Titanium-oxygen cluster composite fiber membrane with broad spectrum light response and preparation method and application thereof

Abstract

This invention belongs to the field of functional polymer composite materials technology, and more specifically relates to a titanium oxide cluster composite fiber membrane with broad-spectrum photoresponse, its preparation method, and its applications. The preparation method includes: using 3-fluorocatechol and titanate as reactants, a solvothermal reaction is carried out under an inert atmosphere to obtain trifluorocatechol-modified titanium oxide cluster crystals; then, these crystals are dissolved with thermoplastic polyurethane particles in an organic solvent to prepare a composite spinning solution, which is then electrospun and dried to obtain the composite fiber membrane. In this fiber membrane, the titanium oxide clusters are uniformly dispersed at the nanoscale, forming a three-dimensional porous network structure with a diameter of 100-1000 nm, exhibiting broad-spectrum strong absorption (300-1000 nm), superhydrophobicity, and excellent photothermal properties. This invention effectively solves the problem of inorganic nanoclusters agglomeration in organic matrices through surface modification, achieving synergistic antibacterial effects through photothermal and photocatalytic processes, and has broad application prospects in medical protection, intelligent thermal management textiles, and environmental purification.

Description

Technical Field

[0001] This invention belongs to the field of functional polymer composite materials technology, and more specifically relates to a titanium oxide cluster composite fiber membrane with broad-spectrum light response, its preparation method and application. Background Technology

[0002] With the development of materials science, smart materials with photoresponsive properties have shown great potential in fields such as environmental purification, personal protection, and biomedicine. Titanium oxide clusters, as a type of well-defined semiconductor cluster material, have attracted much attention due to their excellent photocatalytic activity. However, traditional titanium oxide clusters typically absorb mainly ultraviolet light or part of the visible light, failing to fully utilize the near-infrared light that accounts for about 50% of solar energy, thus limiting their full-spectrum solar energy utilization efficiency. Furthermore, as inorganic nanocluster units, titanium oxide clusters have poor compatibility with organic polymers, easily agglomerating during composite and processing, leading to functional failure and a decline in material mechanical properties.

[0003] Polyurethane fiber membranes are ideal flexible substrate materials due to their excellent elasticity, film-forming properties, and processability. Electrospinning technology is an effective means of preparing micro / nanofiber membranes, which can endow materials with high specific surface area and porous structure. Currently, some studies have combined photothermal agents (such as gold nanorods and carbon materials) or photocatalysts with polymers to prepare functional fiber membranes. However, these systems often have the following problems: 1. It has a single function, possessing only one function of photothermal or photocatalytic, and cannot make synergistic use of different wavelengths of sunlight; 2. Narrow spectral response: the material only responds to a specific wavelength range, failing to fully utilize the solar spectrum; 3. Poor stability and compatibility; inorganic functional units are prone to leaching or agglomeration from the polymer matrix, leading to performance degradation and short service life. 4. Lack of multi-effect integration makes it difficult to achieve high waterproofness, high antibacterial efficiency, and stable photothermal performance in the same material at the same time.

[0004] Therefore, developing a high-performance fiber membrane that can synergistically utilize the broad spectrum of sunlight, has good inorganic-organic compatibility, and integrates multiple protective functions has significant practical application value. Summary of the Invention

[0005] The purpose of this invention is to provide a titanium oxide cluster composite fiber membrane with broad-spectrum light response, its preparation method, and its application, so as to solve the problems existing in the prior art.

[0006] To achieve the above objectives, the present invention provides the following solution: One of the technical solutions of this invention is to provide a method for preparing a titanium oxide cluster composite fiber membrane with broad-spectrum photoresponse, comprising the following steps: Trifluorocatechol-modified titanium oxide cluster crystals (TOC) were prepared by solvothermal reaction of 3-fluorocatechol and titanate under an inert atmosphere. The composite spinning solution was prepared by dissolving the trifluorocatechol-modified titanium oxide cluster crystals, polyurethane particles (PU), and polyethylene glycol in an organic solvent. The composite spinning solution is electrospun to obtain a nascent fiber membrane. After the nascent fiber membrane is dried, the titanium oxide cluster composite fiber membrane (TOC-PU) with broad-spectrum light response is obtained.

[0007] Furthermore, the titanate includes at least one of tetraethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate.

[0008] Furthermore, the ratio of 3-fluorocatechol to titanate is 0.2-0.3g:0.2-0.3mL.

[0009] Furthermore, the inert atmosphere is a nitrogen atmosphere or an argon atmosphere.

[0010] Furthermore, the temperature of the solvothermal reaction is 100-120 °C, and the time is 3-5 days.

[0011] Furthermore, the solvent for the solvothermal reaction includes at least one of toluene (TOL), formic acid (FA), isopropanol (IPA), dimethyl sulfoxide (DMSO), and N,N-dimethylformamide (DMF).

[0012] Furthermore, the mass ratio of the trifluorocatechol-modified titanium oxide cluster crystals, polyurethane particles, and polyethylene glycol is 1:10-100:5-50.

[0013] Furthermore, the polyethylene glycol is polyethylene glycol with a molecular weight of 6000.

[0014] Furthermore, the polyurethane particles are thermoplastic polyurethane particles, including polyether-type thermoplastic polyurethane; the polyether-type thermoplastic polyurethane has a Shore A hardness of 60-80, an elongation at break ≥700%, and an abrasion amount ≤50 mm. 3 .

[0015] Furthermore, the organic solvent includes at least one of N,N-dimethylformamide (DMF), tetrahydrofuran (THF), and N-methylpyrrolidone (NMP).

[0016] Furthermore, the solid content of the composite spinning solution is 6-15 wt.%.

[0017] Furthermore, the parameters for electrospinning are as follows: spinning voltage is 15-25 kV, receiving distance is 10-20 cm, spinning solution propulsion speed is 0.5-2.0 mL / h, ambient humidity is controlled at 30%-50%, and the receiving device is a flat plate receiver or a roller receiver.

[0018] Furthermore, the drying process is vacuum drying, with a temperature of 30-80℃ and a time of 12-48 hours.

[0019] The second technical solution of the present invention provides a titanium oxide cluster composite fiber membrane with broad-spectrum light response, wherein the titanium oxide cluster composite fiber membrane with broad-spectrum light response is prepared by the above-described preparation method.

[0020] In this titanium oxide cluster composite fiber membrane, trifluorocatechol-modified titanium oxide clusters are uniformly dispersed at the nanoscale inside and on the surface of polyurethane fibers. The fiber membrane is formed by the interlacing of fibers with diameters in the range of 100-1000 nm, forming a three-dimensional porous network structure. The fiber membrane has a wide and strong light absorption in the wavelength range of 300-1000 nm. The fiber membrane has superhydrophobic properties. Under sunlight irradiation, the surface temperature of the fiber membrane can rapidly rise by about 45°C within 5 minutes.

[0021] The third technical solution of the present invention provides an application of the above-mentioned titanium oxide cluster composite fiber membrane with broad-spectrum light response in the preparation of medical protective materials, outdoor intelligent thermal management textiles, photothermal driven water or air purification devices, or photoresponsive antibacterial packaging materials.

[0022] Among them, medical protective materials include protective clothing, surgical gowns, masks, wound dressings, etc.; outdoor intelligent thermal management textiles include thermal clothing, de-icing coatings, adaptive temperature regulating fabrics, etc.

[0023] The present invention discloses the following technical effects: This invention employs trifluorocatechol as a modifying ligand, utilizing its strongly electronegative F atom and the catechol structure to perform surface engineering on titanium oxide clusters. This not only significantly broadens the light absorption range of titanium oxide clusters from the ultraviolet-visible region to the near-infrared region, achieving full-spectrum capture of sunlight, but also greatly improves the compatibility between inorganic titanium oxide clusters and organic polyurethane matrices, solving the problem of nanoparticle aggregation.

[0024] This invention combines modified titanium oxide clusters with polyurethane via electrospinning. This process, on the one hand, "locks" the functional units in situ within the fibers to prevent leaching; on the other hand, it forms micro- and nano-scale fibers and a three-dimensional porous structure, endowing the material with superhydrophobicity and high air permeability. The process is simple and suitable for large-scale preparation.

[0025] The titanium oxide cluster composite fiber membrane provided by this invention combines a micro-nano-scale rough fiber structure with a low surface energy trifluorine-modified layer. These two elements synergistically construct a superhydrophobic interface resembling a lotus leaf surface, effectively blocking liquid permeation. Under illumination, the titanium oxide clusters generate a photothermal effect in the near-infrared band, significantly raising the surface temperature of the composite fiber membrane. Simultaneously, the titanium oxide clusters are excited to generate reactive oxygen species in the visible light band. This synergistic effect of photothermal and photocatalytic mechanisms enables the composite fiber membrane to achieve significant antibacterial effects against various bacteria (such as Escherichia coli and Staphylococcus aureus) after light treatment. This material has significant application value in multiple high-tech fields such as advanced personal protective equipment, smart wearables, and environmental engineering. Attached Figure Description

[0026] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings: Figure 1 The image shows the crystal structure of the trifluorocatechol-modified titanium oxide cluster prepared in Example 1.

[0027] Figure 2 The diffraction pattern (X-ray powder diffraction pattern) of the trifluorocatechol-modified titanium oxide cluster powder prepared in Example 1 is shown.

[0028] Figure 3 The absorption spectrum of the trifluorocatechol-modified titanium oxide cluster prepared in Example 1 is shown.

[0029] Figure 4 The absorption spectrum of commercially available P25 (TiO2 nanoparticles) used in Comparative Example 1 is shown.

[0030] Figure 5 Photographs illustrating the flexibility of TOC-PU film.

[0031] Figure 6 This is a SEM image of the TOC-PU film.

[0032] Figure 7 This is a scanning electron microscope elemental diagram of the TOC-PU film.

[0033] Figure 8 This is a hydrophobicity test result of the TOC-PU membrane. Figure 9 A comparison graph showing the surface temperature of P25-PU film, PU film and TOC-PU film changing over time under simulated sunlight irradiation.

[0034] Figure 10 A comparison graph showing the surface temperature of P25-PU film, PU film and TOC-PU film under 808nm irradiation over time.

[0035] Figure 11 Comparative photographs showing the antibacterial performance test results of P25-PU membrane and TOC-PU membrane against Staphylococcus aureus. Detailed Implementation

[0036] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0037] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0038] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0039] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be readily apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0040] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0041] Unless otherwise specified, all raw materials and reagents involved in the specific embodiments of this invention are commercially available products. Specifically, the polyether-type thermoplastic polyurethane used in the specific embodiments of this invention has a Shore A hardness of 71, an elongation at break of 850%, and an abrasion tolerance of 50 mm. 3 .

[0042] Unless otherwise specified, room temperature and ambient temperature in the specific embodiments of this invention refer to 20-30℃.

[0043] It should be noted that any aspects not described in detail in this invention are conventional practices in the field and are not the focus of this invention.

[0044] Example 1 The preparation steps of the titanium oxide cluster composite fiber membrane with broad-spectrum light response include: S1. Weigh 0.2792 g of 3-fluorocatechol and place it in a reaction flask. Then, add 50 μL of formic acid, 6 mL of toluene, and 0.3 mL of tetraisopropyl titanate sequentially. After purging the flask with nitrogen to replace the air, seal it and sonicate it for 10 min. After sonication, transfer the reaction flask to a reaction vessel and place it in a 120 ℃ oven for constant temperature reaction for 5 days. After the reaction is complete, allow it to cool naturally, collect the precipitate, wash it three times with ethanol, and finally dry it in a 40 ℃ vacuum oven to obtain trifluorocatechol-modified titanium oxide cluster crystals.

[0045] S2. Dissolve 0.02 g of the titanium oxide cluster crystals prepared in step S1, 0.325 g of polyethylene glycol and 0.65 g of polyether-type thermoplastic polyurethane particles together in 7 mL of DMF / THF mixed solvent (volume ratio 1:1), and magnetically stir in a water bath at 60℃ for 24 hours to obtain a uniform, dark red spinning solution with a solid content of 12 wt.%.

[0046] S3. Inject the spinning solution into a 10 mL syringe, install a 21G stainless steel needle, and set the electrospinning parameters: voltage 18 kV, receiving distance 15 cm, feed speed 1.0 mL / h, ambient temperature 25℃, humidity 40%. Use flat aluminum foil as the receiving substrate, and the spinning time is about 3 hours to obtain the nascent fiber membrane.

[0047] S4. Carefully peel the collected nascent fiber membrane off the aluminum foil and dry it in a vacuum oven at 40°C for 24 hours to obtain the final composite fiber membrane, which is a titanium oxide cluster composite fiber membrane with a broad-spectrum light response, denoted as TOC-PU membrane.

[0048] Example 2 Compared with Example 1, the difference is that in step S2, the mass ratio of titanium oxide cluster crystals to thermoplastic polyurethane particles is 1:50, that is, 0.06g of titanium oxide cluster crystals and 0.65g of thermoplastic polyurethane particles.

[0049] Example 3 Compared with Example 1, the difference is that the electrospinning voltage in step S3 is adjusted to 20 kV and the receiving distance is adjusted to 12 cm.

[0050] Comparative Example 1 The preparation steps of commercial nano-titanium dioxide polyurethane films include: S1. Dissolve 0.02 g TiO2 nanoparticles (P25, particle size approximately 25 nm), 0.325 g polyethylene glycol, and 0.65 g polyether-type thermoplastic polyurethane particles together in 7 mL of DMF / THF mixed solvent (volume ratio 1:1). Stir magnetically in a 60°C water bath for 24 hours to obtain a spinning solution with a solid content of 12 wt.% (with slight precipitation and uneven dispersion).

[0051] S2. Inject the spinning solution into a 10 mL syringe, install a 21G stainless steel needle, and set the electrospinning parameters: voltage 18 kV, receiving distance 15 cm, feed speed 1.0 mL / h, ambient temperature 25℃, humidity 40%. Use flat aluminum foil as the receiving substrate, and the spinning time is about 3 hours (occasional filament breakage occurs during the process) to obtain the nascent fiber membrane.

[0052] S3. Carefully peel the collected nascent fiber membrane off the aluminum foil and dry it in a vacuum oven at 40°C for 24 hours to obtain the final composite fiber membrane, which is the commercial nano-titanium dioxide polyurethane membrane, denoted as P25-PU membrane.

[0053] Comparative Example 2 The preparation steps of pure polyurethane membrane include: S1. Dissolve 0.325g of polyethylene glycol and 0.65g of polyether-type thermoplastic polyurethane particles together in 7 mL of DMF / THF mixed solvent (volume ratio 1:1), and stir magnetically in a 60℃ water bath for 24 hours to obtain a spinning solution with a solid content of 12 wt.%.

[0054] S2. Inject the spinning solution into a 10 mL syringe, install a 21G stainless steel needle, and set the electrospinning parameters: voltage 18 kV, receiving distance 15 cm, feed speed 1.0 mL / h, ambient temperature 25℃, humidity 40%. Use flat aluminum foil as the receiving substrate, and the spinning time is about 3 hours to obtain the nascent fiber membrane.

[0055] S3. Carefully peel the collected nascent fiber membrane off the aluminum foil and dry it in a vacuum oven at 40°C for 24 hours to obtain the final fiber membrane, which is a pure polyurethane membrane, denoted as PU membrane.

[0056] Test case Figure 1 The image shows the crystal structure of the trifluorocatechol-modified titanium oxide cluster prepared in Example 1.

[0057] Figure 2 The image shows the diffraction pattern of the trifluorocatechol-modified titanium oxide cluster powder prepared in Example 1.

[0058] The results were obtained using a UV-Vis-NIR spectrophotometer. Figures 3-4 As shown.

[0059] Figure 3 The absorption spectrum of the trifluorocatechol-modified titanium oxide cluster prepared in Example 1 is shown.

[0060] Figure 4 The absorption spectrum of commercially available P25 (TiO2 nanoparticles) used in Comparative Example 1 is shown.

[0061] Depend on Figures 3-4 It can be seen that the titanium oxide cluster crystal of Example 1 exhibits sustained high absorption in the 300-1000 nm range, confirming its broad-spectrum photoresponse characteristics. In contrast, P25 of Comparative Example 1 mainly absorbs ultraviolet light (<400 nm).

[0062] Figure 5 This is a photographic image demonstrating the flexibility of the TOC-PU film. As can be seen from the image, the TOC-PU film of Example 1 exhibits good flexibility and can be bent in different directions without deformation.

[0063] Figure 6 The image shows a SEM image of the TOC-PU membrane. As can be seen, the TOC-PU membrane has continuous fibers, a smooth surface, no obvious titanium oxide clusters, and an average diameter of approximately 350 nm, forming a well-developed porous network.

[0064] Figure 7 This is a scanning electron microscope elemental diagram of the TOC-PU film.

[0065] Figure 8 This is a hydrophobicity test result of the TOC-PU membrane. As can be seen from the figure, the TOC-PU membrane has good hydrophobicity, and water droplets can form a water droplet pattern.

[0066] The sample surface was illuminated vertically using a simulated solar light source, and temperature changes were recorded using an infrared thermal imager. The results are as follows: Figure 9 As shown.

[0067] Figure 9 The graphs show a comparison of the surface temperature changes of P25-PU film, PU film, and TOC-PU film under simulated sunlight irradiation over time. As can be seen from the graphs, the surface temperature of the TOC-PU film in Example 1 rose to 45°C after 5 minutes of illumination. The temperature rise of the P25-PU film in Comparative Example 1 was only 27°C, and the temperature rise of the pure PU film in Comparative Example 2 was almost zero.

[0068] The sample surface was vertically irradiated with an 808 laser source, and the temperature change was recorded using an infrared thermal imager. The results are as follows: Figure 10 As shown.

[0069] Figure 10The graphs show a comparison of the surface temperature changes of P25-PU film, PU film, and TOC-PU film under 808nm irradiation over time. As can be seen from the graphs, the surface temperature of the TOC-PU film in Example 1 rose to 45°C after 5 minutes of irradiation. The temperature rise of the P25-PU film in Comparative Example 1 was only 26°C, and the temperature rise of the pure PU film in Comparative Example 2 was almost zero.

[0070] The shaking method according to GB / T 20944.3-2008 standard was adopted. Staphylococcus aureus was used as the test strain, and the antibacterial performance was tested after treatment under simulated sunlight for 15 minutes. The results are as follows: Figure 11 As shown.

[0071] Figure 11 The figures show a comparison of the antibacterial performance test results of P25-PU membrane and TOC-PU membrane against Staphylococcus aureus. As can be seen from the figures, the antibacterial rate of the TOC-PU membrane in Example 1 reached 99.99%, indicating that the TOC-PU membrane of Example 1 has excellent antibacterial activity under light irradiation. However, Comparative Example 1 did not show any antibacterial effect.

[0072] Overall, this invention successfully prepared a high-performance composite fiber membrane integrating broad-spectrum photoresponse, superhydrophobicity, and efficient photothermal antibacterial properties by combining specific modification with trifluorocatechol with electrospinning. Its comprehensive performance is significantly superior to unmodified composite systems or single-component materials, demonstrating outstanding inventiveness and practicality.

[0073] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on the differences from other embodiments. The same or similar parts between the various embodiments can be referred to each other.

[0074] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a titanium oxide cluster composite fiber membrane with broad-spectrum photoresponse, characterized in that the steps include... include: Trifluorocatechol-modified titanium oxide cluster crystals were prepared by solvothermal reaction of 3-fluorocatechol and titanate under an inert atmosphere. The composite spinning solution was prepared by dissolving the trifluorocatechol-modified titanium oxide cluster crystals, polyurethane particles, and polyethylene glycol in an organic solvent. The composite spinning solution is electrospun to obtain a nascent fiber membrane. After the nascent fiber membrane is dried, the titanium oxide cluster composite fiber membrane with broad-spectrum light response is obtained.

2. The preparation method according to claim 1, characterized in that, The titanate includes at least one of tetraethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate; And / or, the inert atmosphere is a nitrogen atmosphere or an argon atmosphere; And / or, the solvent for the solvothermal reaction includes at least one of toluene, formic acid, isopropanol, dimethyl sulfoxide, and N,N-dimethylformamide.

3. The preparation method according to claim 1, characterized in that, The ratio of 3-fluorocatechol to titanate is 0.2-0.3 g: 0.2-0.3 mL; And / or, the temperature of the solvothermal reaction is 100-120 °C, and the time is 3-5 days.

4. The preparation method according to claim 1, characterized in that, The mass ratio of the trifluorocatechol-modified titanium oxide cluster crystals, polyurethane particles and polyethylene glycol is 1:10-100:5-50. And / or, the polyethylene glycol is polyethylene glycol with a molecular weight of 6000.

5. The preparation method according to claim 1, characterized in that, The polyurethane particles are thermoplastic polyurethane particles; And / or, the organic solvent includes at least one of N,N-dimethylformamide, tetrahydrofuran, and N-methylpyrrolidone.

6. The preparation method according to claim 1, characterized in that, The solid content of the composite spinning solution is 6-15 wt.%.

7. The preparation method according to claim 1, characterized in that, The parameters for electrospinning are as follows: spinning voltage is 15-25 kV, receiving distance is 10-20 cm, spinning solution propulsion speed is 0.5-2.0 mL / h, ambient humidity is controlled at 30%-50%, and the receiving device is a flat plate receiver or a roller receiver.

8. The preparation method according to claim 1, characterized in that, The drying process is vacuum drying, with a temperature of 30-80℃ and a time of 12-48 hours.

9. A titanium oxide cluster composite fiber membrane with broad-spectrum light response, characterized in that, The titanium oxide cluster composite fiber membrane with broad-spectrum light response is prepared by the preparation method according to any one of claims 1-8.

10. The application of the titanium oxide cluster composite fiber membrane with broad-spectrum photoresponse as described in claim 9 in the preparation of medical protective materials, outdoor intelligent thermal management textiles, photothermal driven water or air purification devices, or photoresponsive antibacterial packaging materials.

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