Preparation method of rare earth oxide nanoparticle-rare earth monatomic / titanium dioxide composite material for improving ultraviolet resistance of material

Abstract

The invention discloses a preparation method of a rare earth oxide nanoparticle-rare earth monatomic / titanium dioxide composite material for improving the anti-ultraviolet performance of a material, and belongs to the technical field of anti-ultraviolet materials. The preparation method comprises the following steps: adding titanium dioxide into a cerium metal salt solution, stirring to obtain a turbid liquid, then removing a solvent, drying to obtain solid powder, and finally calcining the obtained solid powder at high temperature to obtain the cerium-doped titanium dioxide photocatalyst. According to the method for improving the anti-ultraviolet performance of the material by loading titanium dioxide on the rare earth elements, the preparation method of the composite material is simple, the rare earth elements can be uniformly loaded on titanium dioxide, the material performance is stable, impurity energy levels are introduced into band gaps of titanium dioxide in a rare earth (monatomic) doping mode, and the anti-ultraviolet performance of the material is improved. Compared with the traditional non-loaded titanium dioxide, the titanium dioxide has the advantages that the anti-ultraviolet performance is greatly improved, and the titanium dioxide has important application significance in the sun-proof fiber shell fabric, so that the electronic structure of the titanium dioxide is changed, an intermediate energy level is formed, and the absorption of the titanium dioxide on ultraviolet light is enhanced.

Description

Technical Field

[0001] The present invention relates to the technical field of anti-ultraviolet materials, and in particular to a method for preparing a rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material for improving the anti-ultraviolet performance of the material. Background Art

[0002] With the growing demand for functional clothing in modern society, outdoor wear products such as sun-protective clothing are placing higher demands on material performance, particularly for ultraviolet (UV) protection. UV exposure can significantly shorten the lifespan of products. Therefore, developing fiber materials with excellent UV resistance is a key approach to improving the durability, comfort, and protection of sun-protective clothing, and a research hotspot in materials science and functional textile engineering. These materials effectively block harmful UV rays, providing more reliable protection for extended outdoor activities.

[0003] Rare earth elements possess a unique 4f orbital structure that can absorb ultraviolet light or some visible light, forming intermediate energy levels. This synergistic effect with the energy bands of TiO2 enhances titanium dioxide's absorption of ultraviolet light. However, achieving a uniform distribution of rare earth elements within the TiO2 matrix is often difficult, especially when high rare earth doping levels occur, where aggregation is prone to occur. Many preparation methods, such as sol-gel and solvothermal methods, require high process equipment requirements, making large-scale production uneconomical.

[0004] CN109529793B discloses a preparation method and application of a magnetic hydrotalcite-loaded titanium dioxide composite material. Using zinc and aluminum nitrates, sodium hydroxide, anhydrous sodium carbonate, ferrosoferric oxide, and titanium dioxide as raw materials, coprecipitation and hydrothermal crystallization are performed sequentially. The resulting composite material has good adsorption properties and can remove toxic Cr(VI) from water, but has not yet demonstrated UV resistance. Furthermore, because the coprecipitation method used in the preparation of the loaded titanium dioxide results in a physical bond between the titanium dioxide and the carrier hydrotalcite, the interaction force is weak, resulting in loss of catalyst activity and deactivation.

[0005] The above patents modify titanium dioxide, but its anti-ultraviolet performance still needs to be solved.

[0006] CN202111580098.9 discloses an antibacterial and anti-ultraviolet regenerated polyester fiber and a preparation method thereof. The invention blends and melt-modifies inorganic nano-zinc oxide with antibacterial and ultraviolet absorption functions and submicron-level cerium oxide inorganic materials with ultraviolet reflection functions with recycled polyester chips, so that the fiber has both antibacterial and anti-ultraviolet functions. However, the specific industrial implementation process has relatively cumbersome steps and operating procedures, and agglomeration is prone to occur during the production process and use. Therefore, it is necessary to develop new composite materials to improve the anti-ultraviolet performance of the fiber.

[0007] Therefore, studying the design and preparation of TiO2 loaded with rare earth elements and its role in improving anti-ultraviolet performance is of great significance to the development of high-performance anti-ultraviolet materials. Summary of the Invention

[0008] In order to solve the above technical problems, the purpose of the present invention is to provide a method for preparing rare earth oxide nanoparticles-rare earth single atoms / titanium dioxide composite materials that improve the anti-ultraviolet properties of materials, so as to solve the problem of long-term anti-ultraviolet effect of functionalized fibers and the lack of composite materials that can effectively improve the anti-ultraviolet properties of functionalized fibers.

[0009] The technical solution of the present invention to solve the above technical problems is as follows:

[0010] A method for preparing a rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material for improving the material's UV resistance comprises the following steps:

[0011] First, titanium dioxide is added to a cerium metal salt solution and stirred to obtain a suspension, then water is evaporated and dried to obtain a solid powder, and finally the obtained solid powder is calcined at a high temperature to obtain the product.

[0012] The beneficial effects of the present invention are as follows: the present invention loads cerium into titanium dioxide through rare earth element loading technology. On the one hand, it can more accurately control the distribution of active sites, while reducing crystal structure defects and improving the comprehensive performance of the material; on the other hand, a stable coordination structure is formed between the cerium rare earth atoms and the titanium dioxide surface through bonding, which provides a new mechanism for improving anti-ultraviolet performance. Cerium single atom doping can introduce impurity energy levels into the titanium dioxide band gap, causing the electronic structure of titanium dioxide to change. Because rare earth elements have a unique 4f electron orbital structure, they can form intermediate energy levels, reduce titanium dioxide's absorption of ultraviolet light, and improve visible light absorption capacity. Ce 4+ / Ce 3+Redox pairs promote electron transport and enhance the lifetime of photogenerated carriers, thereby improving the durability and stability of the material. Rare earth element doping introduces oxygen vacancies (Ov), which can capture photogenerated electrons and enhance the photostability of TiO2. The presence of oxygen vacancies also reduces the direct impact of high-energy ultraviolet light, making the material more durable in UV radiation environments.

[0013] Further, the cerium metal salt includes cerium sulfate or cerium nitrate.

[0014] Furthermore, the concentration of the cerium metal salt solution is 10-100 mg / mL.

[0015] Furthermore, the mass of the cerium element is 10-20% of the mass fraction of the titanium oxide.

[0016] Furthermore, the stirring time is 2-4 hours, and the stirring speed is 200-1000 rpm.

[0017] Furthermore, the method for removing the solvent is water evaporation or centrifugal filtration; the temperature for evaporating water is 60-100°C, and the temperature for drying is 60-120°C.

[0018] Furthermore, the high temperature calcination temperature is 500-700° C. and the time is 2-4 hours.

[0019] Preferably, the high-temperature calcination temperature is 600° C. and the time is 3 hours.

[0020] Furthermore, the high-temperature calcination environment is an air atmosphere or an argon atmosphere.

[0021] Preferably, the high-temperature calcination environment is air atmosphere.

[0022] A rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material for improving the anti-ultraviolet performance of the material is prepared by adopting the above preparation method.

[0023] The application of the above-mentioned rare earth oxide nanoparticles-rare earth single atom / titanium dioxide composite material for improving the ultraviolet resistance of materials in improving the ultraviolet resistance of fiber materials.

[0024] The present invention has the following beneficial effects:

[0025] The present invention provides a preparation method for a rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material for improving the anti-ultraviolet performance of the material. The method is simple, the rare earth elements can be evenly loaded on the titanium dioxide, the material performance is stable, and impurity energy levels are introduced into the band gap of the titanium dioxide by rare earth doping, so that the electronic structure of the titanium dioxide is changed, an intermediate energy level is formed, and the absorption of ultraviolet light by the titanium dioxide is reduced. Compared with traditional unloaded titanium dioxide, the anti-ultraviolet performance is greatly improved, and the application significance in sun-proof fiber fabrics is important. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 is a transmission electron microscope (TEM) image of titanium dioxide without cerium loading;

[0027] Figure 2 This is a transmission electron microscope image of titanium dioxide loaded with rare earth element cerium prepared in Example 1;

[0028] Figure 3 XRD patterns of TiO2 before and after loading rare earth elements;

[0029] Figure 4 The wavelength-transmittance diagram of different samples in the experimental example. DETAILED DESCRIPTION

[0030] The principles and features of the present invention are described below in conjunction with the accompanying drawings. The examples are only used to explain the present invention and are not intended to limit the scope of the invention. In the embodiments, if specific conditions are not specified, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer of the reagents or instruments is not specified, they are all conventional products that can be purchased commercially.

[0031] Example 1:

[0032] A method for preparing a rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material for improving the UV resistance of the material comprises the following steps:

[0033] (1) Add 144.26 mg of cerium sulfate tetrahydrate to 3 mL of deionized water, mix thoroughly with ultrasonic waves, and stir at 500 rpm for 30 min.

[0034] (2) adding 500 mg of titanium dioxide to the solution obtained in step (1) to form a suspension, and continuing to stir at 500 rpm for 3 h;

[0035] (3) evaporating most of the water from the suspension obtained after stirring in step (2) at 80° C., then drying at 100° C., and grinding to obtain a solid powder of titanium dioxide loaded with rare earth elements;

[0036] (4) The powder obtained in step (3) was calcined at 600° C. for 3 h in an air atmosphere and then cooled in the furnace to obtain a titanium dioxide-loaded rare earth element composite material.

[0037] Figure 1 is a transmission electron microscope (TEM) image of titanium dioxide without cerium loading. Figure 2 This is a transmission electron microscope image of titanium dioxide loaded with rare earth element cerium prepared in this embodiment. It can be seen that the morphology and size before and after loading are significantly different. There is loading of rare earth oxide particles. In addition, according to Figure 3The XRD pattern in the figure shows that the (110) crystal plane of titanium dioxide loaded with cerium element has an obvious shift, which proves that the cerium atoms have been successfully loaded into the titanium dioxide lattice. Due to the relatively large radius of the cerium ion, the XRD diffraction peak shifts to a low angle, which proves the successful preparation of the earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material.

[0038] Example 2:

[0039] A method for preparing a rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material for improving the UV resistance of the material comprises the following steps:

[0040] The preparation method is the same as that of Example 1, except that step (3) is changed to washing the suspension with water and alcohol in sequence, centrifuging it, drying it at 60°C for 8h, and grinding it to obtain a solid powder of titanium dioxide loaded with rare earth elements.

[0041] Example 3:

[0042] A method for preparing a rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material for improving the UV resistance of the material comprises the following steps:

[0043] The preparation method is the same as that of Example 2, except that the mass of cerium sulfate tetrahydrate in step (1) is changed to 216.39 mg. At this time, the loading amount of cerium element is 15% of the mass of titanium dioxide.

[0044] Example 4:

[0045] A method for preparing a rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material for improving the UV resistance of the material comprises the following steps:

[0046] The preparation method is the same as that of Example 2, except that the mass of cerium sulfate tetrahydrate in step (1) is changed to 288.52 mg. At this time, the loading amount of cerium element is 20% of the mass of titanium dioxide.

[0047] Example 5:

[0048] A method for preparing a rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material for improving the UV resistance of the material comprises the following steps:

[0049] The preparation method is the same as that of Example 2, except that the air atmosphere in step (4) is changed to an argon atmosphere.

[0050] Comparative Example 1:

[0051] A method for preparing titanium dioxide loaded with transition metals comprises the following steps:

[0052] The preparation method is the same as that of Example 1, except that the cerium sulfate tetrahydrate in step (1) is replaced by ferric nitrate nonahydrate.

[0053] Comparative Example 2:

[0054] A method for preparing titanium dioxide loaded with rare earth elements comprises the following steps:

[0055] (1) calcining titanium dioxide in a mixed gas of argon and hydrogen at 300°C for 2 hours to obtain defective titanium dioxide;

[0056] (2) suspending the defective titanium dioxide obtained in step (1) in 50 mL of deionized water and stirring for 15-30 minutes;

[0057] (3) dissolving cerium nitrate in deionized water, then dripping it into the suspension obtained in step (2), stirring at room temperature for 2 h, centrifuging, and drying to obtain a solid powder;

[0058] (4) The solid powder obtained in step (3) is calcined at 200° C. for 2 h in a mixed gas of argon and hydrogen to obtain a titanium dioxide-loaded rare earth metal material.

[0059] Comparative Example 3:

[0060] A method for preparing titanium dioxide loaded with rare earth metals comprises the following steps:

[0061] The preparation method is the same as that of Comparative Example 2, except that the cerium nitrate in step (3) is replaced by lanthanum nitrate.

[0062] Test example:

[0063] The titanium dioxide-loaded composite materials obtained in Examples 1-5 and Comparative Examples 1-3, as well as blank PET fibers, blank titanium dioxide, and titanium dioxide-loaded composite materials were physically mixed with PET fibers (the mixing mass was titanium dioxide-loaded composite material: PET fiber = 1:50) to obtain the materials for UV resistance testing. The test items and methods are as follows:

[0064] The UV transmittance of the above samples was tested using solid UV diffuse reflectance. The solid powder was evenly spread on a barium sulfate substrate for testing, and the test scanning range was 200-800nm. The wavelength-transmittance coefficient of different samples is shown in the figure below. Figure 4 shown.

[0065] Figure 4 The wavelength-transmittance graph of titanium dioxide loaded with different elements and physically mixed with PET is shown in the figure. The results show that the anti-ultraviolet performance UPF is calculated based on the curve in the figure.

[0066] In the figure, PET: blank PET fiber; La-TiO2-PET: physical mixing of comparative example 3+PET fiber, TiO2: blank titanium dioxide; evaporated Ce-TiO2: Example 1; 10% Ce-TiO2: Example 2; 15% Ce-TiO2: Example 3; 20% Ce-TiO2: Example 4; Fe-TiO2: Comparative Example 1; Ce-TiO2-PET: Example 2+PET fiber; argon: Example 5; vacancy calcination method loading: Comparative Example 2.

[0067] UPF (Ultraviolet Protection Factor) value: Each sample was tested according to the GB / T 18830-2009 test standard to calculate the UPF. The results are shown in Table 1 below.

[0068] Table 1 UPF values of samples

[0069] sample UPF value Example 1 15.08 Example 2 14.83 Example 3 15.56 Example 4 16.37 Example 5 12.83 Comparative Example 1 11.51 Comparative Example 2 6.13 Comparative Example 3 6.83 Blank titanium dioxide 6.65 Blank PET fiber 4.44 Example 2+PET fiber 12.37

[0070] According to the data in Table 1, compared with the comparative example and unloaded titanium dioxide, the rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material prepared in the embodiment of the present invention has significant anti-ultraviolet performance. At the same time, the rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material prepared in the present invention can significantly improve the UPF value of the PET fiber and significantly improve the anti-ultraviolet performance of the PET fiber by simply mixing with the PET fiber by physical mixing. The rare earth element cerium-loaded titanium dioxide prepared in the present invention has broad application prospects and feasibility in the production process of sunscreen fabrics.

[0071] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material for improving the UV resistance of the material, characterized in that: The following steps are involved: First, titanium dioxide is added to a cerium metal salt solution and stirred to obtain a suspension, then the solvent is removed and the solution is dried to obtain a solid powder, and finally the obtained solid powder is calcined at a high temperature to obtain the product.

2. The method for preparing a rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material for improving the UV resistance of the material according to claim 1, characterized in that: The cerium metal salt includes cerium sulfate or cerium nitrate.

3. The method for preparing a rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material for improving the UV resistance of the material according to claim 1, characterized in that: The concentration of the cerium metal salt solution is 10-100 mg / mL.

4. The method for preparing a rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material for improving the UV resistance of the material according to claim 1, characterized in that: The mass of the cerium element is 10-20% of the mass fraction of titanium dioxide.

5. The method for preparing a rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material for improving the UV resistance of the material according to claim 1, characterized in that: The stirring time is 2-4 hours, and the stirring speed is 200-1000 rpm.

6. The preparation of the rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material for improving the UV resistance of the material according to claim 1, characterized in that: The method for removing the solvent is water evaporation or centrifugal filtration; the temperature for evaporating water is 60-100°C, and the temperature for drying is 60-120°C.

7. The method for preparing a rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material for improving the UV resistance of the material according to claim 1, characterized in that: The high-temperature calcination temperature is 500-700° C. and the time is 2-4 hours.

8. A rare earth oxide nanoparticle-rare earth single atom / titanium dioxide composite material for improving the UV resistance of the material, characterized in that: The method is prepared according to any one of claims 1 to 7.

9. Use of the rare earth oxide nanoparticles-rare earth single atom / titanium dioxide composite material for improving the UV resistance of materials as claimed in claim 8 in improving the UV resistance of fiber materials.

Images