Copper-doped titanium-based energy-storage antibacterial material as well as preparation method and application thereof

Abstract

The invention discloses a copper-doped titanium-based energy-storage antibacterial material as well as a preparation method and application thereof, and belongs to the technical field of biological fouling prevention and control. The preparation method comprises the following steps that a titanium-based material is pretreated and then subjected to anodic oxidation twice, then the titanium-based material is placed in a copper ion solution to be subjected to electro-deposition, cleaning and drying and then subjected to annealing treatment, then a three-electrode system is adopted for charging treatment, and the copper-doped titanium-based energy-storage antibacterial material is obtained. The composite material has charge storage and chemical sterilization functions, is good in antibacterial durability, has a good antibacterial effect on corrosion and fouling leading electroactive bacteria such as pseudomonas aeruginosa in a marine environment, and can remarkably reduce the drug resistance risk of the bacteria at the same time; and the device can be recycled.

Description

Technical Field

[0001] The present invention relates to the technical field of biofouling prevention and control, and in particular to a copper-doped titanium-based energy storage antibacterial material, a preparation method thereof, and applications thereof. Background Art

[0002] The information disclosed in the background of the invention is only intended to enhance understanding of the overall background of the invention and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art.

[0003] Titanium and its alloys are widely used in marine engineering due to their excellent mechanical properties and corrosion resistance. However, their surfaces are susceptible to biofouling. Biofouling not only increases ship resistance and fuel consumption but can also cause pipeline blockage and perforation, seriously threatening equipment safety. Controlling the initial adhesion and aggregation of microorganisms is key to preventing and controlling biofouling.

[0004] In the existing antibacterial technology, relying solely on chemical coatings to inhibit bacteria can easily induce bacteria to develop drug resistance; photocatalytic TiO2-based antibacterial materials such as Cu + / TiO2 nanotube array heterojunction, which generates hole-electron pairs through ultraviolet irradiation to excite reactive oxygen species (ROS) to achieve sterilization, but the wide bandgap characteristics of TiO2 limit its applicability to UV irradiation environments, and the problems of electron transfer rate and electron-hole recombination rate further reduce the sterilization efficiency. Another type of electrochemically active titanium-based antibacterial material, such as the carbon / TiO2 nanotube array antibacterial platform, relies on double-layer capacitance to store charge and destroy bacterial membranes; there are also two-dimensional porous titanium-based antibacterial materials such as titanium micro-arc oxidation copper-loaded coatings, which achieve antibacterial effects by changing the bacterial adhesion microenvironment through chemical copper plating. However, these technologies generally have problems with limited sterilization response range and insufficient capacitance content, resulting in poor antibacterial durability, and most antibacterial materials are difficult to recycle.

[0005] In addition, some electroactive bacteria in the ocean (such as Pseudomonas, sulfate-reducing bacteria, etc.) directly or indirectly accelerate the electrochemical corrosion of metals through extracellular electron transfer (EET) and biofilm formation. However, the antibacterial materials in the existing technology are not sufficiently targeted against these electroactive bacteria, which restricts the application effect of existing materials in the prevention and control of biological fouling of marine engineering equipment.

[0006] Therefore, how to provide a titanium-based antibacterial material that has both charge antibacterial and chemical bactericidal effects, strong antibacterial durability, good bactericidal effect on electroactive bacteria, simple preparation method, and can be recycled is an urgent problem to be solved. Summary of the Invention

[0007] In view of this, the present invention provides a copper-doped titanium-based energy storage antibacterial material, a preparation method and application thereof. The energy storage antibacterial material provided by the present invention has both charge antibacterial and chemical sterilization effects, and has a good antibacterial effect on electroactive bacteria, strong antibacterial durability, and at the same time, the preparation method is simple and can be recycled.

[0008] In a first aspect, the present invention provides a method for preparing a copper-doped titanium-based energy storage antibacterial material, comprising the following steps: The titanium-based material is pretreated and then anodized twice to obtain a titanium-based material containing a TiO2 nanotube array; The titanium-based material containing the TiO2 nanotube array is placed in a copper ion solution for electrodeposition, and then annealed after cleaning and drying to obtain a copper-doped titanium-based material; A three-electrode system is used to charge the copper-doped titanium-based material to obtain the copper-doped titanium-based energy storage antibacterial material.

[0009] Preferably, the titanium-based material is selected from pure titanium or titanium alloy, and the titanium-based material further includes a pretreatment step before anodizing treatment, and the pretreatment is acid washing, acetone washing, ethanol washing and water washing in sequence.

[0010] Preferably, the anodic oxidation adopts a two-electrode system, with a titanium-based material as the anode and a graphite electrode or a platinum sheet as the cathode. The voltage of the anodic oxidation treatment is 40~80V and the time is 0.5~2h; the electrolyte of the anodic oxidation treatment is an ethylene glycol aqueous solution containing ammonium fluoride.

[0011] Preferably, after the first anodizing treatment, the generated TiO2 nanotube array is removed by acid washing, and then a second anodizing treatment is performed.

[0012] Preferably, the concentration of copper ions in the copper ion solution is 0.3-1 mol / L; the anions in the copper ion solution are selected from one or more of nitrate ions, chloride ions, sulfate ions, pyrophosphate ions or cyanide ions.

[0013] Preferably, the electrodeposition process uses a titanium-based material containing a TiO2 nanotube array as a cathode and a platinum sheet or a graphite electrode as an anode; the electrodeposition voltage is 10-20 V and the time is 50-150 s.

[0014] Preferably, the annealing temperature is 400-500° C., and the annealing time is 2-5 hours.

[0015] Preferably, the three-electrode system includes a working electrode, a counter electrode and a reference electrode, and the working electrode is a copper-doped titanium-based material; the voltage of the charging process is 0.8~1.2V, and the charging time is 10~30min.

[0016] In a second aspect, the present invention provides a copper-doped titanium-based energy storage antibacterial material prepared by the above preparation method.

[0017] In a third aspect, the present invention provides the application of the above-mentioned copper-doped titanium-based energy storage antibacterial material in the prevention and treatment of biological fouling.

[0018] Compared with the prior art, the present invention has achieved the following beneficial effects: (1) The present invention constructs a titanium-based material containing highly ordered TiO2 nanotube arrays (TNTs) through a double anodization process, combines copper ion electrodeposition with annealing treatment to achieve uniform copper doping and TNTs stabilization, and forms a composite antibacterial material with both charge storage and chemical sterilization functions after charging treatment. It has good antibacterial durability and solves the technical defects of traditional TiO2-based materials such as dependence on ultraviolet light, insufficient capacitance of electrochemically active materials, and poor antibacterial durability.

[0019] (2) The present invention can achieve charge storage by charging at a low voltage of 0.8 to 1.2 V for 10 to 30 minutes. In the subsequent discharge process, it can interfere with the extracellular electron transfer of electroactive bacteria. At the same time, it uses the chemical bactericidal effect of copper ions to form a synergistic antibacterial mechanism, which has good broad-spectrum antibacterial properties. At the same time, it has a good inhibitory effect on electroactive bacteria such as Pseudomonas aeruginosa that dominate corrosion and fouling in the marine environment, and can significantly reduce the risk of bacterial resistance. After the discharge is completed, it can also be recycled by recharging.

[0020] (3) The preparation method of the present invention is easy to operate. The titanium-based material pretreatment and anodizing process are compatible with industrial pure titanium and titanium alloy substrates. The copper doping concentration and charge and discharge parameters are controllable. The obtained material can be stably used in complex environments such as the ocean and soil, providing a practical and long-term solution for the prevention and control of biofouling of marine engineering equipment. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The drawings, which constitute part of the present invention, are intended to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are intended to explain the present invention and do not constitute undue limitations thereon. It is obvious that one of ordinary skill in the art could derive other drawings based on these drawings without inventive effort.

[0022] Figure 1Surface scanning electron microscope (SEM) images of the copper-doped titanium-based energy storage antibacterial materials of Examples 1 to 4 of the present invention at magnifications of 300 and 50K, wherein (a) is TNTs-0.35Cu of Example 3, (b) is TNTs-0.55Cu of Example 2, (c) is TNTs-0.75Cu of Example 1, and (d) is TNTs-0.55Cu-2 of Example 4; Figure 2 3D topography of the surface of the TNTs-0.75Cu sample of Example 1 of the present invention, wherein (a) is a top view and (b) is a side view; Figure 3 1 is a graph showing the elemental analysis results of the surface of the TNTs-0.75Cu sample of Example 1 of the present invention; Figure 4 1 is an X-ray photoelectron spectroscopy (XPS) graph of the surface of the TNTs-0.75Cu sample of Example 1 of the present invention, wherein (a) is the XPS spectrum of the C 1s energy level, (b) is the XPS spectrum of the O 1s energy level, (c) is the XPS spectrum of the Ti 2p energy level, and (d) is the XPS spectrum of the Cu 2p energy level; Figure 5 Figure 1 is a characterization of the capacitance of TNTs-0.75Cu of Example 1 of the present invention and the Ti foil of Comparative Example 1, wherein (a) is the cyclic voltammetry (CV) curve of TNTs-0.75Cu at different scan rates, (b) is the CV curve of TNTs-0.75Cu and Ti foil at a scan rate of 1 V / s, (c) is the constant current charge-discharge (GCD) curve of TNTs-0.75Cu at different scan current densities, and (d) is the constant current charge-discharge (GCD) curve of TNTs-0.75Cu and Ti foil at a scan current density of 1 mA·cm -2 The GCD curve below; Figure 6 Corrosion resistance tests of the UC-TNTs-0.75Cu and CD-TNTs-0.75Cu samples of Example 1 of the present invention, as well as the UC-Ti of Comparative Example 1 and the CD-Ti of Comparative Example 2 are shown; (a) is the Nyquist curve of the UC-TNTs-0.75Cu and CD-TNTs-0.75Cu samples; (b) is the Bode modulus plot of the UC-TNTs-0.75Cu and CD-TNTs-0.75Cu samples; (c) is the Nyquist curve of the UC-Ti and CD-Ti; and (d) is the Bode modulus plot of the UC-Ti and CD-Ti. Figure 7These are images showing the antibacterial performance of the UC-TNTs-0.75Cu and CD-TNTs-0.75Cu samples of Example 1 of the present invention, as well as the UC-Ti of Comparative Example 1 and the CD-Ti of Comparative Example 2. (a) is a fluorescence microscope image, (b) is the anti-adhesion rate, and (c) is the sterilization rate. Figure 8 The samples of Example 1, Comparative Example 1 and Comparative Example 2 are P. aeruginosa SEM images of bacteria attached to the surface after immersion in bacterial solution for 12 h, at magnifications of 5K and 50K; (a) is the UC-Ti sample of Comparative Example 1, (b) is the CD-Ti sample of Comparative Example 2, (c) is the UC-TNTs-0.75Cu sample of Example 1, and (d) is the CD-TNTs-0.75Cu sample of Example 1. Figure 9 The samples of Example 1, Comparative Example 1 and Comparative Example 2 are P. aeruginosa Pictures of bacterial colonies attached to the surface after immersion in bacterial solution for 12 hours; (a1), (a2), and (a3) ​​are respectively the UC-Ti samples of comparative example 1 after immersion in bacterial solution for 10 4 times, 10 5 times, 10 6 (b1), (b2), (b3) are the colony pictures of CD-Ti sample in comparative example 2 after the bacterial solution was diluted 10 4 times, 10 5 times, 10 6 Colony pictures after 10 times of dilution; (c1), (c2), (c3) are the colony pictures of UC-TNTs-0.75Cu sample in Example 1 after 10 times of dilution 4 times, 10 5 times, 10 6 Colony pictures after 10 times of dilution; (d1), (d2), (d3) are the colony pictures of CD-TNTs-0.75Cu sample in Example 1 after 10 times of dilution 4 times, 10 5 times, 10 6 Colony picture after magnification. DETAILED DESCRIPTION

[0023] It should be noted that the following detailed descriptions are exemplary and intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention belongs.

[0024] The present invention provides a method for preparing a copper-doped titanium-based energy storage antibacterial material, comprising the following steps: The titanium-based material is pretreated and then anodized twice to obtain a titanium-based material containing a TiO2 nanotube array; The titanium-based material containing the TiO2 nanotube array is placed in a copper ion solution for electrodeposition, and then annealed after cleaning and drying to obtain a copper-doped titanium-based material; A three-electrode system is used to charge the copper-doped titanium-based material to obtain the copper-doped titanium-based energy storage antibacterial material.

[0025] The present invention uses two anodization processes on the surface of the titanium-based material and an electrochemical oxidation reaction to construct a highly ordered titanium dioxide nanotube array structure on the surface of the metal substrate. The nanotube array not only provides a carrier framework with a high specific surface area for subsequent copper doping, but its tubular structure itself can also realize the charge storage function through the double layer effect; the nanotube array is then placed in a copper ion solution for electrodeposition, and the copper ions are driven to migrate in a directional manner and embed into the tube walls and gaps inside the nanotubes through an external electric field. After annealing, the copper elements are stably present in the titanium dioxide lattice in the form of oxides or doped atoms, forming a composite structure with redox activity; finally, a three-electrode system is used for charging treatment to realize rapid storage and slow release of charge. The stored charge can interfere with the extracellular electron transfer of microorganisms through electrostatic action during application, while the slow release of copper ions exerts a chemical bactericidal effect. The two work together to construct an energy storage and antibacterial system with both physical and chemical mechanisms.

[0026] In the present invention, the titanium-based material is selected from pure titanium or a titanium alloy, and specifically any one of Ti-6Al-4V alloy, TC4 titanium alloy, TA2 industrial pure titanium, or TA3 industrial pure titanium, which can be selected according to actual application requirements. The titanium-based material also includes a pretreatment step before anodizing, and the pretreatment step is acid washing, acetone washing, ethanol washing, and water washing. The multi-step cleaning step effectively removes oxide scale, oil stains, and impurities on the surface of the titanium-based material, improves surface cleanliness and activity, and lays a good foundation for the subsequent anodization preparation of high-quality TiO2 nanotube arrays.

[0027] In the present invention, the anodic oxidation adopts a two-electrode system, with a titanium-based material as the anode and a graphite electrode or a platinum sheet as the cathode. The voltage of the anodic oxidation treatment is 40 to 80V, more preferably 50 to 70V, and even more preferably 55 to 65V; and the time is 0.5 to 2h. The electrolyte for the anodic oxidation treatment is an ethylene glycol aqueous solution containing ammonium fluoride. The present invention does not impose any special restrictions on the specific amount of the electrolyte used, and the ratio commonly used in the art can be used. In one or more embodiments of the present invention, the concentration of ammonium fluoride is 0.08 to 0.12 mol / L, and the volume ratio of ethylene glycol to water is (8 to 12): 1.

[0028] After the first anodizing treatment, the present invention uses acid washing to remove the generated TiO2 nanotube array, and then performs a second anodizing treatment. The TiO2 nanotube array generated by the first anodizing treatment is less uniform and less ordered. After the acid washing treatment removes the TiO2 nanotube array, the second anodizing treatment can be performed on a cleaner and more uniform titanium-based material surface, thereby producing a TiO2 nanotube array with a more regular structure and higher order, which is beneficial for improving the performance of the material.

[0029] In the copper ion solution of the present invention, the copper ion concentration is 0.3 to 1 mol / L, more preferably 0.5 to 0.8 mol / L, and even more preferably 0.6 to 0.8 mol / L. The copper ion concentration affects the Cu doping amount. The anions in the copper ion solution are selected from one or more of nitrate ions, chloride ions, sulfate ions, pyrophosphate ions, or cyanide ions.

[0030] In the present invention, the electrodeposition process uses a titanium-based material containing a TiO2 nanotube array as a cathode and a platinum sheet or a graphite electrode as an anode; the electrodeposition voltage is 10-20V, more preferably 12-18V; the electrodeposition time is 50-150s, more preferably 50-80s. If the electrodeposition time is too long, it will affect the structural integrity of the TiO2 nanotube array, which is not conducive to improving the performance of the material.

[0031] In the present invention, the annealing temperature is 400-500°C, more preferably 420-480°C, and the annealing time is 2-5 hours. Annealing stabilizes the crystal structure of the copper-doped titanium-based material, improving its electrical conductivity and chemical stability. It also promotes the diffusion and uniform distribution of copper within the TiO2 lattice, enhancing the material's energy storage and antibacterial properties.

[0032] In the present invention, the three-electrode system comprises a working electrode, a counter electrode, and a reference electrode. The working electrode is a copper-doped titanium-based material. The counter electrode can be a platinum electrode or a graphite electrode, and the reference electrode can be a saturated calomel electrode, a silver / silver chloride electrode, a mercury / mercuric oxide electrode, or the like, without particular limitation. The electrolyte of the three-electrode system is not particularly limited, and liquid culture medium can be used as the electrolyte.

[0033] In the present invention, the charging voltage is 0.8-1.2V, and the charging time is 10-30 minutes, more preferably 15-20 minutes. The charging process activates the material's energy storage properties, enabling rapid charge storage and slow release during use, thereby exerting an energy storage antibacterial effect. The present invention does not impose any particular restrictions on the device used for the three-electrode system charging process; however, the present invention preferably uses an electrochemical workstation for the charging process.

[0034] The present invention also provides a copper-doped titanium-based energy storage antibacterial material prepared by the above preparation method.

[0035] The present invention also provides the use of the copper-doped titanium-based energy storage antibacterial material in the prevention and treatment of biofouling, and is particularly suitable for the prevention and treatment of biofouling by electroactive bacteria.

[0036] During application, the copper-doped titanium-based energy storage antibacterial material of the present invention can release electric charge through its own energy storage performance, interfering with the extracellular electron transfer of electroactive bacteria. At the same time, the copper element can play an antibacterial role, thereby effectively inhibiting the growth of electroactive bacteria and the attachment of biofilms. The electroactive bacteria can be of the genus Geobacter ( Geobacter ), Shewanella spp. ( Shewanella ), Pseudomonas aeruginosa ( P. aeruginosa ), Leuconostoc mesenteroides ( L. mesenteroides ), Lactococcus lactis ( L. lactis ), iron-reducing red bacteria and sulfur-reducing soil bacteria, etc. In one or more embodiments of the present invention, the electroactive bacteria are Pseudomonas aeruginosa ( P. aeruginosa ).

[0037] The technical solution of the present invention is further described below with reference to specific examples. The present invention has no particular limitation on the sources of the reagents used in the following examples, and commercially available products known to those skilled in the art can be used.

[0038] In the following examples, LB liquid culture medium included 10 g of tryptone, 5 g of yeast extract, 10 g of sodium chloride, and 1 L of deionized water.

[0039] Example 1 This embodiment provides a copper-doped titanium-based energy storage antibacterial material and a preparation method thereof.

[0040] (1) Pretreatment: Soak a titanium foil (TA2 industrial pure titanium) with a size of 10 mm × 10 mm × 0.1 mm in a 1 mol / L hydrochloric acid solution for 3 h. Then, ultrasonically clean the titanium foil in acetone, anhydrous ethanol, and deionized water for 15 min, and dry it for later use.

[0041] (2) Anodic oxidation: The titanium foil (Ti foil) cleaned and dried in step (1) was used as the anode, the graphite electrode was used as the cathode, and the electrolyte solution was an organic solvent system (1.15 g NH4F dissolved in 300 mL ethylene glycol and 33 mL deionized water). The distance between the two electrodes was kept at about 1 cm, and a constant voltage of 60 V was applied between the cathode and anode using a DC power supply system. The first anodization treatment was performed under magnetic stirring for 1 h. The Ti foil after the first anodization was removed and ultrasonically cleaned with a 0.7 mol / L hydrochloric acid solution for 1 h to remove the first oxide layer to obtain a Ti foil with a bright surface. The Ti foil was cleaned and dried for later use. The Ti foil with the first oxide film removed was subjected to a second anodization under the same conditions for 1 h to obtain a Ti foil containing highly ordered TNTs.

[0042] (3) Copper deposition and annealing: A two-electrode system was used, with the Ti foil containing highly ordered TNTs prepared in step (2) as the cathode and the platinum electrode as the anode. The solution was placed in a 0.75 mol / L Cu(NO3)2·3H2O solution, with a DC voltage of 15 V maintained for 60 s to allow copper ions to rapidly deposit on the TNTs surface. The solution was then rinsed three times with anhydrous ethanol and deionized water, dried, and annealed in a muffle furnace at 450°C for 3 h to obtain a copper-doped titanium-based material, designated as TNTs-0.75Cu or UC-TNTs-0.75Cu.

[0043] (4) Charging treatment: A three-electrode system was used, with the TNTs-0.75Cu sample as the working electrode, a metal platinum electrode (1 cm × 1 cm) as the auxiliary electrode, and a saturated calomel electrode (SCE) as the reference electrode; LB liquid culture medium was used as the electrolyte, and the battery was charged at a voltage of 1 V for 15 min; a copper-doped titanium-based energy storage antibacterial material was obtained, which was recorded as CD-TNTs-0.75Cu.

[0044] Example 2 The difference between this embodiment and embodiment 1 is that the concentration of Cu(NO3)2·3H2O in this embodiment is 0.55 mol / L, and the copper-doped titanium-based material obtained in step (3) of this embodiment is recorded as TNTs-0.55Cu.

[0045] Example 3 The difference between this embodiment and embodiment 1 is that the concentration of Cu(NO3)2·3H2O in this embodiment is 0.35 mol / L, and the copper-doped titanium-based material obtained in step (3) of this embodiment is recorded as TNTs-0.35Cu.

[0046] Example 4 The difference between this embodiment and embodiment 2 is that the deposition time in step (3) of this embodiment is 120 s, and the copper-doped titanium-based material obtained in step (3) of this embodiment is recorded as TNTs-0.55Cu-2.

[0047] Comparative Example 1 The difference between this comparative example and Example 1 is that this comparative example only performs step (1) to obtain a pretreated Ti foil, which is recorded as UC-Ti.

[0048] Comparative Example 2 Compared with Comparative Example 1, this comparative example differs in that a three-electrode system is used in this comparative example, with pretreated Ti foil as the working electrode, a metal platinum electrode (1 cm×1 cm) as the auxiliary electrode, and a saturated calomel electrode (SCE) as the reference electrode; LB liquid culture medium is used as the electrolyte, and the battery is charged at a voltage of 1 V for 15 min, which is recorded as CD-Ti.

[0049] 1. Morphology characterization The surface morphologies of TNTs-0.75Cu of Example 1, TNTs-0.55Cu of Example 2, TNTs-0.35Cu of Example 3, and TNTs-0.55Cu-2 of Example 4 were characterized using a field emission scanning electron microscope (FESEM) with a voltage of 5 kV and magnifications of 5K and 50K. Figure 1 As shown in Figure 2, from (a) to (c), the copper ion concentration increases from 0.35 mol / L to 0.75 mol / L. It can be seen that the increase in copper ion concentration affects the morphology of TNTs. When the concentration of Cu(NO3)2·3H2O is 0.75 mol / L, nanotube fragments appear on the surface of TNTs, but the tube mouth is still clearly visible, and the TNTs still maintain a tubular structure. Figure 1 As shown in (b) and (d), when the Cu(NO3)2·3H2O concentration is 0.55 mol / L, increasing the electrodeposition time to 2 min results in severe TNT collapse and irregularity, with the collapsed nanotubes blocking the TNT openings. This suggests that a TNTs-Cu nanoantibacterial platform with the highest Cu doping content and the most complete TNT structure can be obtained when the Cu(NO3)2·3H2O concentration is 0.75 mol / L and the electrodeposition time is 1 min.

[0050] A 3D ultra-depth microscope was used to perform high-precision three-dimensional morphology measurement. The microstructure and size distribution of the Cu coating on the surface of the TNTs-0.75Cu sample of Example 1 were observed and analyzed at both vertical and horizontal viewing angles. The magnification was 300. Figure 2 As shown, Figure 2(a) is a top view, and (b) is a side view. It can be seen intuitively that the size distribution of copper deposits on the surface of the TNTs-0.75Cu sample is large, the surface of the copper coating is undulating, and the copper dendrite particle size is large, which is consistent with the conclusion of the above FESEM.

[0051] 2. Elemental analysis In order to further prove that the deposits on the surface of the TNTs-0.75Cu sample in Example 1 are copper dendrites, energy dispersive spectroscopy (EDS) analysis was performed on the spherical deposits on the surface of the TNTs-0.75Cu sample. The results are as follows: Figure 3 As shown, it shows that the dendrites on the surface of TNTs-0.75Cu sample are mainly composed of three elements: C, O and Cu.

[0052] X-ray photoelectron spectroscopy (XPS) was used to test the composition of the surface of TNTs-0.75Cu samples and the changes in the valence of Cu elements, such as Figure 4 As shown in (a) to (d) in the figure, the characteristic peaks of C 1s, O 1s, Ti 2p, and Cu 2p clearly appeared in the XPS test, indicating that the TNTs-0.75Cu sample contains carbon, oxygen, titanium, and copper. Figure 4 As shown in (b), the strong peak at the binding energy of 529.98 eV in the O 1s spectrum is the characteristic peak of Ti-O, and this part of the O element comes from TNTs. Figure 4 (c) shows that all Ti on the sample surface exists as TiO2. Figure 4 In (d), it can be determined that the Cu element exists in the +2 form on the sample surface, indicating the presence of CuO on the sample surface.

[0053] 3. Capacitance Characterization The capacitance of the TNTs-0.75Cu sample of Example 1 and the Ti foil of Comparative Example 1 was characterized using an electrochemical workstation. Cyclic voltammetry was performed on the TNTs-0.75Cu sample at scan rates of 0.1, 0.3, 1, 5, 0.01, and 10 V / s, and at scan rates of 1, 2, and 10 mA·cm -2 Constant current charge and discharge tests were performed at a constant current density. An electrochemical workstation was used to compare the capacitive performance of Ti and TNTs-0.75Cu.

[0054] Figure 5 (a) and (c) show the cyclic voltammetry (CV) curves and constant current charge-discharge (GCD) curves of TNTs-0.75Cu samples at different scan rates and scan current densities. -1 The maximum area capacitance was observed when the scanning current density was 1 mA·cm -2 When , the longest charge and discharge time is observed, and the sample has the largest capacitance. Figure 5 As shown in (b), at 1 V·s -1 The current of the TNTs-0.75Cu sample is much greater than that of the pure Ti foil sample at the scan rate, and the capacitance of the sample is nearly 3 times higher than that of the pure Ti foil. A similar capacitance trend is observed from the corresponding GCD curve. Figure 5 As shown in (d), at 1 mA·cm -2 At a current density of 1.5 GHz, the charge and discharge time of TNTs-0.75Cu is approximately 1700 s, much longer than that of pure Ti foil. This shows that the capacitance of TNTs-0.75Cu is significantly improved compared to that of Ti foil.

[0055] 4. Corrosion resistance characterization The corrosion resistance of the UC-TNTs-0.75Cu and CD-TNTs-0.75Cu samples of Example 1, as well as the UC-Ti of Comparative Example 1 and the CD-Ti of Comparative Example 2, was further tested by electrochemical impedance spectroscopy (EIS) at an open circuit potential with a test frequency range of 10 mHz to 100 kHz and an AC voltage amplitude of 50 mV.

[0056] In the Nyquist curve, for UC-Ti and CD-Ti, Figure 6 A capacitor ring with a large radius is observed in (c). Compared with the uncharged (UC-Ti), the significant reduction in the radius of the capacitor ring of the charged Ti (CD-Ti) clearly indicates that the charging process has a significant degree of corrosion on the Ti foil. Figure 6 As shown in (a), the radius of the capacitance ring of the TNTs-0.75Cu sample in the high-frequency region does not change much, indicating that the charging process has no obvious corrosion on the TNTs-0.75Cu sample. Figure 6 In (d), the |Z| of the Ti foil (CD-Ti) after charging is observed. 0.01 Compared with the uncharged Ti foil (UC-Ti), it is smaller, indicating that the charging process causes a certain degree of corrosion to the Ti foil. Figure 6 In (b), it can be seen that the |Z| of the UC-TNTs-0.75Cu sample 0.01 There is no obvious change, indicating that it exhibits excellent stability in the electrolyte, which is consistent with the results of the Nyquist curve.

[0057] 5. Antibacterial properties In order to observe the effects of the UC-TNTs-0.75Cu and CD-TNTs-0.75Cu samples of Example 1 and the UC-Ti samples of Comparative Example 1 and the CD-Ti samples of Comparative Example 2 on Pseudomonas aeruginosa ( P. aeruginosa) inhibitory effect, the bacteria treated with the material were stained with a bacterial live / dead staining kit, and the culture medium was LB liquid culture medium. The following formula was used to calculate the inhibitory effect on P. aeruginosa Bacteria elimination rate ( D ) and anti-adhesion rate ( A ): ; ; In the above formula, S 样死亡 is the area of ​​dead bacteria on the sample surface; S 样总 is the total bacterial area on the sample surface; S 空白总 is the total area of ​​bacteria on the uncharged Ti foil surface.

[0058] Figure 7 (a) in the figure shows the different samples in P. aeruginosa Fluorescence microscopy images of bacteria on the Ti foil surface after immersion in bacterial solution for 12 hours show that large areas of fluorescence are observed both before and after charging, indicating that a large number of bacteria are attached to the surfaces of both the uncharged Ti foil (UC-Ti) and the Ti foil after charge and discharge (CD-Ti). However, the green fluorescence on the Ti foil after charge and discharge is significantly dimmer than that on the uncharged foil, interspersed with large areas of red fluorescence. The proportion of dead bacteria on the Ti foil after charge and discharge is higher, while the number of live bacteria is lower, with most of them in the early stages of apoptosis. This indicates that the charge and discharge treatment has a certain bactericidal effect.

[0059] The fluorescence area of ​​uncharged TNTs-0.75Cu (UC-TNTs-0.75Cu) is significantly smaller than that of uncharged Ti foil (UC-Ti), indicating that the amount of bacteria attached to it is much smaller than that of Ti foil. This can be attributed to the release of CuO deposits on the surface of TNTs-0.75Cu. 2+ After charging and discharging, almost no fluorescence can be seen on the surface of CD-TNTs-0.75Cu. Figure 7 As can be seen in images (b) and (c), the anti-adhesion and sterilization rates are as high as 96.0 ± 1.1% and 98.0 ± 0.6%, respectively. Furthermore, a post-charge antibacterial effect proportional to the capacitance is observed. Compared to Ti foil, the TNTs-0.75Cu exhibits significantly higher capacitance, demonstrating superior antibacterial efficacy.

[0060] After three cycles of charging for 15 minutes and discharging for 10 minutes, the TNTs-0.75Cu material maintained its high performance. Furthermore, the cyclic treatment increased its exposure time to bacterial surfaces, significantly improving its anti-adhesion and sterilization rates. Both rates exceeded 99%.

[0061] Normal Pseudomonas aeruginosa cells have regular cell morphology, are distributed in rods, and have complete structures. Figure 8 As can be seen in (a), a large number of Pseudomonas aeruginosa adhere to the uncharged Ti foil in the form of sheets, showing typical biofilm characteristics of membrane wrapping, and multiple secretions can be observed on the surface of the bacteria. Figure 8 (b) shows that after charge and discharge treatment, the cell morphology has changed significantly. There is no obvious cell wall, and the cells have become shorter and rounder. Most of the cells have shrunk and become concave, and some cells have become shriveled or hollow, which indicates that charging promotes cell apoptosis. At the same time, Figure 8 As shown in (c), the middle section of the bacteria on the uncharged TNTs-0.75Cu surface is deformed and shrinking. This may be the result of the bacterial stress response to Cu, including oxidative stress and DNA damage. Figure 8 In (d), the cell morphology is completely destroyed, most of the cells are lysed, and a large amount of cell fragments appear, indicating that the large amount of charge released by the TNTs-0.75Cu sample after charging can effectively inhibit the attachment and growth of Pseudomonas aeruginosa cells, remove bacterial biofilms, destroy cell walls and cell membranes, and ultimately lead to bacterial death.

[0062] from Figure 9 It can be observed that the agar plates coated with bacterial solution on the surface of the uncharged Ti foil and the Ti foil after charge and discharge have large colonies, which are significantly more than those on the TNTs-0.75Cu after charge and discharge (CD-TNTs-0.75Cu) and the uncharged TNTs-0.75Cu (UC-TNTs-0.75Cu). 6 After 10 times, no colony growth was observed on the agar plate of the charged and discharged TNTs-0.75Cu (CD-TNTs-0.75Cu) sample, while single dispersed colonies could be clearly observed in the remaining three groups.

[0063] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A method for preparing a copper-doped titanium-based energy storage antibacterial material, characterized in that: The steps include: The titanium-based material is pretreated and then anodized twice to obtain a titanium-based material containing a TiO2 nanotube array; The titanium-based material containing the TiO2 nanotube array is placed in a copper ion solution for electrodeposition, and then annealed after cleaning and drying to obtain a copper-doped titanium-based material; A three-electrode system is used to charge the copper-doped titanium-based material to obtain the copper-doped titanium-based energy storage antibacterial material.

2. The preparation method according to claim 1, wherein The titanium-based material is selected from pure titanium or titanium alloy. The titanium-based material further includes a pretreatment step before anodizing treatment, and the pretreatment step is acid washing, acetone washing, ethanol washing and water washing in sequence.

3. The preparation method according to claim 1, wherein The anodic oxidation adopts a two-electrode system, with a titanium-based material as the anode and a graphite electrode or a platinum sheet as the cathode. The voltage of the anodic oxidation treatment is 40-80V and the time is 0.5-2h. The electrolyte of the anodic oxidation treatment is an ethylene glycol aqueous solution containing ammonium fluoride.

4. The preparation method according to claim 1, wherein After the first anodizing treatment, the generated TiO2 nanotube arrays are removed by acid washing, and then a second anodizing treatment is performed.

5. The preparation method according to claim 1, wherein In the copper ion solution, the concentration of copper ions is 0.3-1 mol / L; the anions in the copper ion solution are selected from one or more of nitrate ions, chloride ions, sulfate ions, pyrophosphate ions or cyanide ions.

6. The preparation method according to claim 1, wherein The electrodeposition process uses a titanium-based material containing a TiO2 nanotube array as a cathode and a platinum sheet or a graphite electrode as an anode; the electrodeposition voltage is 10-20V and the time is 50-150s.

7. The preparation method according to claim 1, wherein The annealing temperature is 400-500° C., and the annealing time is 2-5 hours.

8. The preparation method according to claim 1, wherein The three-electrode system includes a working electrode, a counter electrode and a reference electrode, wherein the working electrode is a copper-doped titanium-based material; the voltage of the charging process is 0.8-1.2 V, the charging time is 10-30 minutes, and the discharging time is 5-15 minutes.

9. The copper-doped titanium-based energy storage antibacterial material prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the copper-doped titanium-based energy storage antibacterial material according to claim 9 in the prevention and treatment of biofouling.

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