A method for in situ construction of a photoresponsive ternary heterostructure on a titanium surface

Abstract

A method for in situ construction of a photoresponsive ternary heterostructure on a titanium surface is disclosed. This method addresses the limited effectiveness of existing single heterostructure types in separating photogenerated holes and electrons. The method includes: 1. micro-arc oxidation; 2. microwave hydrothermal treatment; 3. ion exchange treatment; and 4. heat treatment. This method is used to in situ construct a photoresponsive ternary heterostructure on a titanium surface.

Description

Technical Field

[0001] The present invention relates to a method for constructing a ternary heterostructure. Background Art

[0002] The commonly used TiO2-based photoresponsive heterojunctions currently have a large bandgap, can only absorb light in the ultraviolet band, and are prone to recombination of photogenerated holes and electrons. Common heterostructure types include Type I, Type II, and Z-type heterostructures. A single heterostructure type has limited effectiveness in separating photogenerated holes and electrons. Therefore, there is an urgent need to prepare ternary heterostructures consisting of Type I with either Type II or Z-type heterostructures, thereby achieving a more negative oxidation potential for photogenerated holes and a more positive reduction potential for photogenerated electrons, thereby improving the heterostructure's photoresponsiveness. Summary of the Invention

[0003] The present invention aims to solve the problem that the existing single heterostructure type has limited effect on separating photogenerated holes and electrons, and further provides a method for in situ constructing a light-responsive ternary heterostructure on a titanium surface.

[0004] A method for in-situ construction of a photoresponsive ternary heterostructure on a titanium surface is carried out in the following steps:

[0005] 1. Micro-arc oxidation treatment:

[0006] The pretreated titanium plate is placed in an electrolyte, with the pretreated titanium plate as the anode and the stainless steel plate as the cathode, and micro-arc oxidation is performed in a pulse constant current mode under the conditions of a current of 0.5A to 2.5A, a pulse frequency of 600Hz to 1000Hz, a duty cycle of 4% to 20%, and an electrolyte temperature of 20°C to 30°C to obtain a titanium plate treated with micro-arc oxidation;

[0007] The electrolyte consists of ethylenediaminetetraacetate, acetate, tungsten salt, metaphosphate, alkali solution and deionized water;

[0008] 2. Microwave hydrothermal treatment:

[0009] The titanium plate treated by micro-arc oxidation is immersed in a tungstate solution for microwave hydrothermal treatment to obtain a titanium plate treated by microwave hydrothermal treatment;

[0010] 3. Ion exchange treatment:

[0011] The titanium plate after microwave hydrothermal treatment is immersed in an acid solution, and finally washed and dried to obtain the titanium plate after ion exchange treatment;

[0012] 4. Heat treatment:

[0013] The titanium plate after ion exchange is placed in a muffle furnace and heat treated for 1h to 8h in an air atmosphere at a temperature of 300°C to 800°C, thereby completing the method of in situ construction of a light-responsive ternary heterostructure on the titanium surface.

[0014] The beneficial effects of the present invention are:

[0015] The present invention aims to construct a photoresponsive ternary TiO2 / CaWO3 / WO3 heterostructure on the surface of a titanium plate in situ. A porous coating containing Ca elements is prepared on the surface of the titanium plate by micro-arc oxidation technology, and then microwave hydrothermal treatment is performed to form a large number of blade-shaped calcium tungstate crystals (Ca2O3) on the surface of the titanium micro-arc oxidation coating. 2+ +WO4 2- ―CaWO4), through acid ion exchange technology, control the ion exchange time (CaWO4+2H + ―H2WO4+Ca 2+ ), converted into a calcium tungstate / tungstic acid composite structure, and after heat treatment, transformed into a TiO2 / CaWO3 / WO3 heterostructure, thereby broadening the absorption band range, improving the light response intensity, and solving the problem that the existing single heterostructure type has limited effect on separating photogenerated holes and electrons.

[0016] The sample treated by the present invention was subjected to EDS energy spectrum detection, and trace elements such as calcium and tungsten were successfully introduced into the coating. XRD diffraction detection showed the presence of calcium tungstate and tungsten oxide in the sample treated by the present invention. Scanning electron microscopy showed that a large amount of leaf-shaped calcium tungstate and granular tungsten oxide were formed on the surface of the coating. The light response ability of the surface of the sample treated by the present invention was characterized. A sample with a size of 10mm×10mm was placed in a subunit blue solution. Under the irradiation of a xenon lamp, the light response intensity of the ternary heterostructure was evaluated based on the degradation ability of the organic dye. Compared with the sample with only titanium dioxide on the titanium plate after micro-arc oxidation treatment, the degradation rate of the organic dye can reach more than 80%. This shows that the sample obtained by the present invention has a certain light response intensity.

[0017] Appendix

[0018] Figure 1 This is the EDS spectrum of the ternary TiO2 / CaWO3 / WO3 heterostructure constructed on the titanium surface in Example 1;

[0019] Figure 2 This is the XRD pattern of the ternary TiO2 / CaWO3 / WO3 heterostructure constructed on the titanium surface in Example 1, where A is the anatase peak, B is the titanium peak, C is calcium tungstate, and D is tungsten oxide;

[0020] Figure 3 This is a scanning electron microscope image of the ternary TiO2 / CaWO3 / WO3 heterostructure constructed on the titanium surface in Example 1;

[0021] Figure 4 The organic dye degradation rates of the titanium plate after micro-arc oxidation treatment prepared in step 1 of Example 1 and the ternary TiO2 / CaWO3 / WO3 heterostructure constructed on the titanium surface in step 4 are shown. DETAILED DESCRIPTION

[0022] Specific embodiment 1: This embodiment is a method for in-situ construction of a photoresponsive ternary heterostructure on a titanium surface, which is carried out in the following steps:

[0023] 1. Micro-arc oxidation treatment:

[0024] The pretreated titanium plate is placed in an electrolyte, with the pretreated titanium plate as the anode and the stainless steel plate as the cathode, and micro-arc oxidation is performed in a pulse constant current mode under the conditions of a current of 0.5A to 2.5A, a pulse frequency of 600Hz to 1000Hz, a duty cycle of 4% to 20%, and an electrolyte temperature of 20°C to 30°C to obtain a titanium plate treated with micro-arc oxidation;

[0025] The electrolyte consists of ethylenediaminetetraacetate, acetate, tungsten salt, metaphosphate, alkali solution and deionized water;

[0026] 2. Microwave hydrothermal treatment:

[0027] The titanium plate treated by micro-arc oxidation is immersed in a tungstate solution for microwave hydrothermal treatment to obtain a titanium plate treated by microwave hydrothermal treatment;

[0028] 3. Ion exchange treatment:

[0029] The titanium plate after microwave hydrothermal treatment is immersed in an acid solution, and finally washed and dried to obtain the titanium plate after ion exchange treatment;

[0030] 4. Heat treatment:

[0031] The titanium plate after ion exchange is placed in a muffle furnace and heat treated for 1h to 8h in an air atmosphere at a temperature of 300°C to 800°C, thereby completing the method of in situ construction of a light-responsive ternary heterostructure on the titanium surface.

[0032] The beneficial effects of this embodiment are:

[0033] This embodiment aims to construct a photoresponsive ternary TiO2 / CaWO3 / WO3 heterostructure on the titanium plate surface in situ. A porous coating containing Ca element is prepared on the titanium plate surface by micro-arc oxidation technology, and then microwave hydrothermal treatment is performed to form a large number of blade-shaped calcium tungstate crystals (Ca2O3) on the surface of the titanium micro-arc oxidation coating. 2+ +WO4 2- ―CaWO4), through acid ion exchange technology, control the ion exchange time (CaWO4+2H +―H2WO4+Ca 2+ ), converted into a calcium tungstate / tungstic acid composite structure, and after heat treatment, transformed into a TiO2 / CaWO3 / WO3 heterostructure, thereby broadening the absorption band range, improving the light response intensity, and solving the problem that the existing single heterostructure type has limited effect on separating photogenerated holes and electrons.

[0034] The sample treated by the present embodiment was subjected to EDS energy spectrum detection, and trace elements such as calcium and tungsten were successfully introduced into the coating. XRD diffraction detection showed the presence of calcium tungstate and tungsten oxide in the sample treated by the present embodiment. Scanning electron microscopy showed that a large amount of leaf-shaped calcium tungstate and granular tungsten oxide were formed on the surface of the coating. The light response ability of the surface of the sample treated by the present embodiment was characterized. A sample with a size of 10mm×10mm was placed in a subunit blue solution. Under the irradiation of a xenon lamp, the light response intensity of the ternary heterostructure was evaluated based on the degradation ability of the organic dye. Compared with the sample with only titanium dioxide on the titanium plate after micro-arc oxidation treatment, the degradation rate of the organic dye can reach more than 80%. This shows that the sample obtained by the present embodiment has a certain light response intensity.

[0035] Specific embodiment 2: This embodiment differs from specific embodiment 1 in that the pretreated titanium plate described in step 1 is prepared by polishing the titanium plate surface using 400# and 1000# metallographic sandpaper, then washing it with deionized water, and finally drying it at a temperature of 20°C to 30°C for 0.5h to 1h to obtain the pretreated titanium plate. Other steps are the same as those in specific embodiment 1.

[0036] Specific embodiment 3: This embodiment differs from specific embodiment 1 or 2 in that the titanium plate is made of titanium, titanium alloy, titanium-based medium entropy alloy or titanium-based high entropy alloy. Other aspects are the same as specific embodiment 1 or 2.

[0037] Specific embodiment 4: This embodiment differs from any one of specific embodiments 1 to 3 in that the titanium plate is an HCP-Ti medium-entropy alloy or high-entropy alloy, a BCC-Ti medium-entropy alloy or high-entropy alloy, a BCC medium-entropy alloy or high-entropy alloy, or a BCC and HCP dual-phase medium-entropy alloy or high-entropy alloy. Other aspects are the same as specific embodiments 1 to 3.

[0038] Specific embodiment 5: This embodiment differs from Specific embodiments 1 to 4 in that the electrolyte described in step 1 is composed of disodium EDTA, calcium acetate, sodium tungstate, sodium hexametaphosphate, sodium hydroxide, and deionized water, and the concentration of disodium EDTA in the electrolyte is 8 g / L to 20 g / L, the concentration of calcium acetate is 4 g / L to 15 g / L, the concentration of sodium tungstate is 2 g / L to 20 g / L, the concentration of sodium hexametaphosphate is 5 g / L to 20 g / L, and the concentration of sodium hydroxide is 5 g / L to 20 g / L. Other embodiments are the same as Specific embodiments 1 to 4.

[0039] Specific embodiment 6: This embodiment differs from Specific embodiments 1 to 5 in that in step 1, micro-arc oxidation is performed for 5 to 40 minutes under the conditions of a current of 0.5 A to 2.5 A, a pulse frequency of 600 Hz to 1000 Hz, a duty cycle of 4% to 20%, and an electrolyte temperature of 20° C. to 30° C. The rest is the same as Specific embodiments 1 to 5.

[0040] Specific embodiment 7: This embodiment differs from specific embodiments 1 to 6 in that the tungstate solution in step 2 is a sodium tungstate solution or a potassium tungstate solution; and the concentration of the tungstate solution in step 2 is 0.01 mol / L to 3.0 mol / L. Other aspects are the same as specific embodiments 1 to 6.

[0041] Specific embodiment 8: This embodiment differs from Specific embodiments 1 to 7 in that, in step 2, the titanium plate after micro-arc oxidation treatment is immersed in a tungstate solution and subjected to microwave hydrothermal treatment at a power of 200W to 1000W and a temperature of 60°C to 200°C for 1 to 8 hours. Other steps are the same as Specific embodiments 1 to 7.

[0042] Specific embodiment 9: This embodiment differs from specific embodiments 1 to 8 in that the acid solution in step 3 is hydrochloric acid, sulfuric acid, and phosphoric acid; and the concentration of the acid solution in step 3 is 6 mol / L to 12 mol / L. Other aspects are the same as specific embodiments 1 to 8.

[0043] Specific embodiment 10: This embodiment differs from specific embodiments 1 to 9 in that in step 3, the titanium plate after microwave hydrothermal treatment is immersed in an acid solution at a temperature of 20°C to 80°C for 6 to 18 minutes. Other aspects are the same as specific embodiments 1 to 9.

[0044] The following examples are used to verify the beneficial effects of the present invention:

[0045] Example 1:

[0046] A method for in-situ construction of a photoresponsive ternary heterostructure on a titanium surface is carried out in the following steps:

[0047] 1. Micro-arc oxidation treatment:

[0048] The pretreated titanium plate was placed in an electrolyte, with the pretreated titanium plate as the anode and the stainless steel plate as the cathode, and micro-arc oxidation was performed for 20 minutes in a pulse constant current mode under the conditions of a current of 2.0 A, a pulse frequency of 800 Hz, a duty cycle of 8%, and an electrolyte temperature of 30°C to obtain a titanium plate treated with micro-arc oxidation;

[0049] The electrolyte is composed of disodium edetate, calcium acetate, sodium tungstate, sodium hexametaphosphate, sodium hydroxide and deionized water, and the concentration of disodium edetate in the electrolyte is 12 g / L, the concentration of calcium acetate is 4.4 g / L, the concentration of sodium tungstate is 12 g / L, the concentration of sodium hexametaphosphate is 10 g / L, and the concentration of sodium hydroxide is 5 g / L;

[0050] The pretreated titanium plate is specifically prepared according to the following steps: polishing the surface of the titanium plate with 400# and 1000# metallographic sandpaper in sequence, then washing it with deionized water, and finally drying it at a temperature of 25°C for 0.5h to obtain a pretreated titanium plate;

[0051] The titanium plate is HCP type titanium;

[0052] 2. Microwave hydrothermal treatment:

[0053] The titanium plate treated by micro-arc oxidation was immersed in a tungstate solution and subjected to microwave hydrothermal treatment at a power of 600 W and a temperature of 200°C for 3 h to obtain a titanium plate treated by microwave hydrothermal treatment;

[0054] The tungstate solution is a sodium tungstate solution; the concentration of the tungstate solution is 0.5 mol / L;

[0055] 3. Ion exchange treatment:

[0056] The titanium plate after microwave hydrothermal treatment was immersed in an acid solution at a temperature of 70°C for 12 minutes, and finally washed and dried to obtain the titanium plate after ion exchange treatment.

[0057] The acid solution is hydrochloric acid; the concentration of the acid solution is 12 mol / L;

[0058] 4. Heat treatment:

[0059] The ion-exchanged titanium plate was placed in a muffle furnace and heat treated for 5 hours in an air atmosphere at 600°C to obtain a ternary TiO2 / CaWO3 / WO3 heterostructure constructed on the titanium surface.

[0060] Figure 1This is the EDS spectrum of the ternary TiO2 / CaWO3 / WO3 heterostructure constructed on the titanium surface in Example 1. As can be seen from the figure, trace elements such as calcium and tungsten have been successfully introduced into the coating.

[0061] Figure 2 This is the XRD pattern of the ternary TiO2 / CaWO3 / WO3 heterostructure constructed on the titanium surface in Example 1. A represents the anatase peak, B represents the titanium peak, C represents calcium tungstate, and D represents tungsten oxide. As can be seen from the figure, XRD diffraction analysis reveals the presence of calcium tungstate and tungsten oxide in the sample treated in this example.

[0062] Figure 3 This is a scanning electron microscope image of the ternary TiO2 / CaWO3 / WO3 heterostructure constructed on the titanium surface in Example 1. As can be seen from the scanning photo, a large amount of leaf-shaped calcium tungstate and granular tungsten oxide are formed on the coating surface.

[0063] A 10 mm × 10 mm titanium plate or a ternary TiO2 / CaWO3 / WO3 heterostructure constructed on a titanium surface after micro-arc oxidation was placed in 10 mL of 10 mg / mL subunit blue solution and irradiated with a 300 W xenon lamp for 120 min. The photoresponse intensity of the ternary heterostructure was evaluated based on the degradation ability of the organic dye. Figure 4 This figure shows the organic dye degradation rate for the titanium plate treated with micro-arc oxidation (MAO) in step 1 of Example 1 and the ternary TiO2 / CaWO3 / WO3 heterostructure constructed on the titanium surface in step 4. Compared to a sample containing only titanium dioxide after MAO, the organic dye degradation rate reached 88%, demonstrating that the samples obtained in this example possess a certain light response intensity.

[0064] Example 2: This example differs from Example 1 in that in step 1, micro-arc oxidation is performed for 20 minutes under the conditions of a current of 2.0 A, a pulse frequency of 600 Hz, a duty cycle of 8%, and an electrolyte temperature of 20° C. Other steps are the same as in Example 1.

[0065] EDS spectroscopy of the treated samples in this example revealed the successful introduction of trace elements such as calcium and tungsten into the coating. XRD diffraction analysis revealed the presence of calcium tungstate and tungsten oxide in the treated samples. Scanning electron microscopy revealed the formation of a large amount of leaf-shaped calcium tungstate and granular tungsten oxide on the coating surface. The photoresponse of the treated samples in this example was characterized using the same testing method as in Example 1, demonstrating an 80% degradation rate for the organic dye. This demonstrates that the samples obtained in this example possess a certain photoresponse intensity.

[0066] Example 3: This example differs from Example 1 in that the concentration of disodium EDTA in the electrolyte in step 1 is 15 g / L and the concentration of calcium acetate is 8.8 g / L. Other steps are the same as Example 1.

[0067] EDS spectroscopy of the treated samples in this example revealed the successful introduction of trace elements such as calcium and tungsten into the coating. XRD diffraction analysis revealed the presence of calcium tungstate and tungsten oxide in the treated samples. Scanning electron microscopy revealed the formation of a large amount of leaf-shaped calcium tungstate and granular tungsten oxide on the coating surface. The photoresponsiveness of the treated sample surface was characterized using the same testing method as in Example 1, demonstrating an 82% degradation rate for the organic dye. This demonstrates that the sample obtained in this example possesses a moderate photoresponsiveness.

[0068] Example 4: This example differs from Example 1 in that the concentration of the tungstate solution in step 2 is 1.0 mol / L. Other steps are the same as Example 1.

[0069] EDS spectroscopy of the treated samples in this example revealed the successful introduction of trace elements such as calcium and tungsten into the coating. XRD diffraction analysis revealed the presence of calcium tungstate and tungsten oxide in the treated samples. Scanning electron microscopy revealed the formation of a large amount of leaf-shaped calcium tungstate and granular tungsten oxide on the coating surface. The photoresponsiveness of the treated sample surface was characterized using the same testing method as in Example 1, demonstrating an 85% degradation rate for the organic dye. This demonstrates that the sample obtained in this example possesses a certain photoresponsiveness.

[0070] Example 5: This example differs from Example 1 in that the concentration of the sodium tungstate solution in step 2 is 3.0 mol / L. Other aspects are the same as Example 1.

[0071] EDS spectroscopy of the treated samples in this example revealed the successful introduction of trace elements such as calcium and tungsten into the coating. XRD diffraction analysis revealed the presence of calcium tungstate and tungsten oxide in the treated samples. Scanning electron microscopy revealed the formation of a large amount of leaf-shaped calcium tungstate and granular tungsten oxide on the coating surface. The photoresponse of the treated samples in this example was characterized using the same testing method as in Example 1, demonstrating an 80% degradation rate for the organic dye. This demonstrates that the samples obtained in this example possess a certain photoresponse intensity.

[0072] Example 6: This example differs from Example 1 in that the acid solution in step 3 is hydrochloric acid with a concentration of 8 mol / L. Other steps are the same as Example 1.

[0073] EDS spectroscopy of the treated samples in this example revealed the successful introduction of trace elements such as calcium and tungsten into the coating. XRD diffraction analysis revealed the presence of calcium tungstate and tungsten oxide in the treated samples. Scanning electron microscopy revealed the formation of a large amount of leaf-shaped calcium tungstate and granular tungsten oxide on the coating surface. The photoresponse of the treated samples in this example was characterized using the same testing method as in Example 1, demonstrating an 83% degradation rate for the organic dye. This demonstrates that the samples obtained in this example possess a certain photoresponse intensity.

[0074] Example 7: This example differs from Example 1 in that the soaking temperature in step 3 is 80° C. The rest is the same as Example 1.

[0075] EDS spectroscopy of the treated samples in this example revealed the successful introduction of trace elements such as calcium and tungsten into the coating. XRD diffraction analysis revealed the presence of calcium tungstate and tungsten oxide in the treated samples. Scanning electron microscopy revealed the formation of a large amount of leaf-shaped calcium tungstate and granular tungsten oxide on the coating surface. The photoresponsiveness of the treated sample surface was characterized using the same testing method as in Example 1, demonstrating an 86% degradation rate for the organic dye. This demonstrates that the sample obtained in this example possesses a moderate photoresponsiveness.

[0076] Example 8: This example differs from Example 1 in that the soaking time in step 3 is 18 minutes. Other steps are the same as Example 1.

[0077] EDS spectroscopy of the treated samples in this example revealed the successful introduction of trace elements such as calcium and tungsten into the coating. XRD diffraction analysis revealed the presence of calcium tungstate and tungsten oxide in the treated samples. Scanning electron microscopy revealed the formation of a large amount of leaf-shaped calcium tungstate and granular tungsten oxide on the coating surface. The photoresponsiveness of the treated sample surface was characterized using the same testing method as in Example 1, demonstrating an 84% degradation rate for the organic dye. This demonstrates that the sample obtained in this example possesses a certain photoresponsiveness.

[0078] Example 9: This example differs from Example 1 in that in step 4, the heat treatment is performed in an air atmosphere at a temperature of 800° C. for 8 hours. Other steps are the same as in Example 1.

[0079] EDS spectroscopy of the treated samples in this example revealed the successful introduction of trace elements such as calcium and tungsten into the coating. XRD diffraction analysis revealed the presence of calcium tungstate and tungsten oxide in the treated samples. Scanning electron microscopy revealed the formation of a large amount of leaf-shaped calcium tungstate and granular tungsten oxide on the coating surface. The photoresponsiveness of the treated sample surface was characterized using the same testing method as in Example 1, demonstrating an 85% degradation rate for the organic dye. This demonstrates that the sample obtained in this example possesses a certain photoresponsiveness.

Claims

1. A method for in situ construction of a photoresponsive ternary heterostructure on a titanium surface, characterized in that It is carried out in the following steps:

1. Micro-arc oxidation treatment: The pretreated titanium plate is placed in an electrolyte, with the pretreated titanium plate as the anode and the stainless steel plate as the cathode, and micro-arc oxidation is performed in a pulse constant current mode under the conditions of a current of 0.5A to 2.5A, a pulse frequency of 600Hz to 1000Hz, a duty cycle of 4% to 20%, and an electrolyte temperature of 20°C to 30°C to obtain a titanium plate treated with micro-arc oxidation; The electrolyte is composed of disodium edetate, calcium acetate, sodium tungstate, sodium hexametaphosphate, sodium hydroxide and deionized water, and the concentration of disodium edetate in the electrolyte is 8g / L-20g / L, the concentration of calcium acetate is 4g / L-15g / L, the concentration of sodium tungstate is 2g / L-20g / L, the concentration of sodium hexametaphosphate is 5g / L-20g / L, and the concentration of sodium hydroxide is 5g / L-20g / L; 2. Microwave hydrothermal treatment: The titanium plate treated by micro-arc oxidation is immersed in a tungstate solution for microwave hydrothermal treatment to obtain a titanium plate treated by microwave hydrothermal treatment; 3. Ion exchange treatment: The titanium plate after microwave hydrothermal treatment is immersed in an acid solution, and finally washed and dried to obtain the titanium plate after ion exchange treatment; 4. Heat treatment: The titanium plate after ion exchange is placed in a muffle furnace and heat treated for 1h to 8h in an air atmosphere at a temperature of 300°C to 800°C, thereby completing the method of in situ construction of a light-responsive ternary heterostructure on the titanium surface.

2. The method for in situ construction of a photoresponsive ternary heterostructure on a titanium surface according to claim 1, characterized in that The pretreated titanium plate described in step 1 is specifically prepared according to the following steps: polishing the surface of the titanium plate with 400# and 1000# metallographic sandpaper in sequence, then washing it with deionized water, and finally drying it at a temperature of 20°C to 30°C for 0.5h to 1h to obtain a pretreated titanium plate.

3. The method for in situ construction of a photoresponsive ternary heterostructure on a titanium surface according to claim 2, characterized in that The titanium plate is made of titanium, titanium alloy, titanium-based medium entropy alloy or titanium-based high entropy alloy.

4. The method for in situ construction of a photoresponsive ternary heterostructure on a titanium surface according to claim 2, characterized in that The titanium plate is an HCP-Ti medium entropy alloy or high entropy alloy, a BCC-Ti medium entropy alloy or high entropy alloy, a BCC medium entropy alloy or high entropy alloy, or a BCC and HCP dual-phase medium entropy alloy or high entropy alloy.

5. The method for in situ construction of a photoresponsive ternary heterostructure on a titanium surface according to claim 1, characterized in that In step 1, micro-arc oxidation is performed for 5 min to 40 min under the conditions of a current of 0.5 A to 2.5 A, a pulse frequency of 600 Hz to 1000 Hz, a duty cycle of 4% to 20% and an electrolyte temperature of 20° C. to 30° C.

6. The method for in situ construction of a photoresponsive ternary heterostructure on a titanium surface according to claim 1, characterized in that The tungstate solution in step 2 is a sodium tungstate solution or a potassium tungstate solution; the concentration of the tungstate solution in step 2 is 0.01 mol / L to 3.0 mol / L.

7. The method for in situ construction of a photoresponsive ternary heterostructure on a titanium surface according to claim 1, characterized in that In step 2, the titanium plate after micro-arc oxidation treatment is immersed in a tungstate solution and subjected to microwave hydrothermal treatment for 1 h to 8 h at a power of 200 W to 1000 W and a temperature of 60° C. to 200° C.

8. The method for in situ construction of a photoresponsive ternary heterostructure on a titanium surface according to claim 1, characterized in that The acid solution described in step 3 is hydrochloric acid, sulfuric acid and phosphoric acid; the concentration of the acid solution described in step 3 is 6 mol / L to 12 mol / L.

9. The method for in-situ construction of a photoresponsive ternary heterostructure on a titanium surface according to claim 1, characterized in that In step three, the titanium plate after microwave hydrothermal treatment is immersed in an acid solution at a temperature of 20° C. to 80° C. for 6 min to 18 min.

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