CN112295515B - Preparation method of zinc oxide/cerium oxide hollow microspheres with inverted blueberry-shaped structures - Google Patents
Preparation method of zinc oxide/cerium oxide hollow microspheres with inverted blueberry-shaped structures Download PDFInfo
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Abstract
The invention provides a preparation method of a zinc oxide/cerium oxide hollow microsphere with a reverse blueberry type structure, which comprises the following steps: providing an aqueous dispersion of polystyrene microspheres which are not surface-modified or surface-modified; adding zinc salt into the polystyrene microsphere dispersion, heating to 35-95 ℃, adding alkali for reaction for no less than 30 minutes, centrifuging, and washing to obtain polystyrene/zinc oxide composite particles with a blueberry-shaped structure; adding cerium salt into an aqueous dispersion of polystyrene/zinc oxide composite particles, heating to 35-95 ℃, adding a precipitator, and reacting for not less than 30 minutes to obtain polystyrene/zinc oxide/cerium oxide composite particles; and (3) taking the prepared composite particles as a template, and removing the polystyrene microspheres through dissolving with a specific solvent or calcining at high temperature to obtain the zinc oxide/cerium oxide hollow microspheres with the inverted blueberry structure. The particle size and the number of the zinc oxide nanoparticles in the zinc oxide/cerium oxide hollow microspheres and the thickness and the composition of a cerium oxide shell layer have controllability.
Description
Technical Field
The invention belongs to the technical field of functional nano composite materials, and particularly relates to a preparation method of a zinc oxide/cerium oxide hollow microsphere with a reverse blueberry type structure.
Background
One of the main causes of skin aging or skin diseases is intense ultraviolet irradiation, and the correct use of sunscreen products is an effective means for preventing the above problems. Zinc oxide nanoparticles are a very important and widely used physical sunscreen agent. However, the zinc oxide nanoparticles are prone to agglomeration due to the strong van der waals force and high surface energy among the particles, so that the original ultraviolet shielding performance is reduced. Meanwhile, zinc oxide nanoparticles have an enhanced ability to generate Reactive Oxygen Species (ROS) under uv irradiation, as compared to micron-sized zinc oxide, and excessive ROS can cause cell death.
At present, the hollow microspheres with the inverted blueberry-shaped structures are researched more, but the components relate to zinc oxide and cerium dioxide at the same time, namely zinc oxide nanoparticles are fixed on the inner surface of the shell layer of the cerium dioxide hollow microspheres, and reports are not found yet. In order to introduce a plurality of nanoparticles into the interior of the hollow structure, the most common method is a sacrificial template method, which involves successively depositing the nanoparticles and shell material onto a template, followed by selective removal of the template to obtain the hollow structure. Nevertheless, surface pretreatment of the template is an indispensable task for successful deposition of nanoparticles and shell material on the surface of the template, and is considered to be the most critical step in the sacrificial template process. However, the surface pretreatment makes the entire manufacturing process more complicated, the structural controllability of the resulting material is poor, and the yield is low.
Therefore, a preparation method of the zinc oxide/cerium oxide hollow microsphere with the inverted blueberry-shaped structure is urgently needed in the field, and the process needs to be simple and effective and can be suitable for industrial production.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The invention aims to provide a novel method for simply and efficiently preparing a zinc oxide/cerium oxide hollow microsphere with a reverse blueberry type structure. The polystyrene microsphere and the intermediate product polystyrene/zinc oxide composite particle do not need to be subjected to any surface modification and modification in advance, so that the purposes of simplifying the process and reducing the cost are achieved.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a zinc oxide/cerium oxide hollow microsphere with a reverse blueberry type structure comprises the steps of adopting an aqueous dispersion of polystyrene microspheres which are not subjected to surface modification and surface modification; adding zinc salt into the aqueous dispersion of the polystyrene microsphere, heating to 35-95 ℃, adding alkali for reaction for no less than 30 minutes, centrifuging, and washing to obtain polystyrene/zinc oxide composite particles with a blueberry-shaped structure; adding cerium salt into an aqueous dispersion of polystyrene/zinc oxide composite particles with a blueberry-shaped structure, heating to 35-95 ℃, adding a precipitator, and reacting for not less than 30 minutes to obtain polystyrene/zinc oxide/cerium oxide composite particles; and (3) dissolving the polystyrene/zinc oxide/cerium oxide composite particles by using a specific solvent or calcining at high temperature to remove the polystyrene microspheres, thereby obtaining the zinc oxide/cerium oxide hollow microspheres with the inverted blueberry structure.
As an optimal scheme of the preparation method of the zinc oxide/cerium oxide hollow microsphere with the inverted blueberry-shaped structure, the preparation method comprises the following steps: the particle size of the polystyrene microsphere is not less than 200 nanometers; preferably, the particle size of the polystyrene microsphere is 1000-2000 nm.
As an optimal scheme of the preparation method of the zinc oxide/cerium oxide hollow microsphere with the inverted blueberry-shaped structure, the preparation method comprises the following steps: the zinc salt is one of zinc acetate, zinc sulfate, zinc nitrate, zinc carbonate or zinc chloride, and preferably zinc acetate; the alkali is one of sodium hydroxide, potassium hydroxide, lithium hydroxide, urea, hexamethylenetetramine or ammonia water.
As an optimal scheme of the preparation method of the zinc oxide/cerium oxide hollow microsphere with the inverted blueberry-shaped structure, the preparation method comprises the following steps: the molar ratio of the zinc salt to the alkali is 1: 0.25 to 4.
As an optimal scheme of the preparation method of the zinc oxide/cerium oxide hollow microsphere with the inverted blueberry-shaped structure, the preparation method comprises the following steps: in the polystyrene/zinc oxide composite particles, the content of zinc oxide is 3-60% of the mass of the polystyrene microspheres, and the preferred content is 25%.
As an optimal scheme of the preparation method of the zinc oxide/cerium oxide hollow microsphere with the inverted blueberry-shaped structure, the preparation method comprises the following steps: the cerium salt is one of cerium nitrate, cerium sulfate, cerium carbonate, cerium acetate or hydrated cerium acetylacetonate, and is preferably cerium nitrate; the precipitator is one of urea, hexamethylene amine, trimethyl phosphate, dimethyl oxalate, dimethyl sulfate, sulfamic acid, thiophthalide amine, ammonia water, sodium hydroxide or 6-aminocaproic acid.
As an optimal scheme of the preparation method of the zinc oxide/cerium oxide hollow microsphere with the inverted blueberry-shaped structure, the preparation method comprises the following steps: the molar ratio of the cerium salt to the precipitant is 1: 0.25 to 4.
As an optimal scheme of the preparation method of the zinc oxide/cerium oxide hollow microsphere with the inverted blueberry-shaped structure, the preparation method comprises the following steps: in the polystyrene/zinc oxide/cerium oxide composite particles, the content of cerium oxide is 250 to 600%, preferably 300% of that of the polystyrene/zinc oxide composite particles.
As an optimal scheme of the preparation method of the zinc oxide/cerium oxide hollow microsphere with the inverted blueberry-shaped structure, the preparation method comprises the following steps: and calcining at the temperature of 350-1000 ℃.
The invention also aims to provide a product prepared by the preparation method of the zinc oxide/cerium oxide hollow microsphere with the inverted blueberry-shaped structure, wherein zinc oxide particles with the particle size of 10-100 nanometers are loaded on the inner surface of a shell layer of the cerium oxide hollow microsphere, and the thickness of the shell layer of the cerium oxide is 20-200 nanometers.
The invention has the beneficial effects that:
(1) the invention provides a preparation method of a zinc oxide/cerium oxide hollow microsphere with a reverse blueberry-shaped structure, which does not need to carry out specific surface modification and surface modification on a polystyrene microsphere serving as a template microsphere and an intermediate product polystyrene/zinc oxide composite particle in advance, avoids the defect of complex preparation process caused by surface pretreatment on the template in the traditional process, does not need to carry out any previous surface modification and modification on the polystyrene microsphere and the intermediate product polystyrene/zinc oxide composite particle, and is a novel method for simply and efficiently preparing the zinc oxide/cerium oxide hollow microsphere with the reverse blueberry-shaped structure.
(2) The preparation method of the zinc oxide/cerium oxide hollow microspheres with the inverted blueberry-shaped structure realizes the controllability of the composition, the structure and the shape of the hollow microspheres, obtains the zinc oxide/cerium oxide hollow microspheres with the inverted blueberry-shaped structure and different zinc oxide nanoparticle particle sizes and quantities, cerium oxide shell thicknesses and composition by adjusting various preparation conditions, and realizes the further regulation and control of the composition, the structure and the shape of the zinc oxide/cerium oxide hollow microspheres with the inverted blueberry-shaped structure.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
(1) Preparation of polystyrene microsphere dispersion
0.2g of azobisisobutyronitrile, pre-dissolved in 20g of styrene, was added to a four-necked flask equipped with a mechanical stirrer, reflux condenser and nitrogen inlet, together with 3.5g of polyvinylpyrrolidone dissolved in 160mL of isopropanol. The mixed solution was raised to 70 ℃ under a nitrogen atmosphere to initiate the polymerization process. After 24 hours, the reaction mixture was cooled to room temperature, and the synthesized polystyrene microspheres were collected by centrifugation and redispersed in deionized water to give a polystyrene microsphere dispersion with a solid content of 10 wt%. The polystyrene microsphere has good dispersibility and the average grain diameter is 1300 nanometers.
(2) Preparation of polystyrene/zinc oxide composite particles
5g of polystyrene microsphere dispersion (10 wt%) was mixed with 25mL of an ethanol solution of zinc acetate (50mM) and added to a 50mL three-necked flask. The resulting mixture was heated to 55 ℃ and kept at this temperature for 30 minutes with mechanical stirring. Subsequently, 0.625mL of an ethanol solution of sodium hydroxide (0.1M) was added dropwise to the above mixture over 5 minutes. Then, the reaction was continued for 30 minutes. And centrifuging, washing and drying to obtain the polystyrene/zinc oxide composite particles.
(3) Preparation of polystyrene/zinc oxide/cerium oxide composite particles
100mg of polystyrene/zinc oxide composite particles are dispersed in 100mL of deionized water, and are uniformly mixed with 0.45mL of cerium nitrate solution (2M) and then added into a 250mL three-neck flask. The resulting mixture was heated to 60 ℃ and maintained at this temperature for 1 hour with mechanical stirring. Subsequently, 10mL of a hexamethylenetetramine solution (0.2M) was added dropwise to the above mixture, and the reaction was continued for 2 hours. And centrifuging, washing and drying to obtain the polystyrene/zinc oxide/cerium oxide composite particles.
(4) Preparation of zinc oxide/cerium oxide hollow microspheres
And placing the dried polystyrene/zinc oxide/cerium oxide composite particles in a muffle furnace, heating to 400 ℃ at the heating rate of 2 ℃/min, and calcining for 2 hours to obtain the zinc oxide/cerium oxide hollow microspheres.
The zinc oxide/cerium oxide hollow microspheres prepared by analysis of a transmission electron microscope show that zinc oxide particles with the particle size of about 50 nanometers are loaded on the inner surfaces of the cerium oxide hollow microspheres, and the thickness of a cerium oxide shell layer is 40 nanometers.
Example 2
The embodiment provides a preparation method of a zinc oxide/cerium oxide hollow microsphere with a reverse blueberry-shaped structure, which comprises the following steps:
(1) preparation of polystyrene microsphere dispersion
A polystyrene microsphere dispersion was prepared in the same manner as in example 1.
(2) Preparation of polystyrene/zinc oxide composite particles
Polystyrene/zinc oxide composite particles were prepared in the same manner as in example 1.
(3) Preparation of polystyrene/zinc oxide/cerium oxide composite particles
100mg of polystyrene/zinc oxide composite particles are dispersed in 100mL of deionized water, and are uniformly mixed with 0.6mL of cerium nitrate solution (2M) and then added into a 250mL three-neck flask. The resulting mixture was heated to 60 ℃ and maintained at this temperature for 1 hour with mechanical stirring. Subsequently, 14mL of a hexamethylenetetramine solution (0.2M) was added dropwise to the above mixture, and the reaction was continued for 2 hours. And centrifuging, washing and drying to obtain the polystyrene/zinc oxide/cerium oxide composite particles.
(4) Preparation of zinc oxide/cerium oxide hollow microspheres
And placing the dried polystyrene/zinc oxide/cerium oxide composite particles in a muffle furnace, heating to 600 ℃ at the heating rate of 2 ℃/min, and calcining for 2 hours to obtain the zinc oxide/cerium oxide hollow microspheres.
The zinc oxide/cerium oxide hollow microspheres prepared by analysis of a transmission electron microscope show that zinc oxide particles with the particle size of about 50 nanometers are loaded on the inner surfaces of the cerium oxide hollow microspheres, and the thickness of a cerium oxide shell layer is 60 nanometers.
Example 3
The embodiment provides a preparation method of a zinc oxide/cerium oxide hollow microsphere with a reverse blueberry-shaped structure, which comprises the following steps:
(1) preparation of polystyrene microsphere dispersion
A polystyrene microsphere dispersion was prepared in the same manner as in example 1.
(2) Preparation of polystyrene/zinc oxide composite particles
Polystyrene/zinc oxide composite particles were prepared in the same manner as in example 1.
(3) Preparation of polystyrene/zinc oxide/cerium oxide composite particles
100mg of polystyrene/zinc oxide composite particles are dispersed in 100mL of deionized water, and are uniformly mixed with 0.9mL of cerium nitrate solution (2M) and then added into a 250mL three-neck flask. The resulting mixture was heated to 60 ℃ and maintained at this temperature for 1 hour with mechanical stirring. Subsequently, 21mL of a hexamethylenetetramine solution (0.2M) was added dropwise to the above mixture, and the reaction was continued for 2 hours. And centrifuging, washing and drying to obtain the polystyrene/zinc oxide/cerium oxide composite particles.
(4) Preparation of zinc oxide/cerium oxide hollow microspheres
And placing the dried polystyrene/zinc oxide/cerium oxide composite particles in a muffle furnace, heating to 800 ℃ at the heating rate of 2 ℃/min, and calcining for 2 hours to obtain the zinc oxide/cerium oxide hollow microspheres.
The zinc oxide/cerium oxide hollow microspheres prepared by analysis of a transmission electron microscope show that zinc oxide particles with the particle size of about 50 nanometers are loaded on the inner surfaces of the cerium oxide hollow microspheres, and the thickness of a cerium oxide shell layer is 100 nanometers.
Example 4
The embodiment provides a preparation method of a zinc oxide/cerium oxide hollow microsphere with a reverse blueberry-shaped structure, which comprises the following steps:
(1) preparation of polystyrene microsphere dispersion
The polystyrene microspheres with the grain diameter of 1800 nanometers sold in the market are adopted to prepare aqueous dispersion with the solid content of 1 weight percent.
(2) Preparation of polystyrene/zinc oxide composite particles
Polystyrene/zinc oxide composite particles were prepared in the same manner as in example 1.
(3) Preparation of polystyrene/zinc oxide/cerium oxide composite particles
Polystyrene/zinc oxide/cerium oxide composite particles were prepared in the same manner as in example 1.
(4) Preparation of zinc oxide/cerium oxide hollow microspheres
The zinc oxide/cerium oxide hollow microspheres were prepared in the same manner as in example 1.
The zinc oxide/cerium oxide hollow microspheres prepared by analysis of a transmission electron microscope show that zinc oxide particles with the particle size of about 60 nanometers are loaded on the inner surfaces of the cerium oxide hollow microspheres, and the thickness of a cerium oxide shell layer is 50 nanometers.
Example 5
The embodiment provides a preparation method of a zinc oxide/cerium oxide hollow microsphere with a reverse blueberry-shaped structure, which comprises the following steps:
(1) preparation of polystyrene microsphere dispersion
A polystyrene microsphere dispersion was prepared in the same manner as in example 1.
(2) Preparation of polystyrene/zinc oxide composite particles
5g of polystyrene microsphere dispersion (10 wt%) was mixed with 50mL of an ethanol solution of zinc acetate (25mM) and added to a 100mL three-necked flask. The resulting mixture was heated to 60 ℃ and kept at this temperature for 30 minutes with mechanical stirring. Subsequently, 0.625mL of an ethanol solution of sodium hydroxide (0.1M) was added dropwise to the above mixture over 5 minutes. Then, the reaction was continued for 30 minutes. And centrifuging, washing and drying to obtain the polystyrene/zinc oxide composite particles.
(3) Preparation of polystyrene/zinc oxide/cerium oxide composite particles
Polystyrene/zinc oxide/cerium oxide composite particles were prepared in the same manner as in example 1.
(4) Preparation of zinc oxide/cerium oxide hollow microspheres
The zinc oxide/cerium oxide hollow microspheres were prepared in the same manner as in example 1.
The zinc oxide/cerium oxide hollow microspheres prepared by analysis of a transmission electron microscope show that zinc oxide particles with the particle size of about 20 nanometers are loaded on the inner surfaces of the cerium oxide hollow microspheres, and the thickness of a cerium oxide shell layer is 40 nanometers.
Example 6
The embodiment provides a preparation method of a zinc oxide/cerium oxide hollow microsphere with a reverse blueberry-shaped structure, which comprises the following steps:
(1) preparation of polystyrene microsphere dispersion
A polystyrene microsphere dispersion was prepared in the same manner as in example 1.
(2) Preparation of polystyrene/zinc oxide composite particles
5g of polystyrene microsphere dispersion (10 wt%) was mixed with 50mL of an ethanol solution of zinc acetate (25mM) and added to a 100mL three-necked flask. The resulting mixture was heated to 50 ℃ and kept at this temperature for 30 minutes with mechanical stirring. Subsequently, 0.625mL of an ethanol solution of sodium hydroxide (0.1M) was added dropwise to the above mixture over 5 minutes. Then, the reaction was continued for 30 minutes. And centrifuging, washing and drying to obtain the polystyrene/zinc oxide composite particles.
(3) Preparation of polystyrene/zinc oxide/cerium oxide composite particles
Polystyrene/zinc oxide/cerium oxide composite particles were prepared in the same manner as in example 1.
(4) Preparation of zinc oxide/cerium oxide hollow microspheres
The zinc oxide/cerium oxide hollow microspheres were prepared in the same manner as in example 1.
The zinc oxide/cerium oxide hollow microspheres prepared by analysis of a transmission electron microscope show that zinc oxide particles with the particle size of about 80 nanometers are loaded on the inner surfaces of the cerium oxide hollow microspheres, and the thickness of a cerium oxide shell layer is 40 nanometers.
Example 7
The embodiment provides a preparation method of a zinc oxide/cerium oxide hollow microsphere with a reverse blueberry-shaped structure, which comprises the following steps:
(1) preparation of polystyrene microsphere dispersion
A polystyrene microsphere dispersion was prepared in the same manner as in example 1.
(2) Preparation of polystyrene/zinc oxide composite particles
5g of polystyrene microsphere dispersion (10 wt%) was mixed with 50mL of an ethanol solution of zinc acetate (50mM) and added to a 100mL three-necked flask. The resulting mixture was heated to 55 ℃ and kept at this temperature for 30 minutes with mechanical stirring. Subsequently, 1.25mL of an ethanol solution (0.1M) of sodium hydroxide was dropwise added to the above mixture over 5 minutes. Then, the reaction was continued for 30 minutes. And centrifuging, washing and drying to obtain the polystyrene/zinc oxide composite particles.
(3) Preparation of polystyrene/zinc oxide/cerium oxide composite particles
Polystyrene/zinc oxide/cerium oxide composite particles were prepared in the same manner as in example 1.
(4) Preparation of zinc oxide/cerium oxide hollow microspheres
The zinc oxide/cerium oxide hollow microspheres were prepared in the same manner as in example 1.
The zinc oxide/cerium oxide hollow microspheres prepared by analysis of a transmission electron microscope show that zinc oxide particles with the particle size of about 30 nanometers are loaded on the inner surfaces of the cerium oxide hollow microspheres, and the thickness of a cerium oxide shell layer is 40 nanometers.
Example 8
The embodiment provides a preparation method of a zinc oxide/cerium oxide hollow microsphere with a reverse blueberry-shaped structure, which comprises the following steps:
(1) preparation of polystyrene microsphere dispersion
A polystyrene microsphere dispersion was prepared in the same manner as in example 1.
(2) Preparation of polystyrene/zinc oxide composite particles
Polystyrene/zinc oxide composite particles were prepared in the same manner as in example 1.
(3) Preparation of polystyrene/zinc oxide/cerium oxide composite particles
Polystyrene/zinc oxide/cerium oxide composite particles were prepared in the same manner as in example 1.
(4) Preparation of zinc oxide/cerium oxide hollow microspheres
And (3) placing the dried polystyrene/zinc oxide/cerium oxide composite particles in toluene, and standing at room temperature for 24 hours to obtain the zinc oxide/cerium oxide hollow microspheres.
The zinc oxide/cerium oxide hollow microspheres prepared by analysis of a transmission electron microscope show that zinc oxide particles with the particle size of about 50 nanometers are loaded on the inner surfaces of the cerium oxide hollow microspheres, and the thickness of a cerium oxide shell layer is 40 nanometers.
The invention utilizes the coordination action between polyvinylpyrrolidone and zinc oxide precursor on the polystyrene microsphere to promote the zinc oxide nanoparticles to deposit on the surface of the polystyrene microsphere, simultaneously utilizes the electrostatic interaction between the polystyrene/zinc oxide composite particles and cerium salt to promote the polystyrene/zinc oxide composite particles and cerium oxide to realize effective and controllable compounding, and realizes the further regulation and control of the composition, structure and shape of the zinc oxide/cerium oxide hollow microsphere with the inverted blueberry structure by controlling the particle size of the zinc oxide nanoparticles and the thickness and composition of a cerium oxide shell layer. The invention provides a preparation method of a zinc oxide/cerium oxide hollow microsphere with a reverse blueberry-shaped structure, which does not need to carry out specific surface modification and surface modification on a polystyrene microsphere serving as a template microsphere and an intermediate product polystyrene/zinc oxide composite particle in advance, avoids the defect of complex preparation process caused by surface pretreatment on the template in the traditional process, does not need to carry out any previous surface modification and modification on the polystyrene microsphere and the intermediate product polystyrene/zinc oxide composite particle, and is a novel method for simply and efficiently preparing the zinc oxide/cerium oxide hollow microsphere with the reverse blueberry-shaped structure.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (8)
1. A preparation method of a zinc oxide/cerium oxide hollow microsphere with a reverse blueberry type structure is characterized by comprising the following steps: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
preparing polystyrene microsphere dispersion liquid by using polystyrene microspheres containing polyvinylpyrrolidone and water, wherein the particle size of the polystyrene microspheres is not less than 200 nanometers;
adding zinc salt into the polystyrene microsphere dispersion, heating to 35-95 ℃, adding alkali to react for no less than 30 minutes, centrifuging, washing, and dispersing in water to obtain the polystyrene/zinc oxide composite particle dispersion with the blueberry-type structure, wherein the molar ratio of the zinc salt to the alkali is 1: 0.25-4, wherein the content of zinc oxide is 3-60% of the mass of the polystyrene microsphere;
adding cerium salt into polystyrene/zinc oxide composite particle dispersion liquid with a blueberry-shaped structure, heating to 35-95 ℃, adding a precipitator to react for no less than 30 minutes, centrifuging and washing to obtain polystyrene/zinc oxide/cerium oxide composite particles, wherein the content of cerium oxide is 250-600% of the mass of the polystyrene/zinc oxide composite particles;
the method comprises the steps of dissolving polystyrene/zinc oxide/cerium oxide composite particles by a specific solvent or calcining at high temperature to remove polystyrene microspheres to obtain the zinc oxide/cerium oxide hollow microspheres with the inverted blueberry-shaped structure, wherein zinc oxide particles with the particle size of 10-100 nanometers are loaded on the inner surface of a shell layer of the cerium oxide hollow microspheres, and the thickness of the shell layer of the cerium oxide is 20-200 nanometers.
2. The preparation method of the anti-blueberry-structured zinc oxide/cerium oxide hollow microsphere as claimed in claim 1, wherein the preparation method comprises the following steps: the particle size of the polystyrene microsphere is 1000-2000 nm.
3. The preparation method of the anti-blueberry-structured zinc oxide/cerium oxide hollow microsphere as claimed in claim 1, wherein the preparation method comprises the following steps: the zinc salt is one of zinc acetate, zinc sulfate, zinc nitrate or zinc chloride; the alkali is one of sodium hydroxide, potassium hydroxide, lithium hydroxide, urea, hexamethylenetetramine or ammonia water.
4. The preparation method of the anti-blueberry-structured zinc oxide/cerium oxide hollow microsphere as claimed in claim 1, wherein the preparation method comprises the following steps: in the polystyrene/zinc oxide composite particles, the content of zinc oxide is 25% of the mass of the polystyrene microspheres.
5. The preparation method of the anti-blueberry-structured zinc oxide/cerium oxide hollow microsphere as claimed in claim 1, wherein the preparation method comprises the following steps: the cerium salt is one of cerium nitrate, cerium sulfate, cerium acetate or hydrated cerium acetylacetonate; the precipitator is one of urea, hexamethylenetetramine, thiophthalein amine, ammonia water or sodium hydroxide.
6. The preparation method of the anti-blueberry-structured zinc oxide/cerium oxide hollow microsphere as claimed in claim 1, wherein the preparation method comprises the following steps: the molar ratio of the cerium salt to the precipitant is 1: 0.25 to 4.
7. The preparation method of the anti-blueberry-structured zinc oxide/cerium oxide hollow microsphere as claimed in claim 1, wherein the preparation method comprises the following steps: in the polystyrene/zinc oxide/cerium oxide composite particles, the content of cerium oxide was 300% by mass of the polystyrene/zinc oxide composite particles.
8. The preparation method of the anti-blueberry-structured zinc oxide/cerium oxide hollow microsphere as claimed in claim 1, wherein the preparation method comprises the following steps: the calcination temperature is 350-1000 ℃.
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