Preparation method of nano-TiO2@AC@GPs electrocatalytic anode material

Abstract

The present invention relates to the technical field of electrocatalytic material synthesis, specifically a method for preparing a nano-TiO2@AC@GPs electrocatalytic anode material. The method comprises first depositing an amorphous carbon layer AC on the surface of a graphite sheet (GPs) using chemical vapor deposition to obtain an AC@GPs composite material. CTAB is then dissolved in a methanol / deionized water mixed solution and stirred to obtain a solution A. A titanium sulfate solution is added to solution A to obtain a precursor solution B. The precursor solution B and the AC@GPs composite material are mixed and subjected to a hydrothermal reaction. After the reaction, the sample is washed, dried, and calcined to obtain a nano-TiO2@AC@GPs electrocatalytic anode material. The preparation process of the present invention is simple and efficient, and the resulting nano-TiO2@AC@GPs electrocatalytic anode material has excellent electrocatalytic activity and cyclic stability, addressing the problems of poor electrocatalytic performance of traditional graphite anode materials and having broad prospects for industrial application.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrocatalytic material synthesis, and in particular relates to a method for preparing a nano-TiO2@AC@GPs electrocatalytic anode material. Background Art

[0002] Electrocatalytic oxidation technology has attracted widespread attention in wastewater treatment and pollutant degradation due to its advantages such as high efficiency, controllability, and zero secondary pollution. As one of the core components of electrocatalytic technology, the performance of electrocatalytic anode materials directly affects the efficiency and stability of the entire electrocatalytic system.

[0003] Currently, commonly used electrocatalytic anode materials include titanium-coated electrodes (such as DSA electrodes), diamond film electrodes, and graphite electrodes. Traditional graphite electrodes suffer from uneven conductivity, a limited number of surface active sites, and susceptibility to oxidation loss, limiting their application at high current densities. Therefore, improving the electrocatalytic activity and stability of graphite-based anode materials has become a pressing technical challenge.

[0004] TiO2 is an excellent photocatalyst and electrocatalyst carrier with excellent chemical stability and corrosion resistance. Loading nano-TiO2 onto carbon-based materials can effectively enhance their electron transport capacity and catalytic activity. However, the existing technology lacks a simple and efficient method to uniformly and stably anchor nano-TiO2 onto the surface of a graphite substrate and achieve chemical epitaxial growth to enhance interfacial bonding and catalytic performance. Summary of the Invention

[0005] The purpose of the present invention is to provide a method for preparing a nano-TiO2@AC@GPs electrocatalytic anode material. An amorphous carbon layer is deposited as an intermediate layer on a graphite sheet by a simple and efficient method. TiO2 is then chemically epitaxially grown on the surface of the amorphous carbon layer by a hydrothermal method, so that TiO2 grows uniformly on the surface of the substrate, thereby improving the interfacial bonding strength and stability between TiO2 and the substrate, enhancing the electrocatalytic effect and cycle stability of the material, and solving the problems of poor electrocatalytic performance of traditional graphite anode materials.

[0006] The present invention is specifically implemented by the following technical solutions. According to the present invention, a method for preparing a nano-TiO2@AC@GPs electrocatalytic anode material includes the following steps:

[0007] (1) Deposition of amorphous carbon coating: Using methane as a carbon source, a layer of amorphous carbon layer AC was deposited on the surface of graphite sheets GPs by chemical vapor deposition to obtain AC@GPs composite materials;

[0008] (2) Preparation of precursor solution: dissolve hexadecyltrimethylammonium bromide in a mixed solution of methanol and deionized water to obtain solution A, and make the concentration of hexadecyltrimethylammonium bromide in solution A be 2-4 g / L; add titanium sulfate solution to solution A and stir evenly to obtain solution B;

[0009] (3) Hydrothermal synthesis of nano-TiO2: The AC@GPs composite material obtained in step (1) and the solution B obtained in step (2) are transferred to a hydrothermal reactor and subjected to a hydrothermal reaction at 120-200°C to allow TiO2 nanomaterials to grow epitaxially on the surface of the AC coating of the AC@GPs composite material;

[0010] (4) Post-treatment: After the hydrothermal reaction is completed, the sample is taken out and washed, dried and calcined at high temperature in sequence to obtain nano-TiO2@AC@GPs electrocatalytic anode material.

[0011] Furthermore, the process parameters of the chemical vapor deposition method in step (1) are: deposition temperature 800-1100° C., reaction time 30-120 min, and protective atmosphere of argon or nitrogen.

[0012] Furthermore, the volume ratio of methanol to deionized water in the mixed solution of step (2) is 1:1 to 3:1.

[0013] Furthermore, Ti in solution B of step (2) 4+ The concentration is controlled at 0.0045~0.0083 mol / L.

[0014] Furthermore, the hydrothermal reaction time in step (3) is 6 to 24 h.

[0015] Furthermore, in step (4), the sample is washed alternately with deionized water and ethanol for 6 times (the sample is washed with deionized water for the 1st, 3rd and 5th time, and the sample is washed with anhydrous ethanol for the 2nd, 4th and 6th time), the washed sample is dried in an oven at 80°C, and high-temperature calcination is carried out under inert gas at a calcination temperature of 300-600°C and a calcination time of 1-4 hours.

[0016] Furthermore, in the TiO2@AC@GPs electrocatalytic anode material finally prepared according to the aforementioned preparation method, TiO2 is anatase-type, and TiO2 grows uniformly on the surface of AC@GPs in the form of small particles. The TiO2 particles are uniform in size, with an average diameter of 25~50nm.

[0017] The present invention also provides an application of the TiO2@AC@GPs electrocatalytic anode material prepared according to the above preparation method in the electrocatalytic degradation of organic wastewater, especially for the electrocatalytic degradation of the organic dye Rhodamine B. Under the same conditions, the degradation rate of the organic dye Rhodamine B by the TiO2@AC@GPs electrocatalytic anode material is much greater than that of the original graphite sheet GPs and AC@GPs composite material. The first-order kinetic equation rate constant of the TiO2@AC@GPs electrocatalytic anode material for the degradation of Rhodamine B is 6 times that of the original graphite sheet.

[0018] Compared with the prior art, the present invention has obvious advantages and beneficial effects. By means of the above technical solution, the present invention can achieve considerable technological advancement and practicality, and has a wide range of utilization value. It has at least the following advantages:

[0019] By introducing an amorphous carbon interlayer onto the graphite sheet surface, this method enhances the subsequent nucleation and growth of nano-TiO2, improving the overall interfacial bonding strength, stability, and service life of the material, resulting in an electrocatalytic anode material with excellent cycling and catalytic properties. The chemical vapor deposition (CVD) and hydrothermal methods employed are both mature and easily scalable industrial technologies suitable for large-scale production.

[0020] Compared to pristine graphite flakes (GPs) and AC@GPs composites, the nano-TiO2@AC@GPs electrocatalytic anode material prepared by this invention exhibits superior electrocatalytic activity, cyclic stability, and corrosion resistance. After 14 electrocatalytic cycles over 1680 minutes, the degradation rate of the organic dye Rhodamine B remained within a reasonable range, demonstrating stable and reliable electrocatalytic effect. Under the same conditions, the nano-TiO2@AC@GPs electrocatalytic anode material exhibited far greater degradation of the organic dye Rhodamine B than pristine graphite flakes, demonstrating excellent application in organic wastewater treatment and electrochemical oxidation degradation of pollutants.

[0021] The present invention does not use toxic or harmful reagents in the material preparation process, conforms to the development direction of green chemistry, requires less raw materials, and has a simple and efficient preparation process. It solves the problem of poor electrocatalytic performance of traditional graphite anode materials and has broad industrial application prospects in the field of wastewater treatment. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] FIG1(a) is a SEM image of the original graphite sheet used in Example 1.

[0023] Figure 1(b) is a SEM image of the AC@GPs composite material obtained in step (1) of Example 1.

[0024] FIG2( a ) is a Raman spectrum of the original graphite sheet used in Example 1. ...

[0025] Figure 2 (b) is the Raman spectrum of the AC@GPs composite material obtained in step (1) of Example 1.

[0026] Figure 3 This is the X-ray diffraction (XRD) pattern of the nano-TiO2@AC@GPs electrocatalytic anode material prepared in Example 1.

[0027] Figure 4 This is the photocurrent curve of the nano-TiO2@AC@GPs electrocatalytic anode material prepared in Example 1.

[0028] Figure 5 (a) is a SEM image of the nano-TiO2@AC@GPs electrocatalytic anode material prepared in Example 1 at a magnification of 30 times.

[0029] Figure 5 (b) is a SEM image of the nano-TiO2@AC@GPs electrocatalytic anode material prepared in Example 1 at a magnification of 20,000 times.

[0030] Figure 5 (c) is a SEM image of the nano-TiO2@AC@GPs electrocatalytic anode material prepared in Example 1 at a magnification of 100,000 times.

[0031] Figure 6 This is the SEM image of the TiO2@GPs electrocatalytic anode material prepared in Comparative Example 1.

[0032] Figure 7 The graph shows the change in degradation rate of the organic dye Rhodamine B with degradation time for the original graphite sheet, the AC@GPs composite material obtained in step (1) of Example 1, and the nano-TiO2@AC@GPs electrocatalytic anode material prepared in Example 1.

[0033] Figure 8 This is a curve showing the change in degradation rate of the organic dye Rhodamine B by the TiO2@GPs material prepared in Comparative Example 1 as a function of degradation time.

[0034] Figure 9 This is the first-order kinetic curve of the degradation of the organic dye Rhodamine B by the original graphite sheet, the AC@GPs composite material obtained in step (1) of Example 1, and the nano-TiO2@AC@GPs electrocatalytic anode material prepared in Example 1.

[0035] Figure 10 This is a graph showing 14 electrocatalytic degradation cycles of the organic dye Rhodamine B by the nano-TiO2@AC@GPs electrocatalytic anode material prepared in Example 1. DETAILED DESCRIPTION

[0036] To make the objectives, technical solutions, and advantages of the embodiments of the present invention more clear, the technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0037] The present invention is described in detail below with reference to specific examples. In the following examples, if specific conditions are not specified, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. The raw materials and reagents used, if the manufacturer is not specified, are all conventional products that can be purchased commercially. The high-purity graphite sheets used in the examples were purchased from Dongguan Tianwang Graphite Products Factory. In the following examples, the ethanol used to wash the product can be anhydrous ethanol or a 95% ethanol solution.

[0038] Example 1:

[0039] (1) High-purity graphite sheets (GPs) with a thickness of 2 mm were ultrasonically cleaned with acetone and placed in a CVD reactor. Argon was introduced as a protective gas (argon flow rate of 180 SCCM). The reactor was heated to 950°C and methane gas was introduced (methane flow rate of 60 SCCM). The reaction was maintained for 60 min to deposit an amorphous carbon layer AC on the surface of the graphite sheet to obtain an AC@GPs composite material.

[0040] (2) Weigh 0.2 g of CTAB and dissolve it in 50 mL of a mixed solution of methanol / deionized water (the volume ratio of methanol to deionized water is 2:1) to obtain solution A; add 10 mL of 0.05 mol / LTi(SO4)2 solution to solution A and stir evenly to obtain solution B;

[0041] (3) The AC@GPs composite material obtained in step (1) and solution B obtained in step (2) were transferred to a hydrothermal reactor and subjected to hydrothermal reaction at 160°C for 12 h to allow TiO2 to chemically grow epitaxially on the surface of the AC coating;

[0042] (4) After the hydrothermal reaction, the sample was taken out and washed alternately with deionized water and ethanol for 6 times (the sample was washed with deionized water for the 1st, 3rd and 5th time, and with anhydrous ethanol for the 2nd, 4th and 6th time). The washed sample was dried in an oven at 80 °C and then calcined at 400 °C for 2 h in an argon atmosphere to obtain nano-TiO2@AC@GPs electrocatalytic anode material.

[0043] Example 2:

[0044] (1) High-purity graphite sheets (GPs) with a thickness of 2 mm were ultrasonically cleaned with acetone and placed in a CVD reactor. Argon was introduced as a protective gas (argon flow rate of 180 SCCM). The reactor was heated to 1000°C and methane gas was introduced (methane flow rate of 60 SCCM). The reaction was maintained for 60 min to deposit an amorphous carbon layer AC on the surface of the graphite sheet to obtain an AC@GPs composite material.

[0045] (2) Weigh 0.1 g of CTAB and dissolve it in 50 mL of a mixed solution of methanol / deionized water (the volume ratio of methanol to deionized water is 2:1) to obtain solution A; add 10 mL of 0.05 mol / LTi(SO4)2 solution to solution A and stir evenly to obtain solution B;

[0046] (3) The AC@GPs composite material obtained in step (1) and solution B obtained in step (2) were transferred to a hydrothermal reactor and subjected to hydrothermal reaction at 160°C for 10 h to allow TiO2 to chemically grow epitaxially on the surface of the AC coating;

[0047] (4) After the hydrothermal reaction, the sample was taken out and washed alternately with deionized water and ethanol for 6 times (the sample was washed with deionized water for the 1st, 3rd and 5th time, and with anhydrous ethanol for the 2nd, 4th and 6th time). The washed sample was dried in an oven at 80 °C and then calcined at 400 °C for 2 h in an argon atmosphere to obtain nano-TiO2@AC@GPs electrocatalytic anode material.

[0048] Example 3:

[0049] (1) High-purity graphite sheets (GPs) with a thickness of 2 mm were ultrasonically cleaned with acetone and placed in a CVD reactor. Nitrogen was introduced as a protective gas (nitrogen flow rate 200 SCCM). The reactor was heated to 950°C and methane gas was introduced (methane flow rate 60 SCCM). The reaction was maintained for 30 min to deposit an amorphous carbon layer AC on the surface of the graphite sheet to obtain an AC@GPs composite material.

[0050] (2) Weigh 0.2 g of CTAB and dissolve it in 50 mL of a mixed solution of methanol / deionized water (the volume ratio of methanol to deionized water is 2:1) to obtain solution A; add 10 mL of 0.05 mol / LTi(SO4)2 solution to solution A and stir evenly to obtain solution B;

[0051] (3) The AC@GPs composite material obtained in step (1) and solution B obtained in step (2) were transferred to a hydrothermal reactor and subjected to hydrothermal reaction at 160°C for 14 h to allow TiO2 to chemically grow epitaxially on the surface of the AC coating;

[0052] (4) After the hydrothermal reaction, the sample was taken out and washed alternately with deionized water and ethanol for 6 times (the sample was washed with deionized water for the 1st, 3rd and 5th time, and with anhydrous ethanol for the 2nd, 4th and 6th time). The washed sample was dried in an oven at 80 °C and then calcined at 400 °C for 2 h in an argon atmosphere to obtain nano-TiO2@AC@GPs electrocatalytic anode material.

[0053] Example 4:

[0054] (1) A 2 mm thick high-purity graphite sheet (GPs) was ultrasonically cleaned with acetone and placed in a CVD reactor. Nitrogen was introduced as a protective gas (nitrogen flow rate 200 SCCM). The reactor was heated to 1000 °C and methane gas (methane flow rate 60 SCCM) was introduced. The reaction was maintained for 30 min to deposit an amorphous carbon layer AC on the surface of the graphite sheet to obtain an AC@GPs composite material.

[0055] (2) Weigh 0.1 g of CTAB and dissolve it in 50 mL of a mixed solution of methanol / deionized water (the volume ratio of methanol to deionized water is 2:1) to obtain solution A; add 5 mL of 0.05 mol / LTi(SO4)2 solution to solution A and stir evenly to obtain solution B;

[0056] (3) The AC@GPs composite material obtained in step (1) and solution B obtained in step (2) were transferred to a hydrothermal reactor and subjected to hydrothermal reaction at 160°C for 12 h to allow TiO2 to chemically grow epitaxially on the surface of the AC coating;

[0057] (4) After the hydrothermal reaction, the sample was taken out and washed alternately with deionized water and ethanol for 6 times (the sample was washed with deionized water for the 1st, 3rd and 5th times, and with anhydrous ethanol for the 2nd, 4th and 6th times). The washed sample was dried in an oven at 80 °C and then calcined at 500 °C for 2 h in an argon atmosphere to obtain nano-TiO2@AC@GPs electrocatalytic anode material.

[0058] Example 5:

[0059] (1) High-purity graphite sheets (GPs) with a thickness of 2 mm were ultrasonically cleaned with acetone and placed in a CVD reactor. Argon was introduced as a protective gas (argon flow rate of 180 SCCM). The reactor was heated to 950°C and methane gas was introduced (methane flow rate of 60 SCCM). The reaction was maintained for 60 min to deposit an amorphous carbon layer AC on the surface of the graphite sheet to obtain an AC@GPs composite material.

[0060] (2) Weigh 0.15 g of CTAB and dissolve it in 50 mL of a mixed solution of methanol / deionized water (the volume ratio of methanol to deionized water is 2:1) to obtain solution A; add 8 mL of 0.05 mol / LTi(SO4)2 solution to solution A and stir evenly to obtain solution B;

[0061] (3) The AC@GPs composite material obtained in step (1) and solution B obtained in step (2) were transferred to a hydrothermal reactor and subjected to hydrothermal reaction at 140°C for 16 h to allow TiO2 to chemically grow epitaxially on the surface of the AC coating;

[0062] (4) After the hydrothermal reaction, the sample was taken out and washed alternately with deionized water and ethanol for 6 times (the sample was washed with deionized water for the 1st, 3rd and 5th time, and with anhydrous ethanol for the 2nd, 4th and 6th time). The washed sample was dried in an oven at 80 °C and then calcined at 600 °C for 2 h in an argon atmosphere to obtain nano-TiO2@AC@GPs electrocatalytic anode material.

[0063] Comparative Example 1

[0064] (1) Take high-purity graphite sheets (GPs) with a thickness of 2 mm and clean them with acetone ultrasonically for later use;

[0065] (2) Weigh 0.2 g of CTAB and dissolve it in 50 mL of a mixed solution of methanol / deionized water (the volume ratio of methanol to deionized water is 2:1) to obtain solution A; add 10 mL of 0.05 mol / LTi(SO4)2 solution to solution A and stir evenly to obtain solution B;

[0066] (3) The high-purity graphite sheets GPs cleaned in step (1) and the solution B obtained in step (2) were transferred to a hydrothermal reactor and subjected to a hydrothermal reaction at 160°C for 12 h;

[0067] (4) After the hydrothermal reaction, the sample was taken out and washed alternately with deionized water and ethanol for 6 times (the sample was washed with deionized water for the 1st, 3rd, and 5th time, and washed with anhydrous ethanol for the 2nd, 4th, and 6th time). The washed sample was dried in an oven at 80 °C and then calcined at 600 °C for 2 h in an argon atmosphere to obtain TiO2@GPs electrocatalytic anode material.

[0068] Figure 1 (a) is an SEM image of the original graphite sheet used in Example 1, and Figure 1 (b) is an SEM image of the AC@GPs composite material obtained after depositing the amorphous carbon layer in step (1) of Example 1. By comparison, it can be seen that an amorphous carbon coating can be formed on the surface of the graphite sheet by chemical vapor deposition.

[0069] Figure 2 (a) is the Raman spectrum of the original graphite sheet used in Example 1, and Figure 2 (b) is the Raman spectrum of the AC@GPs composite material obtained in step (1) of Example 1. Compared with the original graphite sheet, the intensity of the D peak (near 1350 cm⁻¹) is significantly enhanced (compared with the original graphite sheet, the peak height at 1350 cm⁻¹ is significantly increased), the intensity of the G peak (near 1580 cm⁻¹) does not change much, and the ID / IG ratio increases, indicating that a defective carbon coating layer is introduced on the graphite surface.

[0070] Figure 3 This is the X-ray diffraction (XRD) pattern of the nano-TiO2@AC@GPs electrocatalytic anode material prepared in Example 1. The 25.00° peak (intensity 12141.6666) is close to the 25.3° peak of anatase titanium dioxide, and the 48.00° peak (intensity 6191.6666) is close to the 48.1° peak of anatase titanium dioxide, but the peak positions are slightly offset. XRD analysis confirms the presence of titanium dioxide in the prepared nano-TiO2@AC@GPs electrocatalytic anode material. This peak shift may be due to peak broadening caused by the small size of the TiO2 nanoparticles or interaction with graphite. Because the graphite surface is completely covered by anatase titanium dioxide, no diffraction peaks associated with graphite flakes are detected.

[0071] The photocurrent curve of the nano-TiO2@AC@GPs electrocatalytic anode material prepared in Example 1 was tested using a time-current curve in an electrochemical workstation. The test solution was a 1 g / L sodium sulfate solution. The results were as follows: Figure 4 As shown, the peak height and shape of the curves are essentially consistent across multiple cycles, demonstrating a stable photoelectric response and suitability for long-term photoelectric applications. After switching on the light, the current rapidly rises to a steady state, indicating that the composite material effectively generates electron-hole pairs under illumination. After blocking the light, the current decays to a dark current. The high photocurrent and low dark current demonstrate the material's efficient photogenerated charge separation and stable photoelectric response. The good current repeatability and low dark current make it suitable for applications such as photocatalytic water splitting and pollutant degradation.

[0072] Figure 5 shows SEM images of the nano-TiO2@AC@GPs electrocatalytic anode material prepared in Example 1 at different magnifications. Figures 5(a), 5(b), and 5(c) are at magnifications of 30x, 20,000x, and 100,000x, respectively. Figure 5(c) shows that the TiO2 grows uniformly on the AC layer of the AC@GPs composite material in the form of small particles. The TiO2 particles are uniform in size, with an average diameter of approximately 25 to 50 nm.

[0073] Figure 6 This is the SEM image of the TiO2@GPs electrocatalytic anode material prepared in Comparative Example 1. Figure 6It can be seen that in Comparative Example 1, only part of the graphite sheet surface is covered with TiO2, and TiO2 is loosely combined with GPs, resulting in poor material stability. Figure 6 By comparison, it can be seen that depositing an amorphous carbon layer on the surface of the graphite sheet as an intermediate layer can enhance the subsequent nucleation and growth ability of TiO2, so that TiO2 can be evenly covered on the surface of AC@GPs, thereby improving the overall interface bonding ability of the material, forming a stable TiO2@AC@GPs material, and improving the electrocatalytic activity and stability of the TiO2@AC@GPs material.

[0074] Prepare a series of Rhodamine B standard solutions of different concentrations, test the absorbance of the Rhodamine B standard solutions of different concentrations at 554nm, make a standard curve of absorbance versus concentration, and obtain the standard curve equation of the absorbance versus concentration of the Rhodamine B solution. Use a stainless steel mesh (size of 20*20*2mm) as the cathode, and the nano-TiO2@AC@GPs electrocatalytic anode material prepared in Example 1 as the anode (size of 20*20*2mm). Test the electrocatalytic degradation effect of the TiO2@AC@GPs electrocatalytic anode material on Rhodamine B under constant current. The volume of the Rhodamine B solution is 200 mL, the initial concentration is 20 mg / L, the electrolyte is 1g / L sodium sulfate, and the degradation time is 120 min. Test the absorbance of the Rhodamine B solution at time t at 554nm, and substitute the absorbance into the standard curve equation to calculate the concentration C of Rhodamine B in the solution at time t. t , with D%=(C0-C t ) / C0×100% to calculate the degradation rate, where D% represents the degradation rate and C0 represents the initial concentration of the rhodamine B solution. The degradation rate is plotted against the degradation time. The degradation rates of the original graphite sheet and the AC@GPs composite material obtained in step (1) of Example 1 at different degradation times were tested in the same manner. The degradation rate is plotted against the degradation time. The results are shown in Figure 2. Figure 7 As shown in Figure 3, the degradation rate of the organic dye Rhodamine B by the nano-TiO2@AC@GPs electrocatalytic anode material is much greater than that of the original graphite sheet GPs and AC@GPs composite material.

[0075] Figure 8 This is the curve showing the degradation rate of the organic dye Rhodamine B by the TiO2@GPs material prepared in Comparative Example 1 versus degradation time. Figure 7 and Figure 8 By comparison, it can be seen that the electrocatalytic degradation effect of the nano-TiO2@AC@GPs electrocatalytic anode material prepared in Example 1 on Rhodamine B under constant current is also much greater than that of the TiO2@GPs material prepared in Comparative Example 1, indicating that the amorphous carbon coating is beneficial to enhancing the degradation effect of the TiO2@AC@GPs electrocatalytic anode material on Rhodamine B.

[0076] In the above degradation rate test, according to the C t value, calculate ln(C0 / C t ), ln(C0 / C t ) is plotted against the degradation time to obtain the first-order kinetic curves and equations for the degradation of Rhodamine B by the original graphite sheet, the AC@GPs composite material obtained in step (1) of Example 1, and the nano-TiO2@AC@GPs electrocatalytic anode material prepared in Example 1, as shown in FIG. Figure 9 As shown, it can be seen that the first-order kinetic equation rate constant of the degradation of Rhodamine B by nano-TiO2@AC@GPs electrocatalytic anode material is 6 times that of the original graphite sheet.

[0077] Figure 10 This is a graph showing the electrocatalytic degradation cycle experiment of the nano-TiO2@AC@GPs electrocatalytic anode material prepared in Example 1 on the organic dye Rhodamine B for 14 times and 1680 minutes. It can be seen that the nano-TiO2@AC@GPs electrocatalytic anode material has excellent cycle stability and corrosion resistance. After 14 times and 1680 minutes of electrocatalytic cycle experiments, the electrocatalytic effect remains within a reasonable fluctuation range, and the electrocatalytic effect is stable and reliable.

[0078] The above description is merely an embodiment of the present invention and does not constitute any form of limitation to the present invention. The present invention may also have other forms of embodiments based on the above structures and functions, which are not listed here one by one. Therefore, any simple modification, equivalent changes, and modifications made to the above embodiments by any person skilled in the art in accordance with the technical essence of the present invention without departing from the scope of the technical solution of the present invention shall still fall within the scope of the technical solution of the present invention.

Claims

1. A nano-TiO2@AC@GPs electrocatalytic anode material, characterized in that: An amorphous carbon layer (AC) is deposited on the surface of graphite sheets (GPs). TiO2 grows uniformly on the AC layer of AC@GPs in the form of small particles. The TiO2 particles are uniform in size, with an average diameter of 25-50 nm. The nano-TiO2@AC@GPs electrocatalytic anode material is prepared according to the following steps: (1) Using methane as the carbon source, a layer of amorphous carbon layer AC was deposited on the surface of graphite sheets GPs by chemical vapor deposition to obtain AC@GPs composite materials. The thickness of the graphite sheets GPs was 2 mm. (2) Dissolve hexadecyltrimethylammonium bromide in a mixed solution of methanol and deionized water in a volume ratio of 2:1 to obtain solution A, and make the concentration of hexadecyltrimethylammonium bromide in solution A be 2~4 g / L; add titanium sulfate solution to solution A and stir evenly to obtain solution B. 4+ The concentration is controlled at 0.0045~0.0083 mol / L; (3) transferring the AC@GPs composite material obtained in step (1) and the solution B obtained in step (2) to a hydrothermal reactor, and performing a hydrothermal reaction at 120-200° C. to allow TiO2 nanomaterials to epitaxially grow on the surface of the AC coating of the AC@GPs composite material; (4) After the hydrothermal reaction is completed, the sample is taken out and washed, dried and calcined at high temperature in sequence. The calcination temperature is 400℃ or 500℃ to obtain nano-TiO2@AC@GPs electrocatalytic anode material.

2. The nano-TiO2@AC@GPs electrocatalytic anode material according to claim 1, characterized in that: The process parameters of chemical vapor deposition in step (1) are: deposition temperature 850-1100°C, reaction time 30-60 min, and protective atmosphere of argon or nitrogen.

3. The nano-TiO2@AC@GPs electrocatalytic anode material according to claim 1, characterized in that: The hydrothermal reaction time in step (3) is 6 to 24 h.

4. The nano-TiO2@AC@GPs electrocatalytic anode material according to claim 1, characterized in that: In step (4), the sample is washed alternately with deionized water and ethanol for 6 times, and the washed sample is dried in an oven at 80°C. The high-temperature calcination is carried out under inert gas for 1 to 4 h.

5. Use of the nano-TiO2@AC@GPs electrocatalytic anode material as claimed in claim 1 in electrocatalytic degradation of organic wastewater.

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