 2
1) Preparation of TiO on Ti sheets according to the procedure described in example 1 2 Nanotube array films.
2) TiO is mixed with 2 The nanotube array is immersed in AgNO with the concentration of 0.05mo1/L 3 The Ag/TiO is obtained by ultraviolet irradiation for 4 hours in the solution 2 Nanotube array films.
3) Ag/TiO 2 The volume ratio of the nano rod array composite film to the immersed ethanol to the n-octanol is 2:9, temperature of the mixed solutionAfter holding at 50℃for 5h, co (CH) was added in a mass fraction of 0.8 wt% 3 COO) 2 ·H 2 O was further warmed to 65℃for 5 hours, then transferred to an autoclave and kept at 240℃for 6 hours, cooled, and then washed and dried to finally obtain CoO/Ag/TiO of comparative example 2 2 Composite nanotube array photoanode material.
Comparative example 3
1) Preparation of TiO on Ti sheets according to the procedure described in example 1 2 Nanotube array films.
2) TiO is mixed with 2 The nanotube array is immersed in AgNO with the concentration of 0.06mo1/L 3 The Ag/TiO is obtained by ultraviolet irradiation for 4 hours in the solution 2 Nanotube array films.
3) Ag/TiO 2 The volume ratio of the nano rod array composite film to the immersed ethanol to the n-octanol is 2:9, the temperature of the mixed solution is 50 ℃, and after the mixed solution is kept for 5 hours, co (CH) with the mass fraction of 1.5wt.% is added 3 COO) 2 ·H 2 O was further warmed to 65℃for 5 hours, then transferred to an autoclave and kept at 240℃for 6 hours, cooled, and then washed and dried to finally obtain CoO/Ag/TiO of comparative example 3 2 Composite nanotube array photoanode material.
Comparative example 4
1) Preparation of TiO on Ti sheets according to the procedure described in example 1 2 Nanotube array films.
2) TiO is mixed with 2 The nanotube array is immersed in AgNO with the concentration of 0.08mo1/L 3 The Ag/TiO is obtained by ultraviolet irradiation for 4 hours in the solution 2 Nanotube array films.
3) Ag/TiO 2 The volume ratio of the nano rod array composite film to the immersed ethanol to the n-octanol is 2:9, the temperature of the mixed solution is 50 ℃, and after the mixed solution is kept for 5 hours, co (CH) with the mass fraction of 2.0wt.% is added 3 COO) 2 ·H 2 O was further warmed to 65℃for 5 hours, then transferred to an autoclave and kept at 240℃for 6 hours, cooled, and then washed and dried to finally obtain CoO/Ag/TiO of comparative example 4 2 Composite nanotube array photoanode material.
Comparative example 5
1) Preparation of TiO on Ti sheets according to the procedure described in example 1 2 Nanotube array films.
2) TiO is mixed with 2 The nanotube array is immersed in AgNO with the concentration of 0.08mo1/L 3 The Ag/TiO is obtained by ultraviolet irradiation for 4 hours in the solution 2 Nanotube array films.
3) Ag/TiO 2 The volume ratio of the nano rod array composite film to the immersed ethanol to the n-octanol is 2:9, the temperature of the mixed solution is 50 ℃, and after the mixed solution is kept for 5 hours, co (CH) with the mass fraction of 0.5wt.% is added 3 COO) 2 ·H 2 O was further warmed to 65℃for 5 hours, then transferred to an autoclave and kept at 240℃for 6 hours, cooled, and then washed and dried to finally obtain CoO/Ag/TiO of comparative example 5 2 Composite nanotube array photoanode material.
Comparative example 6
1) Preparation of TiO on Ti sheets according to the procedure described in example 1 2 Nanotube array films.
2) TiO is mixed with 2 Nanotube arrays immersed in AgNO at a concentration of 0.04mo1/L 3 The Ag/TiO is obtained by ultraviolet irradiation for 4 hours in the solution 2 Nanotube array films.
3) Ag/TiO 2 The volume ratio of the nano rod array composite film to the immersed ethanol to the n-octanol is 2:9, the temperature of the mixed solution is 50 ℃, and after the mixed solution is kept for 5 hours, co (CH) with the mass fraction of 2.0wt.% is added 3 COO) 2 ·H 2 O was further warmed to 65℃for 5 hours, then transferred to an autoclave and kept at 240℃for 6 hours, cooled, and then washed and dried to finally obtain CoO/Ag/TiO of comparative example 6 2 Composite nanotube array photoanode material.
CoO/Ag/TiO prepared in example 1 and comparative examples 1 to 6 above 2 The photo-anode materials of the composite nanotube array are respectively subjected to photoelectrochemical property test of coupling with 304 stainless steel, and the test results are shown in Table 2:
TABLE 2 CoO/Ag/TiO prepared by various schemes 2 Photo-electrochemical performance of anode material and 304 stainless steel coupling
According to the above comparison, the preparation parameters referred to in example 1 are the optimal solution of the present invention. That is, 0.07mo1/L AgNO was used 3 Preparation of Ag/TiO 2 Nanotube array films employing 1.2wt.% Co (CH) 3 COO) 2 ·H 2 O prepared CoO/Ag/TiO 2 The composite nanotube array photo-anode has the best effect.
In addition, if AgNO 3 When the concentration of AgNO is too high or too low, which is not within the limits of the present invention 3 The photo-induced current density decreases. The invention is limited in scope, and the prepared material has optimal photoproduction cathode protection performance.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. CoO and Ag modified TiO 2 The preparation method of the composite nanotube array photo-anode is characterized by comprising the following steps of 2 Modifying Ag nano particles by the nano tube array film to obtain Ag modified TiO 2 Nanotube array film, and then modifying the Ag with TiO 2 Modifying CoO nano particles by the nanotube array film to obtain the CoO and Ag modified TiO 2 Composite nanotube array photo-anode.
2. A CoO and Ag modified TiO according to claim 1 2 The preparation method of the composite nanotube array photoanode is characterized in that the CoO nanoparticle modification method is a hydrothermal synthesis reaction, and comprises the following steps ofThe method comprises the following steps:
modifying the Ag-modified TiO 2 Soaking the nanotube array film in the mixed alcohol solution for 3-6 hr, and adding Co (CH) in 0.5-2 wt% in the weight ratio 3 COO) 2 ·H 2 The total volume of the O solution is 30-40 mL, the temperature is raised to 65-70 ℃, the temperature is kept for 5-7 h, and finally the mixed solution is transferred into a 50mL reaction kettle to react at 230-250 ℃ for 4-6 h; removing the CoO and Ag modified TiO of the solid after the reaction 2 Composite nanotube array photo-anode.
3. A CoO and Ag modified TiO according to claim 2 2 The preparation method of the composite nanotube array photoanode is characterized in that the mixed alcohol solution is a mixed solution of ethanol and n-octanol, and the volume ratio of the ethanol to the n-octanol is 2: 7-10.
4. A CoO and Ag modified TiO according to claim 2 2 The preparation method of the composite nanotube array photo-anode is characterized in that the temperature of the mixed alcohol solution is 30-60 ℃.
5. A CoO and Ag modified TiO according to any one of claims 1 to 4 2 The preparation method of the composite nanotube array photo-anode is characterized by comprising the following steps of 2 The preparation method of the nanotube array film is a two-step anodic oxidation method, and the two-step anodic oxidation method comprises the following steps:
immersing Ti sheets serving as anodes and Pt sheets serving as cathodes in an electrolyte solution, and electrifying to perform first oxidation; after the first oxidation is finished, removing TiO on the surface of the Ti sheet 2 The nanotube is oxidized for the second time, and the conditions of the second oxidation are the same as those of the first oxidation; after the second oxidation is finished, washing the Ti sheet, drying, calcining the Ti sheet at 450-550 ℃ for 2h after drying to obtain the TiO 2 Nanotube array films.
6. According to claim 5The CoO and Ag modified TiO 2 The preparation method of the composite nanotube array photoanode is characterized in that the purity of Ti in the Ti sheet is more than or equal to 99.99%.
7. A CoO and Ag modified TiO according to claim 5 2 The preparation method of the composite nanotube array photoanode is characterized in that the electrolyte solution contains NH 4 F and H 2 Glycol solution of O, in the electrolyte solution, NH 4 F concentration is 3-7 g/L, H 2 The volume percentage of O is 5-15%.
8. A CoO and Ag modified TiO according to claim 5 2 The preparation method of the composite nanotube array photo-anode is characterized in that constant voltage is applied during the electrifying process in the first oxidation and the second oxidation, the voltage is 20-40V, and the electrifying time of each oxidation is 1-3 h.
9. A CoO and Ag modified TiO according to any one of claims 1 to 4 2 The preparation method of the composite nanotube array photoanode is characterized by comprising the following steps of 2 The Ag nano particle modification of the nanotube array film comprises the following steps:
the TiO is treated with 2 AgNO with the immersion concentration of 0.04-0.08 mo1/L for nanotube array film 3 In the solution, ultraviolet light irradiation is carried out for 1 to 5 hours, thus obtaining the Ag modified TiO 2 Nanotube array films.
10. CoO and Ag modified TiO 2 The composite nanotube array photoanode is characterized by being prepared by adopting the method of any one of claims 1 to 9.
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