Method for rapidly preparing rutile-phase titanium dioxide hollow nanoparticles

Abstract

The invention discloses a method for rapidly preparing rutile-phase titanium dioxide hollow nanoparticles, which comprises the following steps: 1) dispersing silicon dioxide nanoparticles into absolute ethyl alcohol, and adding a potassium chloride aqueous solution to prepare a raw material solution A; 2) adding tetrabutyl titanate into absolute ethyl alcohol to prepare a raw material solution B; (3) simultaneously pumping the raw material solution A and the raw material solution B into a supergravity rotating packed bed reactor for hydrolysis reaction to obtain SiO2 and TiO2 composite particles; 4) placing the SiO2-coated TiO2 composite particles in a muffle furnace for high-temperature calcination; and 5) placing the composite particles in a strong alkali solution for etching, centrifuging, washing and drying to obtain a product. The hollow structure of the final product is obvious; the titanium dioxide hollow nanoparticles are rutile phase, and the particle size is 500-600nm; the technical process is simple, no organic solvent is needed in the preparation process, and the raw materials are low in price and easy to obtain.

Description

Technical Field

[0001] The present invention relates to the technical field of nano material preparation, and more specifically, to a method for rapidly preparing rutile phase titanium dioxide hollow nano particles. Background Art

[0002] Titanium dioxide is an environmentally friendly optical semiconductor material. Due to its excellent structure, optical and chemical properties, it can convert light energy into electrical energy or chemical energy under mild conditions, and has a wide range of application value in many fields. In recent years, the research and application of titanium dioxide in the agricultural field has gradually attracted people's attention, and it has good application prospects in pesticide degradation, crop disease prevention and control, pesticide residue detection, water purification, etc.

[0003] Lhomme et al (LL, SB, D W. Photocatalytic degradation of pesticides inpurewater and a commercial agricultural solution on TiO 2 Coated media. [J]. Chemosphere, 2008, 70 (3): 381-6.) studied the photocatalytic degradation effect of titanium dioxide on two commercial pesticides, chloranil and cyclanazole, in pure water. Under the photocatalytic action of titanium dioxide, the degradation rate reached 70%-80% after 5 hours of illumination, and it was completely degraded after 15-20 hours. Compared with the degradation of pesticides by photolysis (without titanium dioxide), the time required for pesticide degradation was greatly shortened. Chen et al. (Chen SF, Zhao MY, Tao YW. Photocatalytic Degradation of Organophosphoros Pesticides Using TiO 2 Supported on Fiberglass.[J].Microchemical Journal,1996.0076.) Titanium dioxide was loaded onto glass fiber to study the feasibility of photocatalytic degradation of organophosphorus pesticides. The results showed that after 3 hours of illumination, the organophosphorus pesticides could be completely photocatalytically degraded.

[0004] Compared with conventional materials, hollow materials have the advantages of low density, large specific surface area, excellent light absorption efficiency and surface permeability due to their unique hollow structure, so they have attracted extensive attention from researchers. The preparation methods of hollow titanium dioxide nanoparticles mainly include template method and self-template method. Among them, the template method is an earlier studied and widely used method for preparing hollow structures. The preparation process is simple and can accurately control the morphology and size of the hollow sphere structure.

[0005] Ren et al. (Ren H, Sun J, YuR, et al. Controllable Synthesis of Mesostructures from TiO 2 Hollow to Porous Nano Spheres with Superior Rrate Performance for Lithium Ion Batteries[J].Chemical ence, 2015, 7(1):793-798.) Using carbon spheres as templates, TiCl 4 The aqueous solution was used as a titanium source precursor, and TiO composed of ultra-small nanoparticles was finally prepared by a hydrothermal method. 2 Hollow nanospheres.

[0006] Joo et al. (Joo BJ, Zhang Q, Lee I, et al. Mesoporous Anatase Titania Hollow Nanostructures though Silica-Protected Calcination [J]. Advanced Functional Materials, 2012, 22 (1): 166-174.) used silicon dioxide as a template, generated titanium dioxide by a sol-gel method for coating, and prepared anatase-type titanium dioxide hollow particles by a protective calcination method, thereby improving their photocatalytic performance. Under this method, the crystal form of titanium dioxide is inhibited from further transforming to large grains, limiting its transformation from anatase to rutile.

[0007] Among the above preparation methods, the hydrothermal method has harsh operating conditions, long reaction time and certain dangers, while the general sol-gel method also requires a long reaction time in a stirred tank reactor to achieve titanium dioxide coating, which is inefficient and difficult to scale up. Therefore, in view of the shortcomings of the existing methods, a method is needed that has mild conditions, low energy consumption, high efficiency and can quickly prepare rutile phase titanium dioxide hollow nanoparticles. Summary of the invention

[0008] The technical problem to be solved by the present invention is to provide a method for rapidly preparing hollow nanoparticles of titanium dioxide in the rutile phase. The present invention effectively shortens the time required for the preparation process, and the hollow structure of the final product is obvious, and the integrity and sphericity are both excellent; the hollow nanoparticles of titanium dioxide prepared by the present invention are in the rutile phase, and the particle size is 500-600nm; the process of the present invention is simple, no organic solvent is required in the preparation process, and the raw materials are cheap and easy to obtain.

[0009] In order to solve the above technical problems, the technical solutions adopted by the invention are as follows:

[0010] A method for rapidly preparing rutile phase titanium dioxide hollow nanoparticles comprises the following steps:

[0011] 1) dispersing silicon dioxide nanoparticles in anhydrous ethanol, adding potassium chloride aqueous solution to prepare raw material solution A;

[0012] 2) adding tetrabutyl titanate into anhydrous ethanol to prepare raw material liquid B;

[0013] 3) The raw material liquid A and the raw material liquid B are simultaneously pumped into the high gravity rotating packed bed reactor for hydrolysis reaction. After the reaction, the reaction liquid is taken out, and SiO is obtained after centrifugation, washing and drying. 2 @TiO 2 Composite particles;

[0014] 4) SiO 2 @TiO 2 The composite particles are placed in a muffle furnace and calcined at high temperature to convert titanium dioxide into a rutile phase;

[0015] 5) The calcined SiO 2 @TiO 2 The composite particles are placed in a strong alkaline solution to etch the silicon dioxide particles, and after the etching is completed, the particles are centrifuged, washed, and dried to obtain rutile phase titanium dioxide nano hollow nano particles.

[0016] Preferably, in step 1), the silica nanoparticles are spherical particles with a particle size of 400-500 nm; the concentration of the silica nanoparticles in the raw material solution A is 0.25-0.40 wt %; more preferably, the concentration of the silica nanoparticles in the raw material solution A is 0.34 wt %.

[0017] Preferably, in step 1), the concentration of the potassium chloride aqueous solution is 0.006-0.010 mol / L; more preferably, the concentration of the potassium chloride aqueous solution is 0.008 mol / L.

[0018] Preferably, in step 1), the amount of the potassium chloride aqueous solution is 0.5%-0.8% by volume of the anhydrous ethanol; more preferably, the amount of the potassium chloride aqueous solution is 0.65% by volume of the anhydrous ethanol.

[0019] Preferably, in step 2), the concentration of tetrabutyl titanate in the raw material solution B is 5-7.5wt%; more preferably, the concentration of tetrabutyl titanate in the raw material solution B is 6.3wt%.

[0020] Preferably, in step 3), the rotor speed of the high gravity rotating packed bed reactor is 1000-1400 rpm; the temperature of the hydrolysis reaction in the high gravity rotating packed bed reactor is 20-25° C.; and the time is 10-20 min.

[0021] Preferably, in step 3), the centrifugal speed is 10000-12000 rpm; the washing is 3-5 times with anhydrous ethanol; the drying temperature is 55-65°C and the drying time is 8-12h.

[0022] Preferably, in step 4), the high temperature calcination is carried out at a temperature of 750-850° C. and for a time of 3-5 hours.

[0023] Preferably, in step 5), the strong base is sodium hydroxide, and the concentration of the strong base solution is 0.4-0.6 mol / L; more preferably, the concentration of the strong base solution is 0.5 mol / L.

[0024] Preferably, in step 5), the etching temperature is 70-90° C., and the holding time is 2-3 h; more preferably, the etching temperature is 80° C., and the holding time is 3 h.

[0025] Preferably, in step 5), the centrifugal speed is 10000-12000 rpm, the washing is 3-5 times with deionized water, the drying temperature is 55-65° C., and the drying time is 8-12 h.

[0026] Any range described in the present invention includes the end value and any numerical value between the end values ​​and any sub-range formed by the end value or any numerical value between the end values.

[0027] Unless otherwise specified, all raw materials in the present invention can be purchased from the market, and the equipment used in the present invention can adopt conventional equipment in the relevant field or refer to the existing technology in the relevant field.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] 1) The existing method for preparing hollow titanium dioxide nanoparticles mainly uses a stirred tank reactor, and the titanium source needs to undergo a long hydrolysis reaction before it can be completely coated on the template surface to obtain a complete hollow structure. The present invention uses a high-gravity rotating packed bed reactor instead of a stirred tank reactor, which greatly shortens the time required for hydrolysis and achieves rapid preparation of hollow titanium dioxide nanoparticles. The final product has a distinct hollow structure, and its integrity and sphericity are both excellent;

[0030] 2) The hollow titanium dioxide nanoparticles prepared by the present invention are in rutile phase, and the particle size is 500-600nm;

[0031] 3) The process of the present invention is simple, no organic solvent is required in the preparation process, and the raw materials are cheap and easily available, the production efficiency is high, and scale-up production can be carried out. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] The specific embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.

[0033] Figure 1 TEM image of the rutile phase titanium dioxide hollow nanoparticles prepared in Example 1;

[0034] Figure 2 is the XRD pattern of the rutile phase titanium dioxide hollow nanoparticles prepared in Example 1;

[0035] Figure 3 TEM image of the rutile phase titanium dioxide hollow nanoparticles prepared in Example 2;

[0036] Figure 4 TEM image of the rutile phase titanium dioxide hollow nanoparticles prepared in Example 3;

[0037] Figure 5 TEM image of the rutile phase titanium dioxide hollow nanoparticles prepared in Example 5;

[0038] Figure 6 is the XRD pattern of the rutile phase titanium dioxide hollow nanoparticles prepared in Example 6;

[0039] Figure 7 is a SEM image of the rutile phase titanium dioxide hollow nanoparticles prepared in Comparative Example 1;

[0040] Figure 8 is a SEM image of the rutile phase titanium dioxide hollow nanoparticles prepared in Comparative Example 2;

[0041] Fig. 9 is a SEM image of the rutile phase titanium dioxide hollow nanoparticles prepared in Comparative Example 3;

[0042] Fig.10 is a SEM image of the rutile phase titanium dioxide hollow nanoparticles prepared in Comparative Example 4;

[0043] Fig.11 is the XRD pattern of the titanium dioxide hollow nanoparticles prepared in Comparative Example 5;

[0044] Fig.12 This is the SEM image of the rutile phase titanium dioxide hollow nanoparticles prepared in Comparative Example 6. DETAILED DESCRIPTION

[0045] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and accompanying drawings. Similar components in the accompanying drawings are represented by the same reference numerals. It should be understood by those skilled in the art that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the scope of protection of the present invention.

[0046] For the convenience of description, the descriptions of "first", "second", etc. in the present invention are only set for descriptive purposes and cannot be understood as indicating or suggesting their relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In addition, the technical solutions between the various implementation methods can be combined with each other, but they must be based on the ability of ordinary technicians in the field to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such a combination of technical solutions does not exist and is not within the scope of protection required by the present invention.

[0047] As one aspect of the present invention, a method for rapidly preparing rutile phase titanium dioxide hollow nanoparticles comprises the following steps:

[0048] 1) dispersing silicon dioxide nanoparticles in anhydrous ethanol, adding potassium chloride aqueous solution to prepare raw material solution A;

[0049] 2) adding tetrabutyl titanate into anhydrous ethanol to prepare raw material liquid B;

[0050] 3) The raw material liquid A and the raw material liquid B are simultaneously pumped into the high gravity rotating packed bed reactor for hydrolysis reaction. After the reaction, the reaction liquid is taken out, and SiO is obtained after centrifugation, washing and drying. 2 @TiO 2 Composite particles;

[0051] 4) SiO 2 @TiO 2 The composite particles are placed in a muffle furnace and calcined at high temperature to convert titanium dioxide into a rutile phase;

[0052] 5) The calcined SiO 2 @TiO 2 The composite particles are placed in a strong alkaline solution to etch the silicon dioxide particles, and after the etching is completed, the particles are centrifuged, washed, and dried to obtain rutile phase titanium dioxide nano hollow nano particles.

[0053] In certain embodiments of the present invention, in step 1), the silica nanoparticles are spherical particles with a particle size of 400-500 nm; the concentration of the silica nanoparticles in the raw material solution A is 0.25-0.40 wt %; more preferably, the concentration of the silica nanoparticles in the raw material solution A is 0.34 wt %.

[0054] In certain embodiments of the present invention, in step 1), the concentration of the potassium chloride aqueous solution is 0.006-0.010 mol / L; more preferably, the concentration of the potassium chloride aqueous solution is 0.008 mol / L.

[0055] In certain embodiments of the present invention, in step 1), the amount of the potassium chloride aqueous solution is 0.5%-0.8% by volume of the anhydrous ethanol; more preferably, the amount of the potassium chloride aqueous solution is 0.65% by volume of the anhydrous ethanol.

[0056] In certain embodiments of the present invention, in step 2), the concentration of tetrabutyl titanate in the raw material solution B is 5-7.5 wt %; more preferably, the concentration of tetrabutyl titanate in the raw material solution B is 6.3 wt %.

[0057] In certain embodiments of the present invention, in step 3), the rotor speed of the high gravity rotating packed bed reactor is 1000-1400 rpm; the temperature of the hydrolysis reaction in the high gravity rotating packed bed reactor is 20-25° C.; and the time is 10-20 min.

[0058] In certain embodiments of the present invention, in step 3), the centrifugal speed is 10000-12000 rpm; the washing is 3-5 times of washing with anhydrous ethanol; the drying temperature is 55-65°C, and the drying time is 8-12h.

[0059] In certain embodiments of the present invention, in step 4), the high temperature calcination is carried out at a temperature of 750-850° C. and for a time of 3-5 h.

[0060] In certain embodiments of the present invention, in step 5), the strong base is sodium hydroxide, and the concentration of the strong base solution is 0.4-0.6 mol / L; more preferably, the concentration of the strong base solution is 0.5 mol / L.

[0061] In certain embodiments of the present invention, in step 5), the etching temperature is 70-90° C., and the holding time is 2-3 h; more preferably, the etching temperature is 80° C., and the holding time is 3 h.

[0062] In certain embodiments of the present invention, in step 5), the centrifugal speed is 10000-12000 rpm, the washing is 3-5 times with deionized water, the drying temperature is 55-65° C., and the drying time is 8-12 h.

[0063] Example 1

[0064] A method for rapidly preparing rutile phase titanium dioxide hollow nanoparticles comprises the following steps:

[0065] 1) Weigh 0.4 g of silica nanoparticles and disperse them in 150 mL of anhydrous ethanol, then weigh 1 mL of a 0.008 mol / L potassium chloride aqueous solution and add it to the dispersion, and obtain a raw material solution A after ultrasonic dispersion;

[0066] 2) 150 mL of anhydrous ethanol was weighed and placed in a beaker, and tetrabutyl titanate was weighed so that the solution concentration was 6.3 wt %, and added to the anhydrous ethanol, and stirred to make the solution uniform, to obtain raw material solution B;

[0067] 3) The raw material liquid A and the raw material liquid B were simultaneously pumped into the supergravity rotating packed bed reactor through the feed port via a peristaltic pump, and the rotor speed was set to 1200 rpm. After reacting in the reactor for 15 minutes, the reaction liquid was taken out, centrifuged at a speed of 11000 rpm, washed with anhydrous ethanol for 4 times, and then placed in a 65°C forced air drying oven for 8 hours to obtain SiO 2 @TiO 2 Composite particles;

[0068] 4) SiO 2 @TiO 2 The composite particles were placed in a muffle furnace, and the heating rate was set at 10 °C / min, and the temperature was raised to 850 °C and kept at this temperature for 4 h;

[0069] 5) Weigh a certain amount of sodium hydroxide and dissolve it in 400 mL of deionized water to prepare a 0.5 mol / L strong alkaline solution. 2 @TiO 2 The composite particles were placed in a strong alkaline solution, heated to 80°C, kept warm and stirred for 3 hours; after the reaction was completed, they were centrifuged at 11,000 rpm, washed with deionized water 4 times, and dried in a 65°C forced air drying oven for 8 hours to obtain rutile phase titanium dioxide hollow nanoparticles.

[0070] Figure 1 This is a TEM image of the rutile phase titanium dioxide hollow nanoparticles prepared in Example 1, with a particle size of 500-600 nm and a wall thickness of 40-60 nm.

[0071] Figure 2This is the XRD diagram of the rutile phase titanium dioxide hollow nanoparticles prepared in this Example 1. The titanium dioxide is converted into the rutile phase.

[0072] Example 2

[0073] Example 1 was repeated, except that the reaction time in the high gravity rotating packed bed reactor was adjusted to 10 min. The TEM image of the rutile phase titanium dioxide hollow nanoparticles was as follows: Figure 3 As shown, hollow particles with complete structure were prepared.

[0074] Example 3

[0075] Example 1 was repeated, except that the reaction time in the high gravity rotating packed bed reactor was adjusted to 20 min. The TEM image of the prepared particles is shown in FIG. Figure 4 As shown, complete hollow particles were successfully prepared, and their wall thickness increased to a certain extent.

[0076] Example 4

[0077] Example 1 was repeated, except that the rotor speed of the high gravity rotating packed bed reactor was adjusted to 1000 rpm. Under this condition, rutile phase titanium dioxide hollow nanoparticles with complete structure and clear cavity were prepared.

[0078] Example 5

[0079] Example 1 was repeated, except that the rotor speed of the high gravity rotating packed bed reactor was adjusted to 1400 rpm. The TEM image of the rutile phase titanium dioxide hollow nanoparticles is as follows: Figure 5 As shown, the structure of the hollow particles is complete and the wall thickness does not change significantly.

[0080] Example 6

[0081] Example 1 was repeated, except that SiO 2 @TiO 2 The calcination temperature of the composite particles in the muffle furnace was adjusted to 750°C, and the XRD characterization structure was as follows: Figure 6 As shown, most of the titanium dioxide is converted into the rutile phase, and only part of the anatase phase exists.

[0082] Comparative Example 1

[0083] Example 1 was repeated, except that the reaction time in the high gravity rotating packed bed reactor was adjusted to 5 min; the SEM image of the prepared particles was as follows: Figure 7 shown.

[0084] It can be seen that when the reaction time is 5 min, the breakage rate of titanium dioxide hollow nanoparticles increases significantly.

[0085] Comparative Example 2

[0086] Example 1 was repeated, except that the reaction time in the high gravity rotating packed bed reactor was adjusted to 25 min. The SEM image of the prepared particles is shown in FIG. Figure 8 shown.

[0087] It can be seen that when the reaction time is 25 min, under this condition, there is too much titanium dioxide accumulation in the shell of the titanium dioxide hollow nanoparticles and the sphericity is poor.

[0088] Comparative Example 3

[0089] Example 1 was repeated, except that the rotor speed of the high gravity rotating packed bed reactor was adjusted to 800 rpm. The SEM image of the prepared particles is shown in FIG. Fig. 9 shown.

[0090] It can be seen that when the rotor speed is 800 rpm, the breakage rate of titanium dioxide hollow nanoparticles increases significantly under this condition.

[0091] Comparative Example 4

[0092] Example 1 was repeated, except that the rotor speed of the high gravity rotating packed bed reactor was adjusted to 1600 rpm. The SEM image of the prepared particles is shown in FIG. Fig.10 shown.

[0093] It can be seen that when the rotor speed is 1600 rpm, the shell of the prepared titanium dioxide hollow nanoparticles becomes obviously thicker and the sphericity is poor.

[0094] Comparative Example 5

[0095] Repeat Example 1, except that SiO 2 @TiO 2 The calcination temperature of the composite particles in the muffle furnace was adjusted to 650°C. The XRD characterization of the prepared particles was as follows: Fig.11 shown.

[0096] It can be seen that when the calcination temperature is 650°C, titanium dioxide can only be converted into anatase phase, and only a very small part is converted into rutile phase.

[0097] Comparative Example 6

[0098] In order to study the effect of high gravity technology on the preparation of rutile phase titanium dioxide hollow nanoparticles, the experiment was carried out in a traditional stirred tank reactor. The other reaction conditions were the same as those in Example 1, except that a stirred tank reactor was used instead of a high gravity rotating packed bed reactor. After mixing the raw material liquid A and the raw material liquid B in a stirred tank reactor, the mixture was stirred at room temperature for 3 hours, and then subjected to subsequent calcination, etching and other treatment steps to obtain rutile phase titanium dioxide hollow nanoparticles. The experimental results are as follows: It can be seen from the SEM electron microscope (such as Fig.12 As shown in Figure 2, compared with the high-gravity reactor, the hollow nanoparticles obtained by the stirred tank reactor have a high breakage rate of the hollow structure and uneven wall thickness. In addition, the hydrolysis reaction time required in the stirred tank reactor is greatly increased, and the yield is lower than that of the high-gravity technology.

[0099] Obviously, the above embodiments of the present invention are merely examples for clearly explaining the present invention, and are not intended to limit the implementation methods of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is impossible to list all implementation methods here. Any obvious changes or modifications derived from the technical solution of the present invention are still within the scope of protection of the present invention.

Claims

1. A method for rapidly preparing rutile phase titanium dioxide hollow nanoparticles, characterized in that: The steps include: 1) dispersing silicon dioxide nanoparticles in anhydrous ethanol, adding potassium chloride aqueous solution to prepare raw material solution A; 2) adding tetrabutyl titanate into anhydrous ethanol to prepare raw material liquid B; 3) Pumping the raw material liquid A and the raw material liquid B into a high gravity rotating packed bed reactor at the same time for hydrolysis reaction, taking out the reaction liquid after the reaction, and obtaining SiO2@TiO2 composite particles after centrifugation, washing and drying; 4) placing the SiO2@TiO2 composite particles in a muffle furnace and calcining them at high temperature to convert titanium dioxide into a rutile phase; 5) placing the calcined SiO2@TiO2 composite particles in a strong alkaline solution to etch the silicon dioxide particles, and after the etching is completed, centrifuging, washing, and drying to obtain rutile phase titanium dioxide nano hollow nanoparticles.

2. The method for rapidly preparing rutile phase titanium dioxide hollow nanoparticles according to claim 1, characterized in that: In step 1), the silicon dioxide nanoparticles are spherical particles with a particle size of 400-500 nm; the concentration of the silicon dioxide nanoparticles in the raw material solution A is 0.25-0.40 wt %; more preferably, the concentration of the silicon dioxide nanoparticles in the raw material solution A is 0.34 wt %.

3. The method for rapidly preparing rutile phase titanium dioxide hollow nanoparticles according to claim 1, characterized in that: In step 1), the concentration of the potassium chloride aqueous solution is 0.006-0.010 mol / L; more preferably, the concentration of the potassium chloride aqueous solution is 0.008 mol / L.

4. The method for rapidly preparing rutile phase titanium dioxide hollow nanoparticles according to claim 1, characterized in that: In step 1), the amount of the potassium chloride aqueous solution is 0.5%-0.8% by volume of the anhydrous ethanol; more preferably, the amount of the potassium chloride aqueous solution is 0.65% by volume of the anhydrous ethanol.

5. The method for rapidly preparing rutile phase titanium dioxide hollow nanoparticles according to claim 1, characterized in that: In step 2), the concentration of tetrabutyl titanate in the raw material solution B is 5-7.5wt%; more preferably, the concentration of tetrabutyl titanate in the raw material solution B is 6.3wt%.

6. The method for rapidly preparing rutile phase titanium dioxide hollow nanoparticles according to claim 1, characterized in that: In step 3), the rotor speed of the high gravity rotating packed bed reactor is 1000-1400 rpm; the temperature of the hydrolysis reaction in the high gravity rotating packed bed reactor is 20-25° C.; and the time is 10-20 min.

7. The method for rapidly preparing rutile phase titanium dioxide hollow nanoparticles according to claim 1, characterized in that: In step 3), the centrifugal speed is 10000-12000 rpm; the washing is 3-5 times with anhydrous ethanol; the drying temperature is 55-65° C. and the drying time is 8-12 hours.

8. The method for rapidly preparing rutile phase titanium dioxide hollow nanoparticles according to claim 1, characterized in that: In step 4), the high temperature calcination temperature is 750-850° C. and the time is 3-5 hours.

9. The method for rapidly preparing rutile phase titanium dioxide hollow nanoparticles according to claim 1, characterized in that: In step 5), the strong base is sodium hydroxide, and the concentration of the strong base solution is 0.4-0.6 mol / L; more preferably, the concentration of the strong base solution is 0.5 mol / L.

10. The method for rapidly preparing rutile phase titanium dioxide hollow nanoparticles according to claim 1, characterized in that: In step 5), the etching temperature is 70-90°C, and the holding time is 2-3h; more preferably, the etching temperature is 80°C, and the holding time is 3h; Preferably, in step 5), the centrifugal speed is 10000-12000 rpm, the washing is 3-5 times with deionized water, the drying temperature is 55-65° C., and the drying time is 8-12 h.

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