Titanium dioxide amidoxime modified graphite felt electrode material, preparation method and use thereof

Abstract

The application discloses a kind of titanium dioxide amidoxime modified graphite felt electrode materials and preparation method and purposes thereof.The preparation method comprises the following steps: 1) providing TiO2 solution;2) TiO2 solution is mixed with polyacrylonitrile powder, to obtain mixture;Hydroxylamine hydrochloride is added to the mixture and reacts, to obtain first reactant;Then alkali metal carbonate is added to the first reactant and reacts, to obtain TiO2 / amidoxime solution;3) graphite felt is immersed in the TiO2 / amidoxime solution obtained in step 2), ultrasonic, take out graphite felt, to obtain preliminary loaded graphite felt, and the obtained preliminary loaded graphite felt is dried;Repeat the steps of immersion, ultrasonic, take out graphite felt, drying multiple times, to obtain titanium dioxide amidoxime modified graphite felt electrode material.The titanium dioxide amidoxime modified graphite felt electrode material prepared by the preparation method of the application can be used for seawater uranium extraction, and has good antibacterial performance and good anti-bioadhesion performance.

Description

Technical Field

[0001] This invention relates to a titanium dioxide-modified graphite felt electrode material, its preparation method, and its uses. Background Technology

[0002] Seawater is one of the most important and promising unconventional uranium resources. The total uranium content in seawater reaches 4.5 billion tons, serving as an effective supplement to terrestrial uranium resources. However, the concentration of uranium in seawater is very low, and the environment is complex. During uranium extraction, issues such as material adsorption kinetics and microbial adhesion must be considered, leading to long extraction times and low efficiency. Electrochemical methods utilize electric fields to improve uranium extraction efficiency by adsorbing uranyl ions onto the surface of charged electrodes, concentrating and enriching them. The development of electrode materials is crucial for electrochemical methods. Furthermore, microbial adhesion during seawater uranium extraction severely interferes with the material's uranium adsorption process, reducing the uranium adsorption capacity. This is one of the key challenges restricting seawater uranium extraction.

[0003] Therefore, it is essential to develop seawater uranium extraction electrode materials that possess both good adsorption properties and good resistance to bioattachment in seawater. Summary of the Invention

[0004] One object of this invention is to provide a method for preparing a titanium dioxide-modified graphite felt electrode material. The titanium dioxide-modified graphite felt electrode material prepared by the method of this invention can be used for uranium extraction from seawater and exhibits good antibacterial properties and resistance to bioattachment. Another object of this invention is to provide a titanium dioxide-modified graphite felt electrode material. A further object of this invention is to provide an application of the titanium dioxide-modified graphite felt electrode material. These objects of this invention are achieved through the following technical solutions.

[0005] This invention provides a method for preparing a titanium dioxide-modified amine oxime-based graphite felt electrode material, comprising the following steps:

[0006] 1) Provide a TiO2 solution with a mass concentration of 0.3–1.0 wt%;

[0007] 2) Mix TiO2 solution with polyacrylonitrile powder to obtain a mixture; add hydroxylamine hydrochloride to the mixture and react to obtain the first reactant; then add alkali metal carbonate to the first reactant and react to obtain TiO2 / gammoxime solution;

[0008] 3) Immerse the graphite felt in the TiO2 / mercaptoxime solution obtained in step 2), sonicate, remove the graphite felt to obtain a pre-loaded graphite felt, and dry the pre-loaded graphite felt; then place the dried pre-loaded graphite felt in the TiO2 / mercaptoxime solution again, sonicate again, remove the graphite felt to obtain a re-loaded graphite felt, and dry the re-loaded graphite felt; repeat the above steps of immersion, sonication, removal of graphite felt, and drying to obtain titanium dioxide mecaptoxime modified graphite felt electrode material.

[0009] The mass ratio of TiO2 solution, polyacrylonitrile powder, and hydroxylamine hydrochloride is 30:(0.4~0.6):(0.2~0.3).

[0010] The molar ratio of alkali metal carbonate to hydroxylamine hydrochloride is 1:1.9 to 2.1.

[0011] The resulting titanium dioxide-amine oxime-modified graphite felt electrode material possesses both good adsorption performance for uranium in seawater and good antibacterial properties when adsorbing uranium from seawater.

[0012] In step 1), the mass concentration of the TiO2 solution can be 0.3–1.0 wt%, preferably 0.33–1.0 wt%. The solvent used in the TiO2 solution is an organic solvent selected from N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide, preferably N,N-dimethylformamide.

[0013] In this invention, the TiO2 used in the TiO2 solution can be purchased or made in-house, with in-house preparation being preferred.

[0014] In step 2), TiO2 solution is mixed with polyacrylonitrile powder to obtain a mixture; hydroxylamine hydrochloride is added to the mixture and reacted at 55-85℃ for 3-5.5h to obtain the first reactant; then alkali metal carbonate is added to the first reactant and reacted at 60-85℃ for 8-15h to obtain TiO2 / gammoxime solution.

[0015] In this invention, it is preferable to add polyacrylonitrile powder to the TiO2 solution. The mass ratio of TiO2 solution to polyacrylonitrile powder and hydroxylamine hydrochloride can be 30:(0.4-0.6):(0.2-0.3), preferably 30:(0.5-0.6):(0.2-0.3).

[0016] After adding hydroxylamine hydrochloride, the reaction is carried out under heating. The reaction temperature can be 55–85°C, preferably 60–80°C, for example, 60°C, 65°C, 70°C, 75°C, or 80°C. The reaction time can be 3–5.5 h, preferably 3–5 h, for example, 3 h, 4 h, or 5 h.

[0017] An alkali metal carbonate is added to the first reactant, followed by heating. The reaction temperature can be 60–85°C, preferably 65–85°C, for example, 65°C, 70°C, 75°C, 80°C, or 85°C. The reaction time can be 8–15 hours, preferably 10–15 hours.

[0018] The molar ratio of alkali metal carbonate to hydroxylamine hydrochloride can be 1:1.9 to 2.1, preferably 1:2.0 to 2.05. The alkali metal carbonate can be sodium carbonate or potassium carbonate.

[0019] In step 3), there are no particular restrictions on the size of the graphite felt, which can be (10-30) mm × (10-30) mm × (1-3) mm. The graphite felt is completely immersed in the obtained TiO2 / gammoxime solution.

[0020] In step 3), the ultrasonic time can be 20–30 minutes. Drying can be done by vacuum drying at a temperature of 50–85°C.

[0021] The repeated steps mentioned above include repeating them more than once. Repeating the above steps once involves immersing the dried, reloaded graphite felt again in a TiO2 / amine oxime solution, sonicating it, removing the graphite felt to obtain a third-loaded graphite felt, and then drying the third-loaded graphite felt to obtain the target material product.

[0022] According to the preparation method of the present invention, preferably, the solvent used in the TiO2 solution is an organic solvent, which is selected from N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide.

[0023] According to the preparation method of the present invention, preferably, the TiO2 solution is prepared by the following steps:

[0024] (a) Add an aqueous solution of alkali metal hydroxide to a soluble titanium salt solution, stir and mix to obtain a mixture; place the mixture in a hydrothermal reactor, and then react at 100-120°C, separate the solid and liquid, wash and dry the obtained solid to obtain the TiO2 precursor;

[0025] (b) The TiO2 precursor was placed in an atmosphere resistance furnace and then calcined in an inert gas atmosphere at 600-720°C for 2-4 hours to obtain TiO2 material;

[0026] (c) The TiO2 material is stirred and mixed with the organic solvent, and then sonicated to obtain a TiO2 solution. The titanium dioxide-amine oxime-modified graphite felt electrode material formed from the TiO2 material prepared by the self-made method of the present invention has higher uranium extraction yield from seawater and higher antibacterial efficiency.

[0027] In step (a), the soluble titanium salt is selected from one or more of titanium chloride, titanium nitrate, titanium acetate, and titanium sulfate, preferably titanium chloride. The alkali metal hydroxide is selected from one or more of potassium hydroxide and sodium hydroxide, preferably sodium hydroxide or potassium hydroxide.

[0028] The concentration of the alkali metal hydroxide aqueous solution can be 0.5–0.9 mol / L, preferably 0.5–0.8 mol / L, for example, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, or 0.9 mol / L. This is beneficial for obtaining a TiO2 precursor with higher purity and higher yield, which is conducive to the subsequent loading of graphite felt.

[0029] The reaction temperature in the hydrothermal reactor can be 100–120°C, preferably 110–120°C. The reaction time can be 1–4 hours, preferably 2–4 hours.

[0030] In this invention, solid-liquid separation can be achieved through filtration or centrifugation, with filtration being preferred. Drying can be performed under vacuum at a temperature of 50–70°C.

[0031] In step (b), the inert gas includes nitrogen and argon. The calcination temperature can be 600–720°C, preferably 600–700°C. The calcination time can be 2–4 hours, preferably 2–3 hours.

[0032] In step (c), the mass ratio of TiO2 material to the organic solvent is such that the mass concentration of the formed TiO2 solution is 0.3–1.0 wt%, preferably 0.33–1.0 wt%. The preferred mass ratio of TiO2 material to the organic solvent is 0.1–0.3:30. The organic solvent is selected from N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide.

[0033] According to the preparation method of the present invention, preferably, the soluble titanium salt is selected from one or more of titanium chloride, titanium nitrate, titanium acetate, and titanium sulfate; the alkali metal hydroxide is selected from one or more of potassium hydroxide and sodium hydroxide.

[0034] According to the preparation method of the present invention, preferably, the concentration of the aqueous solution of alkali metal hydroxide is 0.5 to 0.9 mol / L.

[0035] According to the preparation method of the present invention, preferably, the molar ratio of titanium element to alkali metal hydroxide in the soluble titanium salt is 1:3 to 5.5, more preferably 1:3.5 to 5, and even more preferably 1:3.5 to 4.5.

[0036] According to the preparation method of the present invention, preferably, step 2) includes the following specific steps: mixing TiO2 solution with polyacrylonitrile powder to obtain a mixture; adding hydroxylamine hydrochloride to the mixture and reacting at 55-85°C for 3-5.5 h to obtain a first reactant; then adding an alkali metal carbonate to the first reactant and reacting at 60-85°C for 8-15 h to obtain a TiO2 / gammoxime solution.

[0037] According to the preparation method of the present invention, preferably, the molar ratio of alkali metal carbonate to hydroxylamine hydrochloride is 1:2.0 to 2.05; the alkali metal carbonate is selected from sodium carbonate or potassium carbonate.

[0038] On the other hand, the present invention also provides a titanium dioxide-amine oxime-modified graphite felt electrode material, which is prepared according to the preparation method described above.

[0039] Furthermore, the present invention also provides the use of the titanium dioxide-modified graphite felt electrode material according to the above description in uranium extraction from seawater. The titanium dioxide-modified graphite felt electrode material exhibits a uranium extraction capacity of 3.7 mg / g or higher in simulated seawater. Moreover, it demonstrates an inhibition rate of 86% or higher against *Escherichia coli*, preferably 90% or higher, and an inhibition rate of 83% or higher against *Staphylococcus aureus*, preferably 85% or higher.

[0040] The titanium dioxide-modified graphite felt electrode material prepared by the method of this invention can be used for uranium adsorption in seawater while simultaneously improving the antibacterial properties of the material. This results in a product that possesses excellent uranium extraction performance, electrochemical performance, and anti-bioattachment properties. Furthermore, the preparation method of this invention is simple to operate and conducive to industrial production. Attached Figure Description

[0041] Figure 1 This is a scanning electron microscope (SEM) image of the titanium dioxide-amine oxime-modified graphite felt electrode material obtained in Example 1.

[0042] Figure 2 This is the energy dispersive spectroscopy (EDS) scan of the titanium dioxide-amine oxime-modified graphite felt electrode material obtained in Example 1.

[0043] Figure 3 In response to Figure 2 The results were obtained from energy dispersive spectroscopy analysis of 39 points in the medium spectrum.

[0044] Figure 4 The image shows the infrared spectrum of the titanium dioxide-amine oxime-modified graphite felt electrode material obtained in Example 1. Detailed Implementation

[0045] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto.

[0046] In the following example, the application of titanium dioxide-modified graphite felt electrode material involves using titanium dioxide-modified graphite felt electrode material as the working electrode, a graphite sheet electrode as the counter electrode, and a saturated calomel electrode as the reference electrode to form a three-electrode system. A voltage is applied to simulated seawater (natural seawater supplemented with uranyl tricarbonate to a solution uranium concentration of 3.3 mg / L) to electro-adsorb and enrich uranium. The voltage ranges from -3 to 0 V, the pH of the simulated seawater is 8.1, the adsorption time is 5 h, the adsorption temperature is 25 °C, and the uranyl ion concentration is determined according to HJ700.

[0047] The determination of the antibacterial rate of electrode materials was carried out in accordance with GB / T 20944.3~2008.

[0048] Scanning electron microscope images: Tested using a Hitachi S-4800 scanning electron microscope from Japan.

[0049] Energy dispersive spectroscopy (EDS) scans were performed using a Hitachi S-4800 scanning electron microscope.

[0050] Infrared spectrum: The test was performed using a Bruker Tensor II Fourier transform infrared spectrometer.

[0051] In the following examples, the sources and specifications of some of the raw materials used are as follows:

[0052] Polyacrylonitrile powder: purchased from Nanjing Yaojie Energy Saving Technology Co., Ltd., with a number average molecular weight of 50,000;

[0053] Hydroxylamine hydrochloride: purchased from Shanghai Maclean Biochemical Technology Co., Ltd., specification: 500g.

[0054] Graphite felt: purchased from Inner Mongolia Wanxing Carbon Co., Ltd.

[0055] Example 1

[0056] Add 94 mL of 0.8 mol / L potassium hydroxide aqueous solution dropwise to 320 mL of 1.15 wt% titanium chloride solution, stir and mix to obtain a mixture; place the mixture in a hydrothermal reactor, and then react at 100 °C for 3 h, filter, wash and dry the obtained filter cake to obtain TiO2 precursor;

[0057] The TiO2 precursor was placed in an atmosphere resistance furnace and then calcined at 660°C for 2 hours in a nitrogen atmosphere to obtain the TiO2 material.

[0058] 0.1 g of TiO2 material was stirred and mixed with 29.9 g of N,N-dimethylformamide and sonicated to obtain a TiO2 solution.

[0059] Add 0.5g of polyacrylonitrile powder to the TiO2 solution obtained above, stir and mix to obtain a mixture; add 0.2g of hydroxylamine hydrochloride to the mixture, and react at 75℃ for 4h to obtain the first reactant; then add 0.19g of potassium carbonate to the first reactant, and react at 80℃ for 10h to obtain a TiO2 / gammoxime solution.

[0060] A graphite felt measuring 20mm × 20mm × 2mm was placed in the TiO2 / mercaptooxime solution obtained in step 2) and sonicated for 30 minutes. The graphite felt was then removed to obtain a pre-loaded graphite felt, which was then dried. The dried pre-loaded graphite felt was then placed in the TiO2 / mercaptooxime solution again and sonicated for 25 minutes. The graphite felt was then removed to obtain a re-loaded graphite felt, which was then dried. The dried re-loaded graphite felt was then placed in the TiO2 / mercaptooxime solution again and sonicated for 25 minutes. The graphite felt was then removed to obtain a third-loaded graphite felt, which was then dried to obtain the titanium dioxide-mercaptooxime modified graphite felt electrode material.

[0061] The prepared titanium dioxide-modified graphite felt electrode material was subjected to scanning electron microscopy, energy dispersive spectroscopy, and infrared spectroscopy. The results are as follows: Figure 1 , Figure 2 , Figure 3 and Figure 4 As shown. By Figure 1 It can be seen that the surface of the graphite felt fiber in the obtained product becomes rough and has granular substances, indicating that new substances have been loaded onto the surface of the graphite felt fiber. Figure 2 Energy dispersive spectroscopy (EDS) analysis of the particulate matter on the surface of graphite felt fibers indicates that TiO2 was successfully loaded onto the fiber surface. Figure 4 It can be seen that 1639cm -1 The C=N vibration peak at 921 cm⁻¹ and the peak at 921 cm⁻¹ -1 The NO vibration peak at the [location] confirms the presence of the amine oxime group. These characterization results demonstrate the successful preparation of titanium dioxide amine oxime-modified graphite felt electrode material.

[0062] Example 2

[0063] 108 mL of 0.5 mol / L potassium hydroxide aqueous solution was added dropwise to 225 mL of 1.15 wt% titanium chloride solution, and the mixture was stirred to obtain a mixture. The mixture was placed in a hydrothermal reactor and reacted at 120 °C for 2 h. After filtration, the resulting filter cake was washed and dried to obtain the TiO2 precursor.

[0064] The TiO2 precursor was placed in an atmosphere resistance furnace and then calcined at 700°C for 2 hours in a nitrogen atmosphere to obtain the TiO2 material.

[0065] 0.2 g of TiO2 material was stirred and mixed with 29.8 g of N,N-dimethylformamide and sonicated to obtain a TiO2 solution.

[0066] Add 0.6g of polyacrylonitrile powder to the TiO2 solution obtained above, stir and mix to obtain a mixture; add 0.3g of hydroxylamine hydrochloride to the mixture, and react at 70℃ for 4h to obtain the first reactant; then add 0.29g of potassium carbonate to the first reactant, and react at 75℃ for 12h to obtain a TiO2 / gammoxime solution.

[0067] A graphite felt measuring 20mm × 20mm × 2mm was placed in the TiO2 / mercaptooxime solution obtained in step 2) and sonicated for 25 minutes. The graphite felt was then removed to obtain a pre-loaded graphite felt, which was then dried. The dried pre-loaded graphite felt was then placed in the TiO2 / mercaptooxime solution again and sonicated for 30 minutes. The graphite felt was then removed to obtain a re-loaded graphite felt, which was then dried. The dried re-loaded graphite felt was then placed in the TiO2 / mercaptooxime solution again and sonicated for 20 minutes. The graphite felt was then removed to obtain a third-loaded graphite felt, which was then dried to obtain the titanium dioxide-mercaptooxime modified graphite felt electrode material.

[0068] Example 3

[0069] Add 62.5 mL of 0.6 mol / L potassium hydroxide aqueous solution dropwise to 190 mL of 1.15 wt% titanium chloride solution, stir and mix to obtain a mixture; place the mixture in a hydrothermal reactor, and then react at 100 °C for 4 h, filter, wash and dry the obtained filter cake to obtain TiO2 precursor;

[0070] The TiO2 precursor was placed in an atmosphere resistance furnace and then calcined at 650°C for 2 hours in a nitrogen atmosphere to obtain the TiO2 material.

[0071] 0.2 g of TiO2 material was stirred and mixed with 29.8 g of N,N-dimethylformamide and sonicated to obtain a TiO2 solution.

[0072] Add 0.5g of polyacrylonitrile powder to the TiO2 solution obtained above, stir and mix to obtain a mixture; add 0.3g of hydroxylamine hydrochloride to the mixture, and react at 80℃ for 3h to obtain the first reactant; then add 0.16g of sodium carbonate to the first reactant, and react at 75℃ for 15h to obtain a TiO2 / gammoxime solution.

[0073] A graphite felt measuring 20mm × 20mm × 2mm was placed in the TiO2 / mercaptooxime solution obtained in step 2) and sonicated for 20 minutes. The graphite felt was then removed to obtain a pre-loaded graphite felt, which was then dried. The dried pre-loaded graphite felt was then placed in the TiO2 / mercaptooxime solution again and sonicated for 25 minutes. The graphite felt was then removed to obtain a re-loaded graphite felt, which was then dried. The dried re-loaded graphite felt was then placed in the TiO2 / mercaptooxime solution again and sonicated for 30 minutes. The graphite felt was then removed to obtain a third-loaded graphite felt, which was then dried to obtain the titanium dioxide-mercaptooxime-modified graphite felt electrode material.

[0074] Example 4

[0075] Add 50 mL of 0.7 mol / L potassium hydroxide aqueous solution dropwise to 125 mL of 1.15 wt% titanium chloride solution, stir and mix to obtain a mixture; place the mixture in a hydrothermal reactor, and then react at 110 °C for 3 h, filter, wash and dry the obtained filter cake to obtain TiO2 precursor;

[0076] The TiO2 precursor was placed in an atmosphere resistance furnace and then calcined at 600°C for 3 hours in a nitrogen atmosphere to obtain the TiO2 material.

[0077] 0.3 g of TiO2 material was stirred and mixed with 29.7 g of N,N-dimethylformamide and sonicated to obtain a TiO2 solution.

[0078] Add 0.4 g of polyacrylonitrile powder to the TiO2 solution obtained above, stir and mix to obtain a mixture; add 0.2 g of hydroxylamine hydrochloride to the mixture, and react at 60 °C for 5 h to obtain the first reactant; then add 0.15 g of sodium carbonate to the first reactant, and react at 85 °C for 13 h to obtain a TiO2 / gammoxime solution.

[0079] A graphite felt measuring 20mm × 20mm × 2mm was placed in the TiO2 / mercaptooxime solution obtained in step 2) and sonicated for 30 minutes. The graphite felt was then removed to obtain a pre-loaded graphite felt, which was then dried. The dried pre-loaded graphite felt was then placed in the TiO2 / mercaptooxime solution again and sonicated for 20 minutes. The graphite felt was then removed to obtain a re-loaded graphite felt, which was then dried. The dried re-loaded graphite felt was then placed in the TiO2 / mercaptooxime solution again and sonicated for 25 minutes. The graphite felt was then removed to obtain a third-loaded graphite felt, which was then dried to obtain the titanium dioxide-mercaptooxime-modified graphite felt electrode material.

[0080] Comparative Example 1

[0081] The only difference from Example 3 is that this example does not include the preparation of TiO2 precursor and TiO2 material. This example directly uses purchased TiO2 powder material.

[0082] Comparative Example 2

[0083] The only difference from Example 3 is that TiO2 material was not used in this comparative example, and the product obtained was a amine oxime modified graphite felt electrode material.

[0084] The titanium dioxide-modified graphite felt electrode materials obtained in Examples 1-4 and the comparative example were tested according to the aforementioned method, and their adsorption capacity and antibacterial efficiency for uranium in seawater were tested. The results are shown in Table 1.

[0085] Table 1

[0086]

[0087] As can be seen from the comparison of the examples and comparative examples, the titanium dioxide-amine oxime-modified graphite felt electrode material prepared by the method of the present invention has excellent uranium extraction performance, electrochemical performance and anti-bioadhesion performance.

[0088] This invention is not limited to the above-described embodiments. Any modifications, improvements, or substitutions that can be conceived by those skilled in the art without departing from the essential content of this invention fall within the scope of this invention.

Claims

1. A method for preparing a titanium dioxide amidoxime-modified graphite felt electrode material for improving the bacteriostatic rate against Escherichia coli, characterized by, The method comprises the following steps: 1) providing a TiO2 solution with a mass concentration of 0.3-1.0 wt%; the TiO2 solution is prepared by the following steps: (a) adding an aqueous alkali hydroxide solution to a soluble titanium salt solution, stirring and mixing to obtain a mixed solution; placing the mixed solution in a hydrothermal reactor, and then reacting at 100-120 ℃ for 2-4 h, solid-liquid separation, washing and drying the obtained solid to obtain a TiO2 precursor; wherein the molar ratio of titanium element in the soluble titanium salt to the alkali hydroxide is 1:3-5.5; (b) placing the TiO2 precursor in an atmosphere resistance furnace, and then calcining in an inert gas atmosphere at 600-700 ℃ for 2-4 h to obtain a TiO2 material; (c) stirring and mixing the TiO2 material with an organic solvent, and ultrasonicating to obtain a TiO2 solution; wherein the organic solvent is selected from one of N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide; 2) mixing the TiO2 solution with polyacrylonitrile powder to obtain a mixture; adding hydroxylamine hydrochloride to the mixture and reacting at 55-85 ℃ for 3-5.5 h to obtain a first reaction product; then adding an alkali metal carbonate to the first reaction product and reacting at 60-85 ℃ for 8-15 h to obtain a TiO2 / amidoxime solution; wherein the alkali metal carbonate is sodium carbonate; 3) immersing a graphite felt in the TiO2 / amidoxime solution obtained in step 2), ultrasonicating, taking out the graphite felt to obtain a preliminarily loaded graphite felt, and drying the obtained preliminarily loaded graphite felt; then placing the dried preliminarily loaded graphite felt in the TiO2 / amidoxime solution again, ultrasonicating again, taking out the graphite felt to obtain a reloaded graphite felt, and drying the obtained reloaded graphite felt; repeating the above steps of immersing, ultrasonicating, taking out the graphite felt and drying to obtain a TiO2 / amidoxime modified graphite felt electrode material; wherein the mass ratio of the TiO2 solution, the polyacrylonitrile powder and the hydroxylamine hydrochloride is 30:0.4:0.2 or 30:0.5:0.3; wherein the molar ratio of the alkali metal carbonate to the hydroxylamine hydrochloride is 1:1.9-2.

1.

2. The production method according to claim 1, characterized by, The soluble titanium salt is selected from one or more of titanium chloride, titanium nitrate, titanium acetate and titanium sulfate; and the alkali hydroxide is selected from one or more of potassium hydroxide and sodium hydroxide.

3. The method of claim 2, wherein, The concentration of the aqueous alkali hydroxide solution is 0.5-0.9 mol / L.

4. The method of claim 1, wherein, The molar ratio of the titanium element in the soluble titanium salt to the alkali hydroxide is 1:3.5-5.

5.

5. The preparation method according to claim 1, characterized in that, The step 2) comprises the following specific steps: mixing the TiO2 solution with the polyacrylonitrile powder to obtain a mixture; adding the hydroxylamine hydrochloride to the mixture and reacting at 60-80 ℃ for 3-5 h to obtain a first reaction product; then adding the alkali metal carbonate to the first reaction product and reacting at 65-85 ℃ for 10-15 h to obtain a TiO2 / amidoxime solution.

6. The method of any one of claims 1 to 5, wherein, The molar ratio of the alkali metal carbonate to the hydroxylamine hydrochloride is 1:2.0-2.05.

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