Titanium dioxide micromorphs, methods of making and uses thereof

Abstract

The application provides a titanium dioxide microwhisker, a preparation method and an application. The titanium dioxide microwhisker is prepared by the following method: (1) providing a titanium sol solution; (2) adding titanium dioxide nanoparticles into an alcohol solution of sodium dodecyl benzene sulfonate to obtain a titanium dioxide solution; (3) mixing the titanium sol solution and the titanium dioxide solution to obtain an electrostatic spraying solution; and (4) electrostatically spraying the electrostatic spraying solution, collecting the product and drying to obtain the titanium dioxide microwhisker. The obtained titanium dioxide microwhisker has a microscale size and a large specific surface area, and the preparation method is simple and can be used for industrial production in large quantities.

Description

Technical Field

[0001] This invention relates to the field of materials, specifically to a method for preparing titanium dioxide microfiber whiskers, the prepared titanium dioxide microfiber whiskers, and their uses, particularly in the fields of electrospinning / spraying, nanomaterials, and photoelectrocatalysis. Background Technology

[0002] Semiconductor photocatalytic materials can convert light energy into chemical energy when irradiated with light, promoting the decomposition of organic matter into carbon dioxide and water. They are substances that do not change themselves when irradiated with light, but can promote chemical reactions.

[0003] Among numerous semiconductor photocatalysts, anatase TiO2 has become the most widely used semiconductor photocatalyst due to its stable chemical properties, strong redox properties, corrosion resistance, non-toxicity, and low cost. TiO2 as a photocatalyst has the following advantages: 1. It converts solar energy into chemical energy for utilization. 2. It has a fast degradation rate; the ·OH generated by photoexcitation holes is a strong oxidizing free radical, which can successfully decompose most organic matter, including recalcitrant organic matter, in a short time. 3. It exhibits non-selective degradation, capable of degrading almost any organic pollutant. 4. It possesses high stability, resistance to photocorrosion, and non-toxicity, and does not generate secondary pollution during the treatment process; organic pollutants can be oxidized and degraded into CO2 and H2O, which are non-toxic to humans. Because TiO2 photocatalysts can produce antibacterial, deodorizing, oil-decomposing, mildew- and algae-preventing, and air-purifying effects under sunlight or indoor fluorescent light, they are attracting increasing attention.

[0004] On the other hand, titanium dioxide at the micrometer scale and above is certified by the US FDA as a food and additive, and its use is very safe. Nanoscale materials, however, have greater uncertainties regarding biosafety in use, and safety certification will take time. Therefore, in terms of practical application, micrometer-sized titanium dioxide is theoretically more reassuring than nanoscale titanium dioxide.

[0005] To address this problem, combining nanoscale materials into large-scale micron-sized materials is an effective solution. However, this approach often leads to the aggregation of nanomaterials, resulting in a loss of the original large specific surface area. Therefore, further improvements are needed in the preparation of micron-sized titanium dioxide materials. Summary of the Invention

[0006] The present invention aims to at least partially solve one of the technical problems in the related art.

[0007] Specifically, the present invention provides the following technical solution:

[0008] A first aspect of the present invention provides a method for preparing titanium dioxide microfiber whiskers, comprising:

[0009] (1) Provide titanium sol solution;

[0010] (2) Add titanium dioxide nanoparticles to an alcoholic solution of sodium dodecylbenzenesulfonate to obtain a titanium dioxide solution;

[0011] (3) The titanium sol solution and the titanium dioxide alcohol solution are mixed to obtain an electrostatic spray liquid;

[0012] (4) Electrostatic spraying is performed on the electrostatic spray liquid, the product is collected, and the titanium dioxide micron whiskers are obtained after drying.

[0013] This invention uses titanium dioxide nanoparticles as the framework material, titanium sol as the binder, and specific anionic surfactants to adjust the electrical properties and viscosity of the solution. Finally, the desired titanium dioxide microfiber material is obtained through electrostatic spraying. The preparation method provided by this invention is simple, can be mass-produced, and is beneficial for industrial production and application. The obtained titanium dioxide microfiber structure has micron-sized dimensions and a large specific surface area, showing good prospects for practical applications.

[0014] According to embodiments of the present invention, the method for preparing titanium dioxide microfiber whiskers described above may further include the following technical features:

[0015] In some embodiments of the present invention, the voltage of the electrostatic spray in step (4) is 20 to 25 kV.

[0016] In some embodiments of the present invention, step (4) further includes:

[0017] (4-1) Adjust the room temperature to 16 degrees Celsius and use a syringe to draw up the predetermined amount of electrostatic spray liquid;

[0018] (4-2) Install the syringe on the injection pump, adjust the injection rate to 0.3-0.5 mL / h, and adjust the distance between the rolling receiver and the needle to 25-30 cm;

[0019] (4-3) Adjust the voltage to 20-25kV, perform electrostatic spraying, collect the product, and dry it to obtain the titanium dioxide micron whiskers.

[0020] In some embodiments of the present invention, the alcoholic solution of sodium dodecylbenzenesulfonate is an anhydrous ethanol solution of sodium dodecylbenzenesulfonate with a concentration of 3.5 to 8 mmol / L.

[0021] In some embodiments of the present invention, the volume ratio of the added titanium dioxide nanoparticles to the alcoholic solution of sodium dodecylbenzenesulfonate is (0.3-0.5 g): (10-20 mL).

[0022] In some embodiments of the present invention, the titanium sol solution in step (1) is prepared by the following method:

[0023] (1-1) Tetrabutyl titanate was added to anhydrous ethanol, and then glacial acetic acid was added to obtain the first solution;

[0024] (1-2) Add glacial acetic acid and ultrapure water to anhydrous ethanol to obtain a second solution;

[0025] (1-3) The first solution is added dropwise to the second solution to obtain the titanium sol solution.

[0026] In some embodiments of the present invention, the volume ratio of tetrabutyl titanate, anhydrous ethanol and glacial acetic acid in step (1-1) is (2.5-5 mL): (5-15 mL): 3 mL.

[0027] In some embodiments of the present invention, the volume ratio of glacial acetic acid, ultrapure water and anhydrous ethanol in steps (1-2) is (2.5-5 mL): 1 mL: (8-10 mL).

[0028] In some embodiments of the present invention, the dropping rate in step (1-3) is 0.07-0.12 mL / min; step (1-3) further includes: after the dropping is completed, stirring is continued for 3-5 hours.

[0029] A second aspect of the present invention provides a titanium dioxide microfiber whisker, obtained according to any of the preparation methods described in the first aspect.

[0030] The third aspect of the present invention provides the use of titanium dioxide microfibers in the fields of electrospinning / spraying and photoelectrocatalysis, wherein the titanium dioxide microfibers are the titanium dioxide microfibers described in the second aspect above.

[0031] The beneficial effects achieved by this invention are as follows:

[0032] (1) The present invention can obtain titanium dioxide micron whisker structure in one step, that is, by mixing titanium sol and titanium dioxide nanoparticles and using sodium dodecylbenzene sulfonate, titanium dioxide micron whisker structure can be quickly prepared by electrostatic spraying.

[0033] (2) The titanium dioxide micron-sized particles obtained by the method described in this invention have micron-sized dimensions and large specific surface area, and have good safety and practical application prospects.

[0034] (3) The preparation method provided is simple and can be mass-produced, which is conducive to industrial production and application. Attached Figure Description

[0035] Figure 1 A scanning electron microscope (SEM) image of titanium dioxide microfiber whiskers provided according to Example 1 of the present invention.

[0036] Figure 2 A scanning electron microscope (SEM) image of titanium dioxide microfiber whiskers provided according to Example 1 of the present invention.

[0037] Figure 3 This is a scanning electron microscope image of the product obtained using the cationic surfactant CTAB.

[0038] Figure 4 This is a scanning electron microscope image of the product obtained using the nonionic surfactant OP-10.

[0039] Figure 5 These are scanning electron microscope images of the products obtained using the anionic surfactant SDS. Detailed Implementation

[0040] The embodiments of the present invention are described in detail below. Examples of the embodiments are shown in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and intended to explain the present invention, but should not be construed as limiting the present invention.

[0041] This invention provides a method for preparing titanium dioxide microfiber whiskers, comprising:

[0042] (1) Provide titanium sol solution;

[0043] (2) Add titanium dioxide nanoparticles to an alcoholic solution of sodium dodecylbenzenesulfonate to obtain a titanium dioxide solution;

[0044] (3) The titanium sol solution and the titanium dioxide alcohol solution are mixed to obtain an electrostatic spray liquid;

[0045] (4) Electrostatic spraying is performed on the electrostatic spray liquid, the product is collected, and the titanium dioxide micron whiskers are obtained after drying.

[0046] This invention uses titanium dioxide nanoparticles as the framework material, titanium sol as the binder, and specific anionic surfactants to adjust the electrical properties and viscosity of the solution. Finally, the desired titanium dioxide microfiber material is obtained through electrostatic spraying. The preparation method provided by this invention is simple, can be mass-produced, and is beneficial for industrial production and application. The obtained titanium dioxide microfiber structure has micron-sized dimensions and a large specific surface area, showing good prospects for practical applications. During the research process, the inventors discovered that using other anionic surfactants to adjust the electrical properties and viscosity of the solution was not effective. For example, it was found that without any surfactant, or with cationic or nonionic surfactants, conventional spherical or filamentous products were generally obtained after electrostatic spraying. For example, when using the cationic surfactant CTAB, filamentous products were observed (e.g., ...). Figure 3 (as shown); when using the nonionic surfactant OP-10, a particulate product is produced (as shown). Figure 4 As shown); when using the anionic surfactant SDS, structures that are not easily formed (such as...) Figure 5 (As shown).

[0047] In some embodiments of the present invention, the voltage of electrostatic spraying in step (4) is 20-25 kV. During the research, it was found that when the voltage of electrostatic spraying is too high, it will affect the quality of the formed titanium dioxide microfibers; when the voltage of electrostatic spraying is too low, it will affect the size of the formed titanium dioxide microfibers, or even prevent electrostatic spraying.

[0048] According to a specific embodiment of the present invention, step (4) further includes:

[0049] (4-1) Adjust the room temperature to 16 degrees Celsius and use a syringe to draw up the predetermined amount of electrostatic spray liquid;

[0050] (4-2) Install the syringe on the injection pump, adjust the injection rate to 0.3-0.5 mL / h, and adjust the distance between the rolling receiver and the needle to 25-30 cm;

[0051] (4-3) Adjust the voltage to 20-25kV, perform electrostatic spraying, collect the product, and dry it to obtain the titanium dioxide micron whiskers.

[0052] In some embodiments of the present invention, the alcohol solution of sodium dodecylbenzenesulfonate is an anhydrous ethanol solution of sodium dodecylbenzenesulfonate with a concentration of 3.5–8 mmol / L. During the research, it was found that when the concentration was too high, the sprayed product was essentially a paste, lacking shape, which severely affected the product quality; while when the concentration was too low, the product tended to sphericalize, also affecting the quality of the formed titanium dioxide microfibers.

[0053] According to a specific embodiment, the volume ratio of the added titanium dioxide nanoparticles to the alcoholic solution of sodium dodecylbenzenesulfonate is (0.3-0.5g):(10-20mL).

[0054] In some embodiments of the present invention, the titanium sol solution in step (1) is prepared by the following method:

[0055] (1-1) Tetrabutyl titanate was added to anhydrous ethanol, and then glacial acetic acid was added to obtain the first solution;

[0056] (1-2) Add glacial acetic acid and ultrapure water to anhydrous ethanol to obtain a second solution;

[0057] (1-3) The first solution is added dropwise to the second solution to obtain the titanium sol solution.

[0058] In some embodiments of the present invention, the volume ratio of tetrabutyl titanate, anhydrous ethanol and glacial acetic acid in step (1-1) is (2.5-5 mL): (5-15 mL): 3 mL.

[0059] In some embodiments of the present invention, the volume ratio of glacial acetic acid, ultrapure water and anhydrous ethanol in steps (1-2) is (2.5-5 mL): 1 mL: (8-10 mL).

[0060] In some embodiments of the present invention, the dropping rate in step (1-3) is 0.07-0.12 mL / min; step (1-3) further includes: after the dropping is completed, stirring is continued for 3-5 hours.

[0061] The present invention also provides a titanium dioxide microfiber whisker, obtained according to any of the preparation methods described above.

[0062] The present invention also provides the use of titanium dioxide microfibers in electrospinning / spraying and photoelectrocatalysis, wherein the titanium dioxide microfibers are the titanium dioxide microfibers described above.

[0063] The specific embodiments of the present invention will be described below. It should be noted that these embodiments are only for the convenience of those skilled in the art and should not be considered as limitations on the scope of protection of the present invention. Unless otherwise specified, the reagents used in the embodiments can be obtained commercially.

[0064] Example 1

[0065] Example 1 provides a method for preparing titanium dioxide microfiber whiskers, comprising:

[0066] (1) Preparation of titanium sol solution:

[0067] 1) Add 5 mL of tetrabutyl titanate to 15 mL of anhydrous ethanol, stir for 5 minutes, then add 3 mL of glacial acetic acid and stir until homogeneous to obtain the first solution.

[0068] 2) Add 4 mL of glacial acetic acid and 1 mL of ultrapure water to 8 mL of anhydrous ethanol, stir for 10-30 minutes to obtain the second solution;

[0069] 3) Add the first solution dropwise to the second solution while stirring, at a rate of 0.1 mL / min.

[0070] 4) After the addition is complete, continue stirring for 4 hours.

[0071] (2) Preparation of electrostatic spray liquid:

[0072] 1) Dissolve sodium dodecylbenzenesulfonate (SDBS) in anhydrous ethanol solution to a concentration of 6 mmol / L to obtain an alcoholic solution of sodium dodecylbenzenesulfonate.

[0073] 2) Add 0.4g of P25 (commercially available titanium dioxide nanoparticles) to 16mL of an alcoholic solution of sodium dodecylbenzenesulfonate and stir for 20 minutes to obtain an alcoholic solution of titanium dioxide.

[0074] 3) Add the titanium sol solution prepared above to the alcohol solution of titanium dioxide and stir for 40 minutes.

[0075] (3) Preparation of titanium dioxide by electrostatic spraying:

[0076] 1) Adjust the room temperature to 16℃;

[0077] 2) Draw a certain amount of electrostatic spray liquid using a disposable medical syringe;

[0078] 3) Place the syringe on the dual-channel injection pump and adjust the injection rate to 0.4 mL / h;

[0079] 4) Adjust the distance between the rolling receiver and the needle to 30cm;

[0080] 5) Set the high-voltage power supply to 25kV for electrostatic spraying;

[0081] 6) After the experiment, collect the product from the receiver and dry it at 100 degrees Celsius for 12 hours to obtain titanium dioxide microfiber whiskers.

[0082] Scanning electron microscope images of the prepared titanium dioxide microfiber whiskers are as follows: Figure 1 and Figure 2 As shown. Figure 1 and Figure 2 These are photographs taken at different resolutions. From Figure 1 and Figure 2The results show that, according to the method described in this invention, whisker-like aggregates with a length of approximately 10 micrometers were obtained. The diameter of a single whisker is on the order of approximately 100 nanometers. This structure exhibits a unique structure with a distinct binding point at one end and a whisker-like dispersion at the other end, suggesting that this structure likely formed a dandelion-like structure during the electrostatic spraying process. The resulting titanium dioxide microwhiskers are of good quality and are at the micrometer scale.

[0083] In the description of this specification, references to terms such as "one embodiment," "some embodiments," "example," "detailed implementation," or "some implementations," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example.

[0084] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.

Claims

1. A method for preparing titanium dioxide micron-sized whiskers, characterized in that, include: (1) Provide titanium sol solution; (2) Add titanium dioxide nanoparticles to an alcoholic solution of sodium dodecylbenzenesulfonate to obtain an alcoholic solution of titanium dioxide; (3) The titanium sol solution and the titanium dioxide alcohol solution are mixed to obtain an electrostatic spray liquid; (4) Electrostatic spraying is performed on the electrostatic spray liquid, the product is collected, and the titanium dioxide micron whiskers are obtained after drying; Step (4) further includes: (4-1) Adjust the room temperature to 16 degrees Celsius and use a syringe to draw up the predetermined amount of electrostatic spray liquid; (4-2) Install the syringe on the injection pump, adjust the injection rate to 0.3-0.5 mL / h, and adjust the distance between the rolling receiver and the needle to 25-30 cm; (4-3) Adjust the voltage to 20-25kV, perform electrostatic spraying, collect the product, and dry it to obtain the titanium dioxide micron whiskers; The alcoholic solution of sodium dodecylbenzenesulfonate is an anhydrous ethanol solution of sodium dodecylbenzenesulfonate with a concentration of 3.5~8 mmol / L.

2. The preparation method according to claim 1, characterized in that, The volume ratio of the added titanium dioxide nanoparticles to the alcoholic solution of sodium dodecylbenzenesulfonate is (0.3~0.5g):(10~20mL).

3. The preparation method according to claim 1, characterized in that, The titanium sol solution described in step (1) is prepared by the following method: (1-1) Tetrabutyl titanate was added to anhydrous ethanol, and then glacial acetic acid was added to obtain the first solution; (1-2) Add glacial acetic acid and ultrapure water to anhydrous ethanol to obtain a second solution; (1-3) The first solution is added dropwise to the second solution to obtain the titanium sol solution.

4. The preparation method according to claim 3, characterized in that, In step (1-1), the volume ratio of tetrabutyl titanate, anhydrous ethanol, and glacial acetic acid is (2.5~5mL):(5~15mL):3mL; The volume ratio of glacial acetic acid, ultrapure water and anhydrous ethanol in steps (1-2) is (2.5~5mL):1mL:(8~10mL).

5. The preparation method according to claim 3, characterized in that, The dropping rate described in steps (1-3) is 0.07-0.12 mL / min; Further steps include: after the addition is complete, continue stirring for 3-5 hours.

6. A titanium dioxide microfiber whisker, characterized in that, Obtained by the preparation method according to any one of claims 1 to 5.

7. The use of titanium dioxide microfibers in the field of photoelectrocatalysis, wherein the titanium dioxide microfibers are those described in claim 6.

Images