Energy storage type TiO2 / CN X / WO3 composite photoanode and its preparation method
By preparing TiO2/CNX/WO3 composite materials, the problem of insufficient protection performance of TiO2 photocathode was solved, achieving continuous protection and high-efficiency photoelectric performance in the dark state, and improving the light absorption and electron migration capabilities of photocathode.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SUN YAT SEN UNIV
- Filing Date
- 2023-06-27
- Publication Date
- 2026-07-03
AI Technical Summary
TiO2's photocathode protection performance is limited by factors such as its wide band gap and high recombination rate of electrons and holes, and it cannot provide continuous protection in the dark state. Furthermore, it is difficult to directly couple TiO2 with the protected substrate.
TiO2/CNX/WO3 composite materials were prepared by a three-step hydrothermal-ultrasonic-hydrothermal method. By forming a type II heterojunction between TiO2 and WO3 and introducing conductive polymer PPy to form CNX, the migration and separation of photogenerated carriers were improved. The energy storage properties of WO3 were used to release electrons in the dark state, and CNX served as an efficient charge migration channel.
It improves the photocathode protection performance, achieves continuous protection in the dark, enhances light absorption efficiency and electron migration ability, and improves the photocatalytic activity and stability of the material.
Smart Images
Figure CN116798776B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of photoanode technology, specifically to an energy storage type TiO2 / CN. X / WO3 composite photoanode and its preparation method. Background Technology
[0002] The emerging photoelectric cathodic protection (PECP) technology is a novel corrosion protection technique. It utilizes the photovoltaic effect of semiconductors to provide electrons to the metal, making its potential more potent than the natural corrosion potential, thus preventing corrosion. Compared to existing corrosion protection technologies (physical protection and electrochemical cathodic protection), it avoids corrosion failure caused by coating peeling or localized damage in physical protection, as well as the environmental problems and enormous energy consumption associated with cathodic protection.
[0003] TiO2 has long been a key research focus in the field of PECP due to its chemical stability, low cost, and abundant reserves. However, the wide band gap (3.2 eV) and high recombination rate of electrons and holes in TiO2 also limit its PECP performance. Furthermore, TiO2 requires illumination to exert its PECP effect, and cannot provide continuous protection in the dark. In practical applications, direct coupling between TiO2 and the protected substrate is also difficult. These issues restrict the development of TiO2 in PECP applications. Summary of the Invention
[0004] To overcome the shortcomings of the prior art, this invention proposes an energy storage type TiO2 / CN X / WO3 composite photoanode and its preparation method.
[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0006] The first aspect of this invention provides an energy storage type TiO2 / CN X The preparation method of WO3 composite material photoanode includes the following steps:
[0007] (1) Na2WO4·2H2O and Na2SO4 are dissolved in water, pH is adjusted, and a hydrothermal reaction is carried out. The solid obtained after the reaction is WO3 nanorods.
[0008] (2) The WO3 nanorods and anionic surfactant were added to water, sonicated, pyrrole was added, stirred, and then an initiator solution was added dropwise under ice bath conditions, stirred, and the reaction was completed to obtain the WO3 / PPy complex.
[0009] (3) The WO3 / PPy complex and the anionic surfactant were added to an alcohol solution, ultrasonicated and stirred, tetrabutyl titanate, glacial acetic acid and acetone were added, and then an aqueous alcohol solution was added dropwise. The mixture was transferred to a hydrothermal reactor for reaction. After the hydrothermal reaction, the precursor TiO2 / PPy / WO3 complex was obtained.
[0010] (4) The precursor TiO2 / PPy / WO3 composite is coated on a conductive substrate and calcined to obtain TiO2 / CN. X / WO3 composite photoanode.
[0011] WO3 is a binary multivalent metal oxide with energy storage properties, capable of effectively storing electrons. It is also highly stable and can exist in harsh corrosive environments, such as strong acids and strong oxidizing agents. The typical conjugated polymer polypyrrole (PPy) possesses advantages such as high specific capacitance, good conductivity, excellent mechanical properties, and biocompatibility, making it a promising conductive polymer. Furthermore, calcination of PPy under an inert atmosphere can yield pyridine nitrogen or graphitic nitrogen (CN) with even better catalytic activity and conductivity. X ).
[0012] This invention designs an energy storage composite material, TiO2 / CN, consisting of conductive polymer-derived carbon and nitrogen-modified WO3 nanorods supporting TiO2. X / WO3. This ternary composite material combines the advantages of three materials: (1) TiO2 has high chemical stability, low cost, environmental friendliness and ease of preparation, and is a widely recognized photocathode protection material; (2) WO3 nanorods have good chemical stability, strong electron storage capacity and band structure that matches TiO2, and can act as an electron storage pool for the composite material in the photocathode protection process; (3) PPy, as a highly conductive conjugated conductive polymer, has great flexibility and ductility, and can form a dense film on the surface of one-dimensional WO3 nanorods, and the CN formed after calcination X It possesses excellent electrical conductivity and photocatalytic activity, which facilitates the construction of charge transfer bridges between TiO2 and WO3, thereby improving the electron migration efficiency of energy storage composite materials and enhancing their charge-discharge capabilities. The prepared ternary composite material TiO2 / CN... X / WO3, each leveraging its own strengths, demonstrated excellent photoelectric cathodic protection performance.
[0013] Preferably, in step (1), the pH value for adjusting the pH is 1-5.
[0014] Preferably, in step (1), the mass ratio of Na2WO4·2H2O to Na2SO4 is 1:(0.5-2); more preferably, the mass ratio of Na2WO4·2H2O to Na2SO4 is 1:(1-2).
[0015] Preferably, in step (1), the temperature of the hydrothermal reaction is 150-200℃; more preferably, the temperature of the hydrothermal reaction is 170-190℃.
[0016] Preferably, in step (1), the hydrothermal reaction time is 20-28 hours; more preferably, the hydrothermal reaction time is 22-26 hours.
[0017] Preferably, in step (2), the mass ratio of the WO3 nanorods to the anionic surfactant is (25-500):1.
[0018] Preferably, in step (2), the anionic surfactant includes at least one of sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium hexadecylbenzene sulfonate, and sodium dodecylbenzene sulfonate.
[0019] Preferably, in step (2), the mass-to-volume ratio of the WO3 nanorods to pyrrole is 1 g:(20-200) μL; more preferably, the mass-to-volume ratio of the WO3 nanorods to pyrrole is 1 g:(100-200) μL.
[0020] Preferably, in step (2), the stirring time after adding pyrrole is 0.5-1.5h.
[0021] Preferably, in step (2), the concentration of the initiator solution is 0.08-0.12 mol / L.
[0022] Preferably, in step (2), the initiator includes at least one of ferric chloride, potassium permanganate, and ammonium persulfate.
[0023] Preferably, in step (2), the stirring time after the initiator solution is added is 3-5 hours.
[0024] Preferably, in step (3), the mass-to-volume ratio of the WO3 / PPy complex to tetrabutyl titanate is 1 mg:(0.05-2.5) mL; more preferably, the mass-to-volume ratio of the WO3 / PPy complex to tetrabutyl titanate is 1 mg:(0.1-1) mL.
[0025] Preferably, in step (3), the volume ratio of tetrabutyl titanate, glacial acetic acid and acetone is 1:(0.2-5):(0.2-5).
[0026] Preferably, in step (3), the alcohol solution includes at least one of n-butanol, isobutanol, and ethylene glycol.
[0027] Preferably, in step (3), the mass ratio of the WO3 / PPy complex to the anionic surfactant is 1:(0.1-10); more preferably, the mass ratio of the WO3 / PPy complex to the anionic surfactant is 1:(0.5-5).
[0028] Preferably, in step (3), the temperature of the hydrothermal reaction is 100-200℃ and the time is 1-6h.
[0029] Preferably, in step (4), the precursor TiO2 / PPy / WO3 composite is dissolved in an alcohol solution, then Nafion solution is added, followed by sonication, and then coated onto a conductive substrate. After drying and calcination, TiO2 / CN is obtained. X / WO3 composite photoanode.
[0030] More preferably, in step (4), the conductive substrate includes one of FTO and ITO.
[0031] More preferably, in step (4), the drying temperature is 50-70°C.
[0032] More preferably, in step (4), the calcination temperature is 400-550℃ and the time is 1-4h.
[0033] More preferably, in step (4), the heating rate of the calcination is 2-4℃ / min; the calcination is carried out under an argon protective atmosphere.
[0034] A second aspect of the present invention provides an energy storage type TiO2 / CN X The / WO3 composite material photoanode is prepared by the preparation method described above.
[0035] The TiO2 / CN of the present invention X The basic principle of photocathode protection using / WO3 composite materials is: ① The type II heterojunction formed between TiO2 and WO3 effectively improves the migration / separation of photogenerated carriers. Simultaneously, CN... X The introduction of [the substance] further improves the migration / separation efficiency of photogenerated carriers, promoting the improvement of the PECP performance of the material; ② In the dark state, WO3 releases the electrons stored under illumination to provide continuous photocathode protection for the metal, while CN [the substance]... X It serves as a highly efficient charge migration channel, greatly enhancing WO3's ability to store / release electrons; ③CN X During the high-temperature formation process, some WO3 is reduced, resulting in the generation of a small number of oxygen vacancies, which is beneficial to improving the light absorption efficiency of the material.
[0036] Compared with the prior art, the beneficial effects of the present invention are:
[0037] This invention prepares TiO2 / CN using a three-step hydrothermal-ultrasonic-hydrothermal method. X / WO3 composite material. TiO2 / CN X / WO3's excellent sustained photocathode protection performance can be attributed to the highly conductive CN X It works synergistically with WO3, a narrow-bandgap semiconductor with energy storage properties. Specifically, the introduction of carbon and nitrogen compounds improves the material's interface properties, increases its specific surface area and porosity, which is beneficial for accelerating the separation efficiency of electrons and holes, while also increasing the photocatalytically active specific surface area, thereby improving the photocathode protection performance; the introduction of WO3 is also a crucial step, relying on CN... X The excellent electron mobility of TiO2 allows excess photogenerated electrons to be rapidly migrated to the "WO3 core" in the composite material for storage and rapid release in the dark, thus demonstrating its energy storage properties. In addition, the narrow band gap of WO3 can improve the light absorption threshold of the composite material, thereby improving the light utilization efficiency of TiO2. Finally, TiO2 nanoparticles with stable photoelectrochemical properties serve as the host material, ensuring the stability of the photoelectric properties of the ternary material. Attached Figure Description
[0038] Figure 1 Here is a surface morphology (SEM) image of TiO2 from Example 1;
[0039] Figure 2 TiO2 / CN prepared in Example 1 X / WO3 composite material surface morphology (SEM) image;
[0040] Figure 3 TiO2 / CN prepared in Example 1 X / WO3 composite materials and TiO2 / WO3, TiO2 / CN X The photocurrent density changes over time (Light on represents illumination, Light off represents the light source being turned off, i.e., the dark state);
[0041] Figure 4 Example 1 shows the electrode potential changes over time before and after illumination of 403 stainless steel in a 3.65 wt% NaCl solution with different photoanodes (Light on indicates illumination, Light off indicates the light source is cut off, i.e., dark state). Detailed Implementation
[0042] The specific embodiments of the present invention will be further described below. It should be noted that these descriptions are for the purpose of aiding understanding the present invention, but do not constitute a limitation thereof. Furthermore, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.
[0043] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the experimental materials used in the following embodiments are all available through conventional commercial channels.
[0044] Example 1
[0045] This embodiment provides TiO2 / CN X The preparation method of the WO3 composite material photoanode specifically includes the following steps:
[0046] (1) Preparation of WO3 nanorods: WO3 nanorods were prepared by a hydrothermal method. 1 g of Na2WO4·2H2O and 0.5 g of Na2SO4 were dissolved in 30 mL of deionized water, and the pH was adjusted to 2.00 using 2 mol / L HCl solution, followed by stirring for 1 h. The thoroughly stirred solution was then rapidly transferred to a 50 mL container lined with polytetrafluoroethylene and placed in a 180 °C oven for 24 h. The reacted powder was washed multiple times with deionized water and anhydrous ethanol to remove excess inorganic salts. Finally, the sample was dried at 60 °C, and the obtained product, WO3 nanorods, was collected.
[0047] (2) Preparation of WO3 / PPy: 0.1 g of WO3 nanorods and 4 mg of sodium dodecylbenzenesulfonate were added to 40 mL of deionized water and sonicated for 30 min. After the WO3 nanorods were fully dispersed by sonication, 20 μL of pyrrole monomer was added and the mixture was stirred vigorously for 1 h. The uniformly dispersed solution was placed in an ice bath and stirred while slowly adding 0.1 mol / L ammonium persulfate (APS) solution until the solution color changed abruptly from dark green to black, and then the mixture was stirred for another 4 h. The centrifuged sample was washed with ethanol and deionized water, and then dried to obtain the WO3 / PPy composite.
[0048] (3) Precursor TiO2 / CN XPreparation of WO3: 10 mg of WO3 / PPy and 5 mg of sodium dodecylbenzenesulfonate were added to 15 mL of n-butanol, and the mixture was sealed with plastic wrap and sonicated for 30 min. Under stirring, 2.5 mL of tetrabutyl titanate, 2.5 mL of glacial acetic acid, and 2.5 mL of acetone were added sequentially, and the mixture was stirred continuously for 20 min to prepare solution ①. 0.75 mL of deionized water was mixed with 10 mL of n-butanol to prepare solution ②. Solution ② was slowly added dropwise to solution ① and stirred continuously for 2 h. The stirred solution was transferred to a hydrothermal reactor and placed in a 200℃ forced-air oven for 6 h. After natural cooling, the product was washed repeatedly by centrifugation with deionized water and anhydrous ethanol, and dried at 60℃ to collect the precursor TiO2 / PPy / WO3 complex. The preparation of TiO2 is similar, except that WO3 / PPy is not required during the reaction.
[0049] (4) TiO2 / CN X / WO3 photoanode preparation: 0.5 mg of the precursor TiO2 / PPy / WO3 was dissolved in 0.5 mL of anhydrous ethanol, followed by sonication for 30 min in Nafion solution (0.5 g / L). The solution was then dropped onto FTO, dried, and calcined at 450 °C for 2 h under an argon atmosphere at a heating rate of 3 °C / min. The calcined product was TiO2 / CN X / WO3 composite photoanode.
[0050] Test the prepared TiO2 / CN X The photocathode protection effect of WO3 composite material on 403 stainless steel:
[0051] The energy storage type TiO2 / CN described in Example 1 X The photocathodic protection performance of the / WO3 composite photoanode was tested. This performance is mainly reflected in the material's cathodic polarization capability (photopotential) and photoinduced current during illumination. Tests were conducted using a three-electrode single-electrolysis cell system on a Gamry 1010E electrochemical workstation. The loaded TiO2 / CN... X The WO3 composite photoanode was used as the working electrode and coupled to 304 stainless steel for testing. The active material loading was 0.5 mg, a 1×2 cm platinum sheet was used as the counter electrode, and an Ag / AgCl standard reference electrode was used as the reference electrode. The electrolyte in the electrolytic cell was a 3.65 wt% NaCl solution to simulate a marine environment. The three electrodes were placed in simulated seawater, and a xenon lamp filtered through an AM1.5 simulated sunlight filter was used to simulate a power of 100 mW·cm⁻¹. -2 Simulated sunlight was used to observe the photocurrents induced by it using an electrochemical workstation.
[0052] Figure 1 and Figure 2 For the preparation of TiO2 and TiO2 / CN X SEM images of the WO3 composite material. Comparison. Figure 1 and Figure 2 It can be seen that after TiO2 agglomeration, there are large particles with smooth surfaces, and the TiO2 / CN ratio is high. X The SEM images of the / WO3 composite material show more rod-like structures, indicating that WO3 nanorods encapsulated by PPy are dispersed in TiO2 particles during the hydrothermal reaction, which is beneficial to the improvement of the material's active specific surface area and chemical stability.
[0053] Figure 3 The curves showing the photocurrent density versus time for different prepared materials are shown. Among them, TiO2 / WO3 (prepared with TiO2 / CN) is shown. X Similar to WO3, the difference is that pyrrole is not needed during the reaction process (TiO2 / CN). X (Preparation with TiO2 / CN) X Similar to WO3, the difference is that WO3 nanorods do not need to be added during the reaction process, as does TiO2 / CN. X The peak photocurrent density of / WO3 was 12.45 μA·cm⁻¹. -2 14.98 μA·cm -2 and 18.23 μA·cm -2 A higher photocurrent density means that the photoanode has a higher efficiency in separating photogenerated electrons and holes, which indicates that TiO2 / CN X / WO3 exhibited excellent photogenerated carrier separation efficiency and maintained stable photocurrent even after four cycles of lamp switching on / off. Furthermore, TiO2 / CN X The / WO3 composite material exhibits a relatively slow current decay rate after the lights are turned off, and current is generated in the dark. This means that current still flows to 3O4SS even in darkness where photogenerated electrons cannot be generated. Specifically, TiO2 / WO3 and TiO2 / CN... X and TiO2 / CN X The dark-state current of / WO3 in the first photocycle was 0.5 μA·cm. -2 0.7 μA·cm -2 and 0.9 μA·cm -2 These results demonstrate that CN X WO3 has a certain ability to store electrons, which can store excess photogenerated electrons and release them after the illumination ends to improve the continuous cathodic protection of 304SS, confirming that TiO2 / CN X / WO3 is a photoelectric cathode protection material with certain energy storage characteristics.
[0054] Photocathode polarization potential is also one of the important evaluation indicators of the photoelectric cathodic protection effect of materials. Figure 4 The figure shows the OCP changes of different photoanodes coupled with 304SS electrodes under intermittent illumination. It can be seen from the figure that the coupling potential of each sample drops rapidly after illumination, indicating that the photoanode performs cathodic polarization on the 304SS under illumination. When the light source is turned off, the coupling potential begins to rise again, indicating that rapid photogenerated electron-hole pair recombination occurs on the photoanode surface. It is worth noting that TiO2 / CN... X The WO3 composite photoanode exhibits a decreasing potential trend in the dark. Figure 3 The analysis results of the I / O curve (continuous electron release from the photoanode in the dark state) further corroborate that the prepared composite photoanode has a certain energy storage effect and can provide continuous cathodic protection for 304SS in the dark state. Specifically, TiO2 / WO3 and TiO2 / CN X and TiO2 / CN X The peak photocathode polarization potentials of / WO3 reached -238mV, -258mV, and -306mV after four lamp-on / off cycles, respectively. TiO2 / CN X / WO3 exhibits the best photocathode polarization performance, and its potential in the dark environment shifts negatively by approximately 80mV compared to the initial potential, providing continuous cathodic protection for 304SS.
[0055] Example 2
[0056] This embodiment provides an energy storage type TiO2 / CN X The preparation method of the TiO2 / WO3 composite photoanode differs from Example 1 in that the masses of Na2WO4·2H2O and Na2SO4 in step (1) are 0.5 g and 1 g, respectively. The prepared TiO2 / WO3 and TiO2 / CN composite photoanodes... X The peak photocurrent density of / WO3 was 11.4 μA·cm. -2 and 20.23 μA·cm -2 Under conditions of no light, TiO2 / WO3 and TiO2 / CN X The dark-state current of / WO3 in the first photocycle was 0.35 μA·cm. -2 and 0.87 μA·cm -2 Meanwhile, TiO2 / WO3 and TiO2 / CN X The peak photocathode polarization potential of / WO3 reached -262mV and -325mV after four on / off cycles, respectively.
[0057] Example 3
[0058] This embodiment provides an energy storage type TiO2 / CNX The preparation method of the TiO2 / WO3 composite photoanode differs from that in Example 1 in that the pH is adjusted to 1.00 using HCl solution in step (1). The prepared TiO2 / WO3 and TiO2 / CN composite photoanodes... X The peak photocurrent density of / WO3 was 6.3 μA·cm. -2 and 9.41 μA·cm -2 Under conditions of no light, TiO2 / WO3 and TiO2 / CN X The dark-state current of / WO3 in the first photocycle was 0.102 μA·cm. -2 and 0.32 μA·cm -2 Meanwhile, TiO2 / WO3 and TiO2 / CN X The peak photocathode polarization potential of / WO3 reached -75mV and -121mV after four on / off cycles, respectively.
[0059] Example 4
[0060] This embodiment provides an energy storage type TiO2 / CN X The preparation method of the TiO2 / WO3 composite photoanode differs from Example 1 in that, in step (2), the WO3 nanorods and sodium dodecylbenzenesulfonate are 0.5 g and 3 mg, respectively. The prepared TiO2 / WO3 and TiO2 / CN composite photoanodes... X The peak photocurrent density of / WO3 was 10.45 μA·cm. -2 and 16.32 μA·cm -2 Under conditions of no light, TiO2 / WO3 and TiO2 / CN X The dark-state current of / WO3 in the first photocycle was 0.34 μA·cm. -2 and 0.78 μA·cm -2 Meanwhile, TiO2 / WO3 and TiO2 / CN X The peak photocathode polarization potentials of / WO3 reached -210mV and -279mV after four on / off cycles, respectively.
[0061] Example 5
[0062] This embodiment provides an energy storage type TiO2 / CN X The preparation method of the / WO3 composite photoanode differs from Example 1 in that the mass of WO3 / PPy and sodium dodecylbenzenesulfonate in step (3) is 5 mg and 10 mg, respectively. The prepared TiO2 / CN X The peak photocurrent density of / WO3 is 17.36 μA·cm. -2 Under conditions of no light, TiO2 / CN XThe dark-state current of / WO3 in the first photocycle was 0.82 μA·cm. -2 Meanwhile, TiO2 / WO3 and TiO2 / CN X The peak photocathode polarization potential of / WO3 reached -210mV and -281mV after four on / off cycles, respectively.
[0063] Example 6
[0064] This embodiment provides an energy storage type TiO2 / CN X The preparation method of the TiO2 / PPy / WO3 composite photoanode differs from that in Example 1, except that the calcination temperature of the precursor TiO2 / PPy / WO3 in step (3) is 550℃. The prepared TiO2 / WO3 and TiO2 / CN... X The peak photocurrent density of / WO3 was 9.1 μA·cm. -2 and 16.7 μA·cm -2 Under conditions of no light, TiO2 / WO3 and TiO2 / CN X The dark-state current of / WO3 in the first photocycle was 0.3 μA·cm. -2 and 0.67 μA·cm -2 Meanwhile, TiO2 / WO3 and TiO2 / CN X The peak photocathode polarization potential of / WO3 reached -193mV and -260mV after four on / off cycles, respectively.
[0065] The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and these variations still fall within the protection scope of the present invention.
Claims
1. An energy storage type TiO2 / CN X The method for preparing a / WO3 composite material photoanode is characterized by, Includes the following steps: (1) Na2WO4·2H2O and Na2SO4 are dissolved in water, pH is adjusted, and hydrothermal reaction is carried out. The solid obtained after the reaction is WO3 nanorods. (2) The WO3 nanorods and anionic surfactant were added to water, sonicated, pyrrole was added, stirred, and then an initiator solution was added dropwise under ice bath conditions. After stirring, the WO3 / PPy complex was obtained after the reaction. (3) The WO3 / PPy complex and the anionic surfactant were added to an alcohol solution, ultrasonicated and stirred, tetrabutyl titanate, glacial acetic acid and acetone were added, and then an aqueous alcohol solution was added dropwise. The mixture was transferred to a hydrothermal reactor for reaction. After the hydrothermal reaction, the precursor TiO2 / PPy / WO3 complex was obtained. (4) The precursor TiO2 / PPy / WO3 composite is coated on a conductive substrate and calcined to obtain TiO2 / CN. X / WO3 composite photoanode.
2. The energy storage type TiO2 / CN according to claim 1 X The method for preparing a / WO3 composite material photoanode is characterized by, In step (1), the pH value for adjusting pH is 1-5.
3. The energy storage type TiO2 / CN according to claim 1 X The method for preparing a / WO3 composite material photoanode is characterized by, In step (1), the mass ratio of Na2WO4·2H2O to Na2SO4 is 1:(0.5-2).
4. The energy storage type TiO2 / CN according to claim 1 X The method for preparing a / WO3 composite material photoanode is characterized by, In step (2), the mass ratio of the WO3 nanorods to the anionic surfactant is (25-500):
1.
5. The energy storage type TiO2 / CN according to claim 4 X The method for preparing a / WO3 composite material photoanode is characterized by, In step (2), the mass-to-volume ratio of the WO3 nanorods to pyrrole is 1 g: (20-200) μL.
6. The energy storage type TiO2 / CN according to claim 1 X The method for preparing a / WO3 composite material photoanode is characterized by, In step (3), the mass-to-volume ratio of the WO3 / PPy complex and tetrabutyl titanate is 1 mg: (0.05-2.5) mL.
7. The energy storage type TiO2 / CN according to claim 6 X The method for preparing a / WO3 composite material photoanode is characterized by, In step (3), the volume ratio of tetrabutyl titanate, glacial acetic acid and acetone is 1:(0.2-5):(0.2-5).
8. The energy storage type TiO2 / CN according to claim 1 X The method for preparing a / WO3 composite material photoanode is characterized by, In step (3), the temperature of the hydrothermal reaction is 100-200℃ and the time is 1-6h.
9. The energy storage type TiO2 / CN according to claim 1 X The method for preparing a / WO3 composite material photoanode is characterized by, In step (4), the calcination temperature is 400-550℃ and the time is 1-4h.
10. An energy storage type TiO2 / CN X / WO3 composite material photoanode, characterized in that... It is prepared by the preparation method according to any one of claims 1-9.