Hollow artificial microbead and rutile phase titanium oxide composite material and preparation method thereof

Abstract

The invention belongs to the field of preparation of reflective thermal insulation coating functional pigments and fillers, and discloses a hollow artificial microbead and rutile phase titanium oxide composite material and a preparation method thereof. And slowly dropwise adding a titanium source into the structure-modified hollow artificial microbead suspension, hydrolyzing, and filtering to obtain the hollow artificial microbead / titanium dioxide composite material. By adjusting the surface composition of the hollow artificial microbeads, titanium salt hydrolysis nucleation sites and dynamics are improved, the hollow artificial microbead and rutile phase titanium oxide composite material is prepared in a low-temperature liquid phase mode, and the problem that nucleation and growth of rutile phase titanium oxide are inhibited by the surface silica structure characteristics of the hollow artificial microbeads is effectively solved; and the problem that the hollow artificial microbead structure collapses in the high-temperature heat treatment induced rutile conversion process of the hollow artificial microbead and anatase titanium oxide is also solved. According to the hollow artificial microbead and rutile phase titanium oxide composite material, the dosage of titanium oxide-based pigments and fillers is greatly reduced, the reflection and heat insulation capacity is improved, the raw material cost is further reduced, and more excellent reflection performance and heat insulation effect are shown.

Description

Technical Field

[0001] The present invention relates to the field of preparation of functional pigments and fillers for reflective heat-insulating coatings, and particularly to a preparation method of a heat-insulating material. Background Art

[0002] With the rapid growth of global energy consumption, the development of highly efficient energy-saving materials has become a current research hotspot. Solar reflective heat-insulating materials reduce the absorption of heat energy by peripheral enclosing structures such as buildings by reflecting visible light and near-infrared bands (accounting for 90% of the total energy) in sunlight, and can significantly reduce the energy consumption of air conditioners in summer. Rutile titanium oxide has advantages such as high whiteness and high refractive index, and has become the most widely used reflective heat-insulating material. However, rutile-phase titanium oxide has a relatively high thermal conductivity, and there is still heat on the surface of the peripheral enclosing structure that diffuses into the building interior through heat conduction and other means, reducing the reflective heat-insulating effect of the coating. At the same time, due to the micro-nano size of rutile-phase titanium dioxide particles, a certain thickness of titanium oxide coated on the surface of the peripheral enclosing structure usually requires a large amount of titanium oxide material to achieve a high reflective heat-insulating effect, resulting in problems such as a large amount of titanium oxide material used, low resource utilization rate, and high cost.

[0003] Hollow artificial microspheres are filled with media with high thermal resistance such as air and nitrogen inside, and have advantages such as low thermal conductivity and good dispersion fluidity. In recent years, they have been widely used as reflective heat-insulating functional fillers. The traditional method disperses hollow artificial microspheres and rutile-phase titanium oxide materials into the coating matrix by physical mixing means, which can reduce the amount of titanium oxide material used and reduce the thermal conductivity of the pigment and filler to a certain extent, thereby improving the light reflection and heat-insulating ability of the coating. However, due to the poor interfacial compatibility between the hollow artificial microspheres and the titanium oxide material, the distribution of the two is uneven, and heat accumulation and a large increase in surface temperature will still occur on the surface of the building coating after long-term sunlight irradiation. Therefore, the hollow artificial microspheres and the titanium oxide material can be further in-situ integrated to form a novel composite material of hollow artificial microspheres@rutile-phase titanium oxide, giving play to the synergistic effect of the two materials and further improving the reflective heat-insulating ability of the rutile-phase titanium oxide-based pigment and filler.

[0004] The surface of the hollow artificial microspheres contains silicon-oxygen bonds, which will induce the hydrolysis and deposition of titanium sources such as titanium chloride on their surface to form anatase titanium oxide or a mixed phase of anatase and rutile titanium oxide. For example, the prior art CN115029017A discloses a titanium dioxide-coated hollow glass microsphere composite material and its preparation method, but high-temperature calcination is required in the later stage. Although anatase titanium oxide can be transformed into rutile phase through heat treatment, the required heat treatment temperature is often higher than 700 °C, exceeding the softening temperature of the hollow artificial microspheres (about 500 °C), resulting in the collapse of the structure of the hollow artificial microspheres, which will destroy the spherical structure of the hollow microspheres, reduce the fluidity of the pigment filler, increase the thermal conductivity, and reduce the reflection and heat insulation ability of the rutile-phase titanium oxide-based pigment filler. The prior art CN110408239A discloses a high-rutile-type titanium dioxide hollow glass microsphere, its preparation method and a heat insulation filler, and high-temperature treatment at 600-800 °C is required to exert the induced conversion of tin oxide. Thermogravimetric tests on the hollow glass microspheres show a mass decrease at 500 °C, indicating that the high-temperature induced rutile phase conversion conditions of tin oxide will cause the collapse of the glass microsphere structure, thereby reducing the reflection and heat insulation ability of the titanium oxide pigment filler. Summary of the Invention

[0005] Aiming at the technical problems in the prior art that the nucleation and growth of rutile-phase titanium oxide on the surface of artificial microspheres are difficult, and the structure of hollow artificial microspheres collapses during the high-temperature heat treatment-induced rutile conversion process, the present invention proposes a hollow artificial microsphere@rutile-phase titanium oxide composite material and its preparation method. A low-temperature liquid-phase precipitation method with a simple process flow, low cost and environmental protection is proposed. By adjusting the surface structure composition of the hollow artificial microspheres, the hydrolysis thermodynamics and kinetics behavior of the titanium source are regulated to achieve the uniform deposition of rutile-phase titanium oxide on the surface of the hollow artificial microspheres.

[0006] To achieve the above object, the technical solution of the present invention is realized as follows: A preparation method of a hollow artificial microsphere@rutile-phase titanium oxide composite material comprises the following steps: (1) Adding a structure modifier to water to obtain a surface structure modification solution; (2) Adding the hollow artificial microspheres to the surface structure modification solution obtained in step (1), and obtaining modified hollow artificial microspheres through constant-temperature aging, washing and filtration; (3) Dispersing the modified hollow artificial microspheres obtained in step (2) into deionized water under stirring to obtain an aqueous solution of modified hollow artificial microspheres; heating to a certain temperature under stirring and then dropping a titanium source solution thereto, and after the dropping is completed, maintaining constant-temperature aging for a certain time and through cleaning and washing to obtain a hollow artificial microsphere@rutile-phase titanium oxide composite material.

[0007] In the above step (1), the concentration of the surface structure modification solution is 0.001 - 0.1 g / mL; the structure modifier is at least one of germanium tetrachloride, tin chloride, lead chloride, manganese chloride, ruthenium chloride, and tungsten chloride.

[0008] In the above step (2), the mass ratio of the hollow artificial microspheres to the surface structure modification solution is 1:20 - 60.

[0009] In the above step (3), the titanium source is at least one of titanium tetrachloride, titanium trichloride, titanium tetrabromide, and titanium tetraiodide, and the concentration of the titanium source solution is 0.01 - 2.0 g / mL.

[0010] Furthermore, in the above step (3), the concentration of the aqueous solution of the modified hollow artificial microspheres is 0.01 - 1 g / mL; the mass ratio of the aqueous solution of the modified hollow artificial microspheres to the titanium source solution is 1:5 - 100.

[0011] In the above step (3), the dropping rate is 0.05 - 5.0 mL / min.

[0012] In the above steps (2) and (3), the temperature for constant temperature aging is 40 - 95 °C, and the time is 2 - 24 h.

[0013] A hollow artificial microsphere@rutile titanium oxide composite material prepared by the above preparation method.

[0014] The beneficial effects of the present invention are as follows: (1) In the present invention, the hollow artificial microspheres are used as the matrix, the surface structure of the microspheres is adjusted, the hydrolysis thermodynamics and kinetics of the titanium source are precisely controlled, and the uniform deposition of rutile titanium oxide material on the surface of the hollow artificial microspheres is realized, overcoming the problem that it is difficult to deposit rutile titanium oxide on the surface of the hollow artificial microspheres; at the same time, by introducing rutile phase functional oxides, the interfacial force between the hollow artificial microspheres and titanium oxide is improved by using the lattice matching of the rutile phase functional oxides and rutile titanium oxide, and the processability and stability of the hollow artificial microsphere@rutile titanium oxide composite material are improved.

[0015] (2) In the present invention, the mass ratio of tin oxide to titanium dioxide is adjusted to a minimum of 0.02, which greatly increases the content of titanium oxide on the surface of the microspheres, and the content of rutile-type titanium oxide on the surface reaches 100%, and thus shows better reflection and heat insulation capabilities, and the near-infrared reflectance reaches 95.02%. Description of the Drawings

[0016] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the accompanying drawings required for the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other accompanying drawings can be obtained based on these drawings.

[0017] Figure 1 It is the SEM image of the hollow artificial microsphere@rutile titanium oxide composite material prepared in Example 1.

[0018] Figure 2 It is the SEM image of the hollow artificial microsphere@rutile titanium oxide composite material prepared in Example 2.

[0019] Figure 3 It is the SEM image of the hollow artificial microsphere@rutile titanium oxide composite material prepared in Example 3.

[0020] Figure 4 It is the XRD pattern of the hollow artificial microsphere@rutile titanium oxide composite material prepared in Example 1.

[0021] Figure 5 It is the XRD pattern of the hollow artificial microsphere@rutile titanium oxide composite material prepared in Example 2.

[0022] Figure 6 It is the reflection spectrum of the hollow artificial microsphere@rutile titanium oxide composite materials prepared in Examples 1 and 2.

[0023] Figure 7 It is the thermogravimetric diagram of the hollow artificial microsphere@rutile titanium oxide composite materials prepared in Examples 1 - 3. Specific Embodiments

[0024] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0025] Example 1 The preparation method of the hollow artificial microsphere@rutile titanium oxide composite material in this embodiment is as follows: (1) Add 0.28 g of tin chloride to 200 mL of deionized water to obtain a surface structure modification solution (tin chloride solution); (2) Add 5 g of hollow artificial microspheres (abbreviated as HGM, purchased from Zhengzhou Shenglaite New Materials Co., Ltd.) to the tin chloride solution (200.28 g), age at a constant temperature of 60 °C for 4 h, wash and filter to obtain modified hollow artificial microspheres; (3) Disperse 6 g of titanium tetrachloride into 400 mL of water solvent to obtain a titanium source solution (titanium chloride solution); (4) Disperse 5 g of the modified hollow artificial microspheres into 50 mL of deionized water under mechanical stirring. After heating to 80 °C under stirring, add 406 g of the titanium chloride solution dropwise thereto (the dropping rate is 1.0 mL / min). After the dropping is completed, keep the temperature at 80 °C and age for a certain time of 3 h. After washing and cleaning, obtain a hollow artificial microsphere@rutile titanium dioxide composite material, denoted as HGM@SnO2@TiO2.

[0026] Figure 1 The SEM image of the composite material prepared in this example is shown. It can be seen from the figure that a thin layer of dense substance is evenly deposited on the surface of the artificial microspheres.

[0027] Figure 4 The XRD pattern of the composite material prepared in this example shows that characteristic peaks of rutile TiO2 appear at 2θ = 27.4 o 、36.1 o 、41.2 o 、54.3 o 、56.6 o 、69.0 o and no other impurity phases appear. It can be determined that the titanium dioxide deposited on the surface of the artificial microspheres is pure-phase rutile.

[0028] Example 2 The preparation method of the hollow artificial microsphere@rutile titanium dioxide composite material in this example is as follows: (1) Add 0.28 g of germanium tetrachloride to 200 mL of deionized water to obtain a surface structure modification solution (germanium chloride solution); (2) Add 5 g of hollow artificial microspheres (purchased from Zhengzhou Shenglaite New Materials Co., Ltd.) to the tin chloride solution (200.28 g), age at a constant temperature of 70 °C for 12 h, wash and filter to obtain modified hollow artificial microspheres C; (3) Disperse 6 g of titanium tetrachloride into 400 mL of water solvent to obtain a titanium source solution (titanium chloride solution); (4) Disperse 5 g of modified hollow artificial microspheres into 50 mL of deionized water under mechanical stirring. After heating to 70 °C under stirring, add 406 g of titanium chloride solution dropwise thereto (the dropping rate is 1.0 mL / min). After the dropping is completed, keep it at 80 °C for constant aging for a certain time of 8 h, and after washing and cleaning, obtain a hollow artificial microsphere@rutile titanium dioxide composite material, denoted as HGM@GeO2@TiO2.

[0029] Figure 2 This is the SEM image of the composite material prepared in this example. It can be seen that a thin layer of dense substance is evenly deposited on the surface of the artificial microspheres.

[0030] Figure 5 This is the XRD pattern of the composite material prepared in this example. It can be seen that at 2θ = 27.4 o 、36.1 o 、41.2 o 、54.3 o 、56.6 o 、69.0 o The characteristic peaks of rutile TiO2 appear and no other impurity phases appear. It can be determined that the titanium dioxide deposited on the surface of the artificial microspheres is pure-phase rutile.

[0031] Figure 6 This is the reflection spectrum of the composite material prepared in Example 1-2. It can be seen from the figure that when the TiO2 on the surface of the artificial microspheres changes from anatase phase to rutile phase with higher light reflection performance, its solar reflectance and near-infrared reflectance both increase significantly, from the initial 87.35% and 89.69% to 93.14% and 95.02%.

[0032] Example 3 The preparation method of the hollow artificial microsphere@rutile titanium dioxide composite material in this example is as follows: (1) Add 0.28 g of manganese chloride to 200 mL of deionized water to obtain a surface structure modification solution (manganese chloride solution); (2) Add 5 g of hollow artificial microspheres (purchased from Zhengzhou Shenglaite New Materials Co., Ltd.) to the manganese chloride solution (200.28 g), carry out constant aging at 60 °C for 24 h, wash and filter to obtain modified hollow artificial microspheres; (3) Disperse 6 g of titanium tetrabromide into 400 mL of water solvent to obtain a titanium source solution (titanium bromide solution); (4) Disperse 5 g of modified hollow artificial microspheres into 50 mL of deionized water under mechanical stirring. After heating to 90 °C under stirring, add 400.6 g of titanium bromide solution dropwise thereto (the dropping rate is 1.3 mL / min). After the dropping is completed, keep it at 90 °C for constant aging for a certain time of 1 h, and after washing and cleaning, obtain a hollow artificial microsphere@rutile titanium oxide composite material, denoted as HGM@MnO2@TiO2.

[0033] Figure 3 This is the SEM image of the composite material prepared in this example. It can be seen that a dense substance is uniformly deposited on the surface of the artificial microspheres.

[0034] Figure 7 This is the thermogravimetric graph of the composite materials prepared in Examples 1-3. It can be seen that the mass of the artificial microspheres decreases significantly at about 490 °C, mainly due to the collapse of the surface structure of the artificial microspheres, resulting in the escape of gas inside the microspheres and the splashing out of some debris. The obvious weight loss before 150 °C in the thermogravimetric curves of Examples 1-3 is mainly due to the rapid removal of free water adsorbed on the titanium oxide on the surface of the microspheres. The slow weight loss between 150 °C and 490 °C is mainly due to the bonding of titanium oxide on the surface of the microspheres and the gradual loss of some adsorbed water due to heating. The slight weight loss between 490 °C and 550 °C is mainly due to the collapse of the surface structure of the artificial microspheres, resulting in the escape of gas inside the microspheres and the splashing out of some debris.

[0035] Example 4 The preparation method of the hollow artificial microsphere@rutile titanium oxide composite material in this example is as follows: (1) Add 0.28 g of tin chloride to 200 mL of deionized water to obtain a surface structure modification solution (tin chloride solution); (2) Add 5 g of hollow artificial microspheres (purchased from Zhengzhou Shenglaite New Materials Co., Ltd.) to the tin chloride solution (200.28 g), carry out constant aging at 95 °C for 2 h, wash and filter to obtain modified hollow artificial microspheres; (4) Disperse 6 g of titanium tetrachloride into 400 mL of water solvent to obtain a titanium source solution (titanium chloride solution); (5) Disperse 5 g of modified hollow artificial microspheres into 50 mL of deionized water under mechanical stirring. After heating to 40 °C under stirring, add 400.6 g of titanium chloride solution dropwise thereto (the dropping rate is 1.3 mL / min). After the dropping is completed, keep it at 40 °C for constant aging for a certain time of 24 h, and after washing and cleaning, obtain a hollow artificial microsphere@rutile titanium oxide composite material, denoted as HGM@SnO2@TiO2.

[0036] Example 5 The preparation method of the hollow artificial microsphere@rutile titanium oxide composite material of this embodiment is as follows: (1) Add 0.2 g of tungsten chloride to 200 mL of deionized water to obtain a surface structure modification solution (tungsten chloride solution); (2) Add 5 g of hollow artificial microspheres (purchased from Zhengzhou Shenglaite New Materials Co., Ltd.) to stannous chloride solution (100 g), age at 95 °C for 2 h, wash and filter to obtain modified hollow artificial microspheres; (4) Disperse 4 g of titanium trichloride into 400 mL of aqueous solvent to obtain a titanium source solution (titanium chloride solution); (5) Disperse 0.5 g of modified hollow artificial microspheres into 50 mL of deionized water under mechanical stirring, heat to 40 °C under stirring, and then dropwise add 250 g of titanium chloride solution (the dropping rate is 0.05 mL / min). After the dropping is completed, keep the temperature at 95 °C and age for a certain time of 6 h, and after cleaning and washing, obtain the hollow artificial microsphere@rutile titanium oxide composite material.

[0037] Example 6 The preparation method of the hollow artificial microsphere@rutile titanium oxide composite material of this embodiment is as follows: (1) Add 10 g of manganese chloride to 200 mL of deionized water to obtain a surface structure modification solution (manganese chloride solution); (2) Add 3.5 g of hollow artificial microspheres (purchased from Zhengzhou Shenglaite New Materials Co., Ltd.) to manganese chloride solution (210 g), age at 60 °C for 24 h, wash and filter to obtain modified hollow artificial microspheres; (3) Disperse 40 g of titanium tetrabromide into 400 mL of aqueous solvent to obtain a titanium source solution (titanium bromide solution); (4) Disperse 30 g of modified hollow artificial microspheres into 30 mL of deionized water under mechanical stirring, heat to 95 °C under stirring, and then dropwise add 420 g of titanium bromide solution (the dropping rate is 3 mL / min). After the dropping is completed, keep the temperature at 95 °C and age for a certain time of 2 h, and after cleaning and washing, obtain the hollow artificial microsphere@rutile titanium oxide composite material, denoted as HGM@MnO2@TiO2.

[0038] Example 7 The preparation method of the hollow artificial microsphere@rutile titanium oxide composite material of this embodiment is as follows: (1) Add 20 g of tungsten chloride to 200 mL of deionized water to obtain a surface structure modification solution (tungsten chloride solution); (2) Add 4 g of hollow artificial microspheres (purchased from Zhengzhou Shenglaite New Materials Co., Ltd.) to the tin chloride solution (200 g), age at a constant temperature of 40 °C for 24 h, wash and filter to obtain modified hollow artificial microspheres; (4) Disperse 200 g of titanium trichloride into 100 mL of water solvent to obtain a titanium source solution (titanium chloride solution); (5) Disperse 4 g of modified hollow artificial microspheres into 20 mL of deionized water under mechanical stirring, heat to 95 °C under stirring, then add 400 g of titanium chloride solution dropwise thereto (the dropping rate is 5 mL / min), after the dropping is completed, keep the temperature at 95 °C and age for a certain time of 2 h, and after cleaning and washing, obtain a hollow artificial microsphere@rutile titanium oxide composite material.

[0039] Example 8 The preparation method of the hollow artificial microsphere@rutile titanium oxide composite material in this example is as follows: (1) Add 15 g of tin chloride to 200 mL of deionized water to obtain a surface structure modification solution (tin chloride solution); (2) Add 6 g of hollow artificial microspheres (purchased from Zhengzhou Shenglaite New Materials Co., Ltd.) to the tin chloride solution (180 g), age at a constant temperature of 80 °C for 8 h, wash and filter to obtain modified hollow artificial microspheres; (4) Disperse 10 g of titanium tetrachloride into 400 mL of water solvent to obtain a titanium source solution (titanium chloride solution); (5) Disperse 5 g of modified hollow artificial microspheres into 25 mL of deionized water under mechanical stirring, heat to 80 °C under stirring, then add 300 g of titanium chloride solution dropwise thereto (the dropping rate is 2 mL / min), after the dropping is completed, keep the temperature at 80 °C and age for a certain time of 10 h, and after cleaning and washing, obtain a hollow artificial microsphere@rutile titanium oxide composite material, denoted as HGM@SnO2@TiO2.

[0040] Example 9 The preparation method of the hollow artificial microsphere@rutile titanium oxide composite material in this example is as follows: (1) Add 5 g of tin chloride to 200 mL of deionized water to obtain a surface structure modification solution (tin chloride solution); (2) Add 5 g of hollow artificial microspheres (purchased from Zhengzhou Shenglaite New Materials Co., Ltd.) to the tin chloride solution (200 g), age at a constant temperature of 95 °C for 2 h, wash and filter to obtain modified hollow artificial microspheres; (4) Disperse 30 g of titanium tetrachloride into 400 mL of water solvent to obtain a titanium source solution (titanium chloride solution); (5) Disperse 5 g of modified hollow artificial microspheres into 50 mL of deionized water under mechanical stirring. After heating to 40 °C under stirring, add 400 g of titanium chloride solution dropwise thereto (the dropping rate is 4 mL / min). After the dropping is completed, keep it at 40 °C for constant aging for a certain time of 24 h, and after washing and cleaning, obtain a hollow artificial microsphere@rutile titanium oxide composite material, denoted as HGM@SnO2@TiO2.

[0041] Example 10 The preparation method of the hollow artificial microsphere@rutile titanium oxide composite material of this example is as follows: (1) Add 14 g of tin chloride to 200 mL of deionized water to obtain a surface structure modification solution (tin chloride solution); (2) Add 4 g of hollow artificial microspheres (purchased from Zhengzhou Shenglaite New Materials Co., Ltd.) to the tin chloride solution (160 g), carry out constant aging at 60 °C for 12 h, wash and filter to obtain modified hollow artificial microspheres; (4) Disperse 60 g of titanium tetrachloride into 400 mL of water solvent to obtain a titanium source solution (titanium chloride solution); (5) Disperse 4 g of modified hollow artificial microspheres into 50 mL of deionized water under mechanical stirring. After heating to 40 °C under stirring, add 440 g of titanium chloride solution dropwise thereto (the dropping rate is 2.5 mL / min). After the dropping is completed, keep it at 70 °C for constant aging for a certain time of 24 h, and after washing and cleaning, obtain a hollow artificial microsphere@rutile titanium oxide composite material, denoted as HGM@SnO2@TiO2.

[0042] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A preparation method of a hollow artificial microsphere@rutile titanium oxide composite material, characterized in that, The steps are as follows: (1) Add a structure modifier to water to obtain a surface structure modification solution; (2) Add hollow artificial microspheres to the surface structure modification solution obtained in step (1), and obtain modified hollow artificial microspheres through constant-temperature aging, washing, and filtration; (3) Dropwise add a titanium source solution to the aqueous solution of the modified hollow artificial microspheres obtained in step (2), and obtain a hollow artificial microsphere@rutile titanium oxide composite through constant-temperature aging, washing, and filtration.

2. The preparation method of the hollow artificial microsphere@rutile titanium oxide composite material according to claim 1, characterized in that, In step (1), the concentration of the surface structure modification solution is 0.001 - 0.1 g / mL.

3. The preparation method of the hollow artificial microsphere@rutile titanium oxide composite material according to claim 2, characterized in that, In step (1), the structure modifier is at least one of germanium tetrachloride, tin chloride, lead chloride, manganese chloride, ruthenium chloride, and tungsten chloride.

4. The preparation method of the hollow artificial microsphere@rutile titanium oxide composite material according to claim 3, characterized in that, In step (2), the mass ratio of the hollow artificial microspheres to the surface structure modification solution is 1:20 - 60.

5. The preparation method of the hollow artificial microsphere@rutile titanium oxide composite material according to claim 4, characterized in that, In step (3), the titanium source is at least one of titanium tetrachloride, titanium trichloride, titanium tetrabromide, and titanium tetraiodide.

6. The preparation method of the hollow artificial microsphere@rutile titanium oxide composite material according to claim 5, characterized in that, In step (3), the concentration of the titanium source solution is 0.01 - 2.0 g / mL.

7. The preparation method of the hollow artificial microsphere@rutile titanium oxide composite material according to claim 6, characterized in that, In step (3), the concentration of the aqueous solution of the modified hollow artificial microspheres is 0.01 - 1 g / mL; the mass ratio of the aqueous solution of the modified hollow artificial microspheres to the titanium source solution is 1:5 - 100.

8. The preparation method of the hollow artificial microsphere@rutile titanium oxide composite material according to claim 7, characterized in that, In step (3), the dropping rate is 0.05 - 5.0 mL / min.

9. The preparation method of the hollow artificial microsphere@rutile titanium oxide composite material according to claim 8, characterized in that, In steps (2) and (3), the temperature for constant-temperature aging is 40 - 95°C, and the time is 2 - 24 h.

10. A hollow artificial microsphere@rutile titanium oxide composite prepared by the preparation method according to any one of claims 1 - 9.

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