Carbon-doped titanium dioxide nanotube-molybdenum disulfide energy-storage antibacterial material and preparation method thereof

Abstract

The invention discloses a carbon-doped titanium dioxide nanotube-molybdenum disulfide energy-storage antibacterial material and a preparation method thereof. The preparation method comprises the following steps: carrying out primary anodic oxidation on a clean titanium foil in a mixed electrolyte of ethylene glycol, water and ammonium fluoride; after ultrasonic treatment is carried out in a hydrochloric acid solution for set time, secondary anodic oxidation is carried out, and the mixed electrolyte of the secondary anodic oxidation is the same as that of the primary anodic oxidation; annealing the titanium foil subjected to anodic oxidation twice in an argon atmosphere, putting an annealed sample into a mixed solution of sodium molybdate, a sulfur source and glucose, and carrying out hydrothermal treatment; and the titanium foil subjected to hydro-thermal treatment is cleaned and dried, and the carbon-doped titanium dioxide titanium foil with the surface covered with molybdenum disulfide is obtained. The MoS2-coated carbon-doped titanium dioxide nanotube (TNT-C-atMoS2) with high biocompatibility developed by the invention has a synergistic effect of charge antibiosis and chemical sterilization, so that the problem of intractable biological fouling of a titanium-based metal material in ocean engineering equipment is effectively solved.

Description

Technical Field

[0001] The present invention belongs to the technical field of electrode materials, and particularly relates to a carbon-doped titanium dioxide nanotube@molybdenum disulfide energy storage and antibacterial material and a preparation method thereof. Background Art

[0002] The statements herein only provide background art related to the present invention and do not necessarily constitute prior art.

[0003] Marine biofouling is one of the major problems faced in the development and utilization of marine resources, causing economic losses exceeding tens of billions of US dollars globally every year. Especially for titanium alloys known as "marine metals", as new key materials in the marine engineering field, they have been widely used in equipment such as ships, submarines, and offshore drilling platforms. However, their biofouling problem has always been the focus of attention in the industrial and scientific research communities, and its biofouling mechanism and prevention and control methods are also research hotspots at home and abroad. The attachment of organisms on the titanium surface generally includes 4 steps: conditioning film formation - biofilm attachment - attachment of diatoms, etc. - colonization of large organisms. Research shows that controlling the conditioning film formation, initial adhesion, and aggregation process of microorganisms (formation of biofilm) is the only way to effectively prevent and control biofouling.

[0004] Deficiencies of the prior art: Due to limitations in the bactericidal response range and specific capacitance content of materials, the antibacterial persistence is insufficient; the use conditions are complex, including the need to use under ultraviolet light, in acidic conditions, etc., which limits the application environment of these methods; there is a lack of specific antibacterial mechanisms, and there are few similar technologies targeting the "electroactive" characteristics of microorganisms. For example, Pseudomonas aeruginosa is the main bacterium causing metal corrosion and fouling in the ocean, and it is necessary to develop antibacterial methods targeting the "electroactivity" of bacteria; some methods induce bacteria to produce drug resistance. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a carbon-doped titanium dioxide nanotube@molybdenum disulfide energy storage and antibacterial material and a preparation method thereof. The MoS2-coated carbon-doped titanium dioxide nanotubes (TNT-C@MoS2) developed by the present invention, which have high biocompatibility, have the synergistic effect of charge antibacterial and chemical sterilization, thus effectively solving the stubborn biofouling problem of titanium-based metal materials in marine engineering equipment.

[0006] To achieve the above purpose, the present invention is realized through the following technical solutions: In the first aspect, the present invention provides a preparation method of a carbon-doped titanium dioxide nanotube@molybdenum disulfide energy storage and antibacterial material, including the following steps: The clean titanium foil is subjected to the first anodic oxidation in a mixed electrolyte of ethylene glycol, water and ammonium fluoride; then, after ultrasonic treatment in hydrochloric acid solution for a set time, the second anodic oxidation is carried out, and the mixed electrolyte for the second anodic oxidation is the same as that for the first anodic oxidation; After annealing the titanium foil after the two anodic oxidations, it is placed in a mixed solution of sodium molybdate, sulfur source and reducing agent for hydrothermal treatment; The titanium foil after hydrothermal treatment is washed and dried to obtain a carbon-doped titanium dioxide foil coated with molybdenum disulfide on the surface; Or, the titanium foil after the two anodic oxidations is placed in a mixed solution of sodium molybdate, sulfur source and reducing agent for hydrothermal treatment, and the product after hydrothermal treatment is annealed to obtain a carbon-doped titanium dioxide foil coated with molybdenum disulfide on the surface.

[0007] The resistance of ethylene glycol is greater than that of water, which can reduce the anodic oxidation reaction rate, make the titanium dioxide nanotubes reach the stable state with the same growth rate and dissolution rate more slowly, and facilitate the formation of longer nanotubes; ammonium fluoride provides fluoride ions, reacts with TiO2, forms micropores on the titanium dioxide oxide film, and gradually forms titanium dioxide nanotubes.

[0008] The disordered titanium dioxide nanotubes formed by the first anodic oxidation are removed by ultrasonic treatment in hydrochloric acid to expose a flat and uniform titanium surface, which is convenient for the second anodic oxidation to form a more neatly arranged nanotube array.

[0009] Sodium molybdate is used as the molybdenum source for generating MoS2, thiourea or thioacetamide is used as the sulfur source for generating MoS2, and glucose is used as a reducing agent to reduce Mo in sodium molybdate 6+ to a low valence state, promote the generation of MoS2, and at the same time increase the conductivity of the material.

[0010] In the present invention, the surface of the titanium substrate is modified, and a rechargeable MoS2-coated carbon-doped titanium dioxide nano antibacterial material is developed, which realizes an efficient "electroactive" antibacterial effect under the synergistic action of an electric field and chemical antibacterial.

[0011] The present invention combines charge antibacterial and chemical sterilization, and will not cause drug resistance of organisms.

[0012] In some embodiments, the sulfur source is thiourea or thioacetamide; the reducing agent is glucose.

[0013] In some embodiments, when pretreating the titanium foil, first soak the titanium foil in hydrochloric acid with a concentration of 0.5-1.5 mol / L for 1-5 h to smooth the surface; then ultrasonically clean the titanium foil with acetone, ethanol and water in sequence, and finally dry it. If the titanium foil is not soaked in hydrochloric acid, the surface of the titanium foil is rough, and the finally formed titanium dioxide nanotube array is in a disordered state.

[0014] In some embodiments, in the mixed electrolyte, the mass ratio of ethylene glycol, water and ammonium fluoride is 800-1000:50-150:2-5.

[0015] Preferably, the voltage for the first anodic oxidation is 10-100V and the time is 0.5-2h.

[0016] In some embodiments, the annealing temperature is 400-600°C and the annealing time is 1-3h.

[0017] Preferably, the heating rate during the annealing process is 10-20°C / min.

[0018] In some embodiments, during the hydrothermal treatment, the concentration of sodium molybdate is 2-10g / ml, the concentration of thiourea is 2-20g / ml, and the concentration of glucose is 0.02-0.08 mol / L.

[0019] Preferably, during the hydrothermal treatment, the concentration of sodium molybdate is 5-10g / ml, the concentration of thiourea is 10-20g / ml, and the concentration of glucose is 0.03-0.06 mol / L.

[0020] Further preferably, the hydrothermal treatment temperature is 180-250°C and the hydrothermal treatment time is 20-30h.

[0021] Even more preferably, the hydrothermal treatment temperature is 180-220°C and the hydrothermal treatment time is 20-25h.

[0022] In some embodiments, after the hydrothermal treatment, the titanium foil is washed with absolute ethanol and then dried at 50-70°C for 9-11h.

[0023] In a second aspect, the present invention provides a carbon-doped titanium dioxide nanotube@molybdenum disulfide energy storage and antibacterial material, which is prepared by the above preparation method.

[0024] The beneficial effects obtained by one or more of the above embodiments of the present invention are as follows: 1. The surface of the carbon-doped titanium dioxide titanium foil covered with molybdenum disulfide prepared by the present invention is simple to use, only requires a low voltage of 1V, is easy to provide, and can be applied to various environments such as marine environments and soil environments.

[0025] 2. Regarding the surface charge of fouling organisms such as microorganisms, it can block the extracellular electron transfer in their metabolic processes and has a broad-spectrum effect.

[0026] 3. The carbon-doped titanium dioxide titanium foil covered with molybdenum disulfide prepared by the present invention can combine charge antibacterial and chemical sterilization, greatly reducing the probability of bacteria developing drug resistance.

[0027] 4. The antibacterial material developed by the present invention has a significant effect on electroactive bacteria, can exert the maximum effect in scenarios where electroactive bacteria need to be targeted, and has a specific antibacterial mechanism. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] The specification drawings forming a part of the present invention are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention.

[0029] Figure 1 are optical photographs of TNT, TNT-C, and TNT-C@MoS2. Among them, (d) is the planar SEM image of TNT, (e) is the planar SEM image of TNT-C, (f) is the planar SEM image of TNT-C@MoS2, (g) is the cross-sectional SEM image of TNT, (h) is the cross-sectional SEM image of TNT-C, (i) is the cross-sectional SEM image of TNT-C@MoS2, and (m) is the roughness R a comparison chart, and (n) is the roughness R q comparison chart, and (o) is the high-magnification SEM image of TNT-C@MoS2; Figure 2 Among them, (a) is the distribution map of C elements of TNT, TNT-C, and TNT-C@MoS2; (b) is the distribution map of Mo and S elements in TNT-C@MoS2; (c) is the relative atomic weight analysis chart of C, O, Ti, Mo, and S in TNT, TNT-C, and TNT-C@MoS2; (d) is the XPS total spectrum of TNT, TNT-C, and TNT-C@MoS2; (e) is the Mo 3d fine spectrum of TNT-C@MoS2; (f) is the S 2p fine spectrum of TNT-C@MoS2; Figure 3 Among them, (a) is the CV curve of TNT-C@MoS2 at different scan rates, b is the GCD curve of TNT-C@MoS2 at different current densities, (c) is the comparison chart of CV curves at the optimal scan rate of 0.3 V / s, and (d) is the GCD curve comparison chart at a current density of 0.5 mA cm -2 at this time; Figure 4Among them, (a) is the diagram of the activity status of bacteria on uncharged TNT, (b) is the diagram of the activity status of bacteria on uncharged TNT-C, (c) is the diagram of the activity status of bacteria on uncharged MoS2@TNT-C, (g) is the morphology diagram of bacteria on the surface of uncharged TNT, (h) is the morphology diagram of bacteria on the surface of uncharged TNT-C, (i) is the morphology diagram of bacteria on the surface of uncharged TNT-C@MoS2, (j) is the morphology diagram of bacteria on the surface of charged TNT, (k) is the morphology diagram of bacteria on the surface of charged TNT-C, and (l) is the morphology diagram of bacteria on the surface of charged TNT-C@MoS2; Figure 5 Among them, (a) is the diagram of the activity status of free bacteria around uncharged TNT, (b) is the diagram of the activity status of free bacteria around uncharged TNT-C, (c) is the diagram of the activity status of free bacteria around uncharged TNT-C@MoS2, (d) is the diagram of the activity status of free bacteria around charged TNT, (e) is the diagram of the activity status of free bacteria around charged TNT-C, and (f) is the diagram of the activity status of free bacteria around charged TNT-C@MoS2; Figure 6 Among them, (a) is the diagram of the activity status of adherent bacteria on uncharged TNT, (b) is the diagram of the activity status of adherent bacteria on uncharged TNT-C, (c) is the diagram of the activity status of adherent bacteria on uncharged TNT-C@MoS2, (d) is the diagram of the activity status of adherent bacteria on the surface of TNT during the discharging process, (e) is the diagram of the activity status of adherent bacteria on the surface of TNT-C during the discharging process, and (f) is the diagram of the activity status of adherent bacteria on the surface of TNT-C@MoS2 during the discharging process; Figure 7 Among them, (a) is the diagram of the activity status of free bacteria attached to the surface of uncharged TNT, (b) is the diagram of the activity status of free bacteria attached to the surface of uncharged TNT-C, (c) is the diagram of the activity status of free bacteria attached to the surface of uncharged MoS2@TNT-C, (d) is the diagram of the activity status of free bacteria attached to the surface of TNT during the discharging process, (e) is the diagram of the activity status of free bacteria attached to the surface of TNT-C during the discharging process, and (f) is the diagram of the activity status of free bacteria attached to the surface of TNT-C@MoS2 during the discharging process. Detailed implementation mode

[0030] It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used in the present invention have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs.

[0031] The present invention will be further described below in conjunction with embodiments.

[0032] Example 1 Material preparation: Put a titanium foil with a handle of 10×10×0.5 mm into 1 mol / L hydrochloric acid and soak it for 3 h to smooth the surface. Ultrasonically clean the surface with acetone, ethanol, and deionized water for 15 min in sequence, and then dry it. Perform anodic oxidation twice using a two-electrode system. The cleaned titanium foil is used as the working electrode, the graphite electrode is used as the counter electrode, and the electrolyte is ethylene glycol, deionized water, and ammonium fluoride (900 mL:100 mL:3.44 g). Apply a constant voltage of 60 V between the anode and cathode using a DC power supply system. After 1 h, ultrasonically clean the titanium foil in 0.7 mol / L hydrochloric acid for 1 h, and perform the second anodic oxidation for 1 h under the same conditions. During anodic oxidation, use magnetic stirring to keep the solution concentration uniform.

[0033] The anodized sample is annealed in a tubular furnace under an argon atmosphere, heated to 450 °C at a rate of 15 °C / min, and held for 2 h, with a gas flow rate of 80 SCCM. The annealed sample is subjected to hydrothermal treatment. Dissolve 0.2 g of sodium molybdate and 0.4 g of thiourea in 30 mL of 0.05 mol / L glucose solution, put the solution and the sample into a reaction kettle, heat it in an oven at 200 °C for 24 h, take out the sample, clean it with absolute ethanol, and dry it at 60 °C for 9 - 11 h to obtain a titanium foil (TNT-C@MoS2) with a carbon-doped titanium dioxide nanotube coated with molybdenum disulfide on the surface.

[0034] When performing anodic oxidation, use a platinum electrode as the counter electrode. After annealing in a muffle furnace in air, a titanium foil TNT (avoiding carbon doping) with titanium dioxide nanotubes covered on the surface is obtained; Do not add sodium molybdate and thiourea in the hydrothermal stage, and finally obtain a titanium foil TNT-C (not adding sodium molybdate and thiourea is to avoid generating MoS2) with carbon-doped titanium dioxide nanotubes covered on the surface.

[0035] Morphology and roughness characterization: First, take optical photos of TNT, TNT-C, and TNT-C@MoS2 through a camera (overall) and a super-depth-of-field microscope (local). Characterize the microscopic morphology of the plane and cross-section by scanning electron microscopy (SEM). Characterize the roughness of TNT, TNT-C, and TNT-C@MoS2 using an atomic force microscope (AFM).

[0036] Elemental characterization: The energy-dispersive spectrometer (EDS) was used to compare the carbon (C) element distribution in the TNT, TNT-C, and TNT-C@MoS2 samples. The distributions of molybdenum (Mo) and sulfur (S) in the TNT-C@MoS2 sample were specifically studied. In addition, the relative atomic percentages of C, O, Ti, Mo, and S in TNT, TNT-C, and TNT-C@MoS2 were quantitatively analyzed. The chemical states of the samples were determined by X-ray photoelectron spectroscopy (XPS).

[0037] Electrochemical characterization: The three-electrode system was used for electrochemical tests. The titanium foil sample was used as the working electrode, the platinum sheet was used as the counter electrode, and the saturated calomel electrode was used as the reference electrode. The LB solution was used as the electrolyte. The LB medium was prepared with 10 g peptone, 5 g yeast extract, 10 g NaCl, and 1 L deionized water.

[0038] First, the capacitance of TNT-C@MoS2 was characterized using an electrochemical workstation. Cyclic voltammetry characterization of the TNT-C@MoS2 sample was carried out at scan rates of 0.001, 0.01, 0.1, 0.3, 1, 5, and 10 V / s, and galvanostatic charge-discharge tests were carried out at current densities of 0.1, 0.3, 0.5, 1, 2, and 10 mAcm -2 Current density.

[0039] The capacitance performance of TNT, TNT-C, and TNT-C@MoS2 was compared using an electrochemical workstation. Cyclic voltammetry tests were carried out on them at the same scan rate (0.3 V / s), and galvanostatic charge-discharge tests were carried out on them at the same current density (0.5 mA cm -2 )

[0040] Antibacterial characterization: The bacterial strain used in the experiment was Pseudomonas aeruginosa, and LB was used as the culture medium.

[0041] Antibacterial characterization during charging process: The immobilized bacteria and free bacteria during the charging process were characterized respectively.

[0042] TNT, TNT-C, and TNT-C@MoS2 were placed in 10 mL of bacterial liquid that had grown to the logarithmic phase and cultured in a constant temperature incubator at 37 °C for 12 h to allow the bacteria to attach and grow on the samples. The two-electrode system was used to charge the samples. The titanium foil with attached bacteria was used as the working electrode, the platinum electrode was used as the counter electrode, and the electrolyte was 10 mL of bacterial liquid that had grown for 24 h. Charging was carried out at 1 V for 15 min.

[0043] The bacteria attached and grown on TNT, TNT-C, TNT-C@MoS2 for 12 h, as well as the charged TNT, TNT-C, and TNT-C@MoS2 were observed using CLSM and SEM to characterize the status of the adherent bacteria before and after charging.

[0044] 10 mL of bacterial solution soaked with TNT, TNT-C, and TNT-C@MoS2, as well as 10 mL of bacterial solution used as the electrolyte during the charging of TNT, TNT-C, and TNT-C@MoS2 were taken and observed using CLSM to characterize the antibacterial effect of the charging process on free bacteria.

[0045] Antibacterial characterization during discharging process: The adherent bacteria and free bacteria during the discharge process after charging were characterized respectively.

[0046] TNT, TNT-C, and TNT-C@MoS2 were charged using a three-electrode system. The titanium foil was used as the working electrode, the saturated calomel electrode was used as the reference electrode, and the platinum electrode was used as the counter electrode. The electrolyte was LB solution, and the charging was carried out at 1 V for 15 min. After charging, 100 μL of the bacterial solution (centrifugally enriched 10 times) grown for 24 h was immediately dropped onto the charged titanium foil.

[0047] The bacterial solution was dropped onto the uncharged and charged TNT, TNT-C, and TNT-C@MoS2, and allowed to attach and grow for 3 h. Then, it was observed using CLSM to characterize the antibacterial effect of the discharge process after charging of the material on the adherent bacteria.

[0048] The bacterial solution was dropped onto the uncharged and charged TNT, TNT-C, and TNT-C@MoS2. After 15 min, it was observed using CLSM to characterize the antibacterial effect of the discharge process after charging of the material on the free bacteria.

[0049] Material characterization TNT-C@MoS2 was prepared through the material preparation steps ( Figure 1 c), and TNT ( Figure 1 a), TNT-C ( Figure 1 b) used as controls were respectively presented in black, blue, and yellow. The samples were observed using a scanning electron microscope (SEM). MoS2 nanospheres and MoS2 nanopiled spheres were attached to the surface of TNT-C@MoS2 ( Figure 1 f and o). By observing the cross-section ( Figure 1 g, h, and i) through SEM, it was found that compared with the smooth tube walls of TNT and TNT-C, the titanium dioxide nanotube walls of TNT-C@MoS2 were wrapped by MoS2. The roughness of the samples was characterized using AFM ( Figure 1j, k, l), it was found that as the composition increased, the roughness of the samples increased, and TNT-C@MoS2 exhibited the highest roughness. Through R a and R q quantitative analysis of the roughness, the same conclusion was also obtained.

[0050] Elemental characterization Elemental analysis of TNT-C@MoS2 and the control groups TNT-C and TNT found that TiO2 in TNT-C@MoS2 was detected by EDS and XPS ( Figure 2 c and d), C in TNT-C@MoS2 was detected by EDS and XPS ( Figure 2 a, c and d), and MoS2 in TNT-C@MoS2 was detected by EDS and XPS ( Figure 2 b, c, d, e, f), indicating that the MoS2 compound had been completely coated on the TiO2 nanotubes.

[0051] Capacitance characterization The capacitance of TNT-C@MoS2 was analyzed by CV and GCD tests ( Figure 3 a and b). The calculation results showed that at a scan rate of 0.3 V / s, the specific capacitance of the TNT-C@MoS2 sample was 150.13 F / g, and its capacitance was greatly improved compared with the control groups TNT-C and TNT ( Figure 3 c and d).

[0052] Antibacterial performance characterization Antibacterial effect of the charging process on adherent bacteria Figure 4 In a-f, the bacterial activity was observed by CLSM. a, b and c respectively showed the bacterial activity status on uncharged TNT, TNT-C and MoS2@TNT-C. It was found that TNT-C@MoS2 already had an obvious antibacterial effect without charging, which was mainly due to the antibacterial performance of MoS2 itself. d, e and f were the bacterial activity status on TNT, TNT-C and TNT-C@MoS2 after charging. Compared with before charging, it was found that the bacterial activity on the samples after charging was greatly reduced, proving the antibacterial effect of the charging process on bacteria. Through comprehensive comparison, the charged TNT-C@MoS2 sample had the best antibacterial effect, with an anti-adhesion rate of 86.67% and an antibacterial efficiency of over 99%.

[0053] Figure 4In g-l, the bacterial morphology observed by SEM is shown. Dead bacteria are marked in red and live bacteria are marked in green. g, h, and i are the bacterial morphologies on the surfaces of uncharged TNT, TNT-C, and TNT-C@MoS2 respectively, which also shows that TNT-C@MoS2 has certain antibacterial effects even without charging. j, k, and l are the bacterial morphologies on the surfaces of charged TNT, TNT-C, and TNT-C@MoS2 respectively. The bacterial morphologies on the surfaces of the charged samples have all changed, and almost only dead bacteria exist. By comparison, it is found that TNT-C@MoS2 has the best antibacterial effect after charging.

[0054] Antibacterial effect on free bacteria during charging process Figure 5 In a-f, the bacterial viability of free bacteria observed by CLSM is shown. a, b, and c are the viability conditions of free bacteria around uncharged TNT, TNT-C, and TNT-C@MoS2 respectively. By comparison, it is found that the viability of free bacteria around TNT-C@MoS2 is the worst, indicating that TNT-C@MoS2 has significant antibacterial effects on the surrounding free bacteria. d, e, and f show the viability conditions of free bacteria around charged TNT, TNT-C, and TNT-C@MoS2 respectively. Compared with before charging, the viability of free bacteria has decreased significantly. In summary, charged TNT-C@MoS2 shows the best antibacterial effect on the surrounding free bacteria, and the antibacterial rate is over 90%.

[0055] Antibacterial effect on adherent bacteria during discharging process Figure 6 In a-f, the bacterial viability observed by CLSM is shown. a, b, and c are the viability conditions of adherent bacteria on uncharged TNT, TNT-C, and TNT-C@MoS2 respectively. By comparison, it is found that the viability of adherent bacteria on the surface of TNT-C@MoS2 is the worst, indicating that TNT-C@MoS2 itself has an inhibitory effect on adherent bacteria. d, e, and f show the viability conditions of adherent bacteria on the surfaces of TNT, TNT-C, and TNT-C@MoS2 during the discharging process. Compared with the untreated situation, the attached bacteria are significantly reduced and their viability has decreased, indicating that TNT-C@MoS2 also has a significant inhibitory effect on adherent bacteria during the discharging process, and its antibacterial efficiency reaches over 99%.

[0056] Antibacterial effect on free bacteria during discharging process Figure 7Among a-f is the bacterial activity of free bacteria observed by CLSM. a, b, and c respectively show the activity status of free bacteria attached to the surfaces of uncharged TNT, TNT-C, and MoS2@TNT-C. By comparison, it is found that the activity of free bacteria on the surface of TNT-C@MoS2 is the worst, indicating that TNT-C@MoS2 has antibacterial effects on its own free bacteria. d, e, and f are respectively the activity status of free bacteria attached to the surfaces of TNT, TNT-C, and TNT-C@MoS2 during the discharging process. Compared with when the samples were untreated, the activity of free bacteria decreased significantly. The results show that TNT-C@MoS2 during the discharging process has the best antibacterial effect on free bacteria, with an antibacterial rate of over 96%.

[0057] Example 2 Material preparation: Polish with 5000-mesh sandpaper to smooth the surface. Ultrasonically clean the surface with acetone, ethanol, and deionized water in sequence for 15 min, and then dry it. Conduct anodic oxidation twice using a two-electrode system. The cleaned titanium foil serves as the working electrode, the graphite electrode serves as the counter electrode, and the electrolyte is ethylene glycol, deionized water, and ammonium fluoride (900 mL:100 mL:3.44 g). Apply a constant voltage of 30 V between the two electrodes using a DC power supply system. After 30 min, ultrasonically clean the titanium foil in 0.7 mol / L hydrochloric acid for 1 h, and conduct the second anodic oxidation for 1 h under the same conditions. During anodic oxidation, use magnetic stirring to keep the solution concentration uniform.

[0058] The anodized samples are annealed in a tubular furnace under an argon atmosphere, heated to 450 °C at a rate of 15 °C / min, and held for 2 h, with a gas flow rate of 80 SCCM. The annealed samples are subjected to hydrothermal treatment. Dissolve sodium molybdate (Na2MoO4, 30 mg) and thioacetamide (C2H5NS, 60 mg) in deionized water (60 mL). Put the solution and the samples into a reaction kettle and heat them in an oven at 200 °C for 24 h. Take out the samples, clean them with absolute ethanol, and dry them at 60 °C for 9 - 11 h to obtain titanium foils (TNT-C@MoS2) with carbon-doped titanium dioxide coated with molybdenum disulfide on the surface.

[0059] Example 3 Material preparation: A titanium foil with a handle of 10×10×0.5 mm was immersed in 1 mol / L hydrochloric acid for 3 h to smooth the surface. It was ultrasonically cleaned in acetone, ethanol, and deionized water for 10 min in sequence, the surface was cleaned and dried. Two anodic oxidations were carried out using a two-electrode system. The cleaned titanium foil was used as the working electrode, the graphite electrode was used as the counter electrode, and the electrolyte was ethylene glycol, deionized water, and ammonium fluoride (950 mL:50 mL:5 g). A constant voltage of 60 V was applied between the two electrodes using a DC power supply system. After 1 h, the titanium foil was ultrasonically treated in 0.7 mol / L hydrochloric acid for 1 h for the second anodic oxidation, and oxidized under the same conditions for 1 h. During the anodic oxidation, magnetic stirring was used to keep the solution concentration uniform.

[0060] The anodized sample was subjected to hydrothermal treatment. 0.2 g of sodium molybdate and 0.4 g of thiourea were dissolved in 30 mL of 0.05 mol / L glucose solution. The solution and the sample were placed in a reaction kettle and heated in an oven at 200 °C for 24 h. The sample was taken out, cleaned with absolute ethanol, and then annealed in a tubular furnace under an argon atmosphere, heated to 450 °C at a rate of 15 °C / min, and held for 2 h. The gas flow rate was 80 SCCM, and a titanium foil (TNT-C@MoS2) with carbon-doped titanium dioxide coated with molybdenum disulfide on the surface was obtained.

[0061] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A preparation method of a carbon-doped titanium dioxide nanotube@molybdenum disulfide energy storage and antibacterial material, characterized in that: It includes the following steps: The cleaned titanium foil is subjected to the first anodic oxidation in a mixed electrolyte of ethylene glycol, water and ammonium fluoride; then after ultrasonic treatment in hydrochloric acid solution for a set time, the second anodic oxidation is carried out, and the mixed electrolyte for the second anodic oxidation is the same as that for the first anodic oxidation; After annealing the titanium foil after the two anodic oxidations, it is put into a mixed solution of sodium molybdate, sulfur source and reducing agent for hydrothermal treatment; The titanium foil after hydrothermal treatment is washed and dried to obtain a carbon-doped titanium dioxide foil covered with molybdenum disulfide coating on the surface; Or, the titanium foil after the two anodic oxidations is put into a mixed solution of sodium molybdate, sulfur source and reducing agent for hydrothermal treatment, and the product after hydrothermal treatment is annealed to obtain a carbon-doped titanium dioxide foil covered with molybdenum disulfide coating on the surface.

2. The preparation method of the carbon-doped titanium dioxide nanotube @ molybdenum disulfide energy storage and antibacterial material according to claim 1, characterized in that: When pretreating the titanium foil, first soak the titanium foil in hydrochloric acid with a concentration of 0.5 - 1.5 mol / L for 1 - 5 h to smooth the surface; then ultrasonically clean the titanium foil successively with acetone, ethanol and water, and finally blow dry.

3. The preparation method of the carbon-doped titanium dioxide nanotube@molybdenum disulfide energy storage and antibacterial material according to claim 1, characterized in that: In the said mixed electrolyte, the mass ratio of ethylene glycol, water and ammonium fluoride is 800 - 1000:50 - 150:2 - 5; Preferably, the voltage for the first anodic oxidation is 10 - 100 V and the time is 0.5 - 2 h.

4. The preparation method of the carbon-doped titanium dioxide nanotube @ molybdenum disulfide energy storage and antibacterial material according to claim 1, characterized in that: The temperature for annealing is 400 - 600 °C and the time for annealing is 1 - 3 h.

5. The preparation method of the carbon-doped titanium dioxide nanotube @ molybdenum disulfide energy storage and antibacterial material according to claim 4, characterized in that: The heating rate during the annealing process is 10 - 20 °C / min.

6. The preparation method of the carbon-doped titanium dioxide nanotube@molybdenum disulfide energy storage and antibacterial material according to claim 1, characterized in that: During the hydrothermal treatment, the concentration of sodium molybdate is 2 - 10 g / ml, the concentration of thiourea is 2 - 20 g / ml, and the concentration of glucose is 0.02 - 0.08 mol / L.

7. The preparation method of the carbon-doped titanium dioxide nanotube@molybdenum disulfide energy storage and antibacterial material according to claim 6, characterized in that: During the hydrothermal treatment, the concentration of sodium molybdate is 5 - 10 g / ml, the concentration of thiourea is 10 - 20 g / ml, and the concentration of glucose is 0.03 - 0.06 mol / L.

8. The preparation method of the carbon-doped titanium dioxide nanotube @ molybdenum disulfide energy storage and antibacterial material according to claim 7, characterized in that: The temperature for hydrothermal treatment is 180 - 250 °C and the time for hydrothermal treatment is 20 - 30 h; Preferably, the temperature for hydrothermal treatment is 180 - 220 °C and the time for hydrothermal treatment is 20 - 25 h.

9. The preparation method of the carbon-doped titanium dioxide nanotube@molybdenum disulfide energy storage and antibacterial material according to claim 1, wherein: After the hydrothermal treatment is completed, the titanium foil is washed with absolute ethanol and then dried at 50 - 70 °C for 9 - 11 h.

10. A carbon-doped titanium dioxide nanotube@molybdenum disulfide energy storage and antibacterial material, characterized in that: It is prepared by the said preparation method.

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