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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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 310
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 155
- 239000004005 microsphere Substances 0.000 title claims abstract description 128
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 121
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 83
- 239000004793 Polystyrene Substances 0.000 claims abstract description 109
- 229920002223 polystyrene Polymers 0.000 claims abstract description 109
- 239000011246 composite particle Substances 0.000 claims abstract description 65
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 11
- 240000000851 Vaccinium corymbosum Species 0.000 claims abstract description 9
- 235000003095 Vaccinium corymbosum Nutrition 0.000 claims abstract description 9
- 235000017537 Vaccinium myrtillus Nutrition 0.000 claims abstract description 9
- 235000021014 blueberries Nutrition 0.000 claims abstract description 9
- 150000000703 Cerium Chemical class 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 13
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004246 zinc acetate Substances 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 235000013877 carbamide Nutrition 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- PYPNFSVOZBISQN-LNTINUHCSA-K cerium acetylacetonate Chemical compound [Ce+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O PYPNFSVOZBISQN-LNTINUHCSA-K 0.000 claims description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 15
- 238000012986 modification Methods 0.000 abstract description 15
- 239000002105 nanoparticle Substances 0.000 abstract description 11
- 238000005119 centrifugation Methods 0.000 abstract description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 239000011257 shell material Substances 0.000 description 15
- 230000005540 biological transmission Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 7
- 239000013067 intermediate product Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003642 reactive oxygen metabolite Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000516 sunscreening agent Substances 0.000 description 2
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000030833 cell death Effects 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000009759 skin aging Effects 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- -1 thiophthalide amine Chemical class 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Cosmetics (AREA)
Abstract
本发明提供了一种具有反蓝莓型结构的氧化锌/氧化铈中空微球的制备方法，包括：提供未经表面改性与表面修饰的聚苯乙烯微球的水分散液；将锌盐加入所述的聚苯乙烯微球分散液中，升温至35～95℃，加入碱反应不少于30分钟，经离心、洗涤，得到蓝莓型结构的聚苯乙烯/氧化锌复合粒子；在聚苯乙烯/氧化锌复合粒子的水分散液中加入铈盐，升温至35～95℃后，加入沉淀剂反应不少于30分钟，得到聚苯乙烯/氧化锌/氧化铈复合粒子；以上述所制备的复合粒子为模板，通过特定溶剂溶解或高温煅烧除去聚苯乙烯微球，得到反蓝莓型结构的氧化锌/氧化铈中空微球。氧化锌/氧化铈中空微球中氧化锌纳米粒子粒径与数量、氧化铈壳层的厚度及组成具有可控性。The invention provides a preparation method of zinc oxide/cerium oxide hollow microspheres with an inverse blueberry structure, comprising: providing an aqueous dispersion of polystyrene microspheres without surface modification and surface modification; adding zinc salt to In the polystyrene microsphere dispersion liquid, the temperature is raised to 35-95° C., alkali is added to react for no less than 30 minutes, and after centrifugation and washing, polystyrene/zinc oxide composite particles with blueberry structure are obtained; Add cerium salt to the aqueous dispersion of ethylene/zinc oxide composite particles, and after the temperature is raised to 35-95 ° C, add a precipitant to react for not less than 30 minutes to obtain polystyrene/zinc oxide/cerium oxide composite particles; The composite particles are used as templates, and the polystyrene microspheres are removed by dissolving in a specific solvent or calcining at high temperature to obtain zinc oxide/cerium oxide hollow microspheres with an inverse blueberry structure. The particle size and quantity of zinc oxide nanoparticles, the thickness and composition of the cerium oxide shell layer in the zinc oxide/cerium oxide hollow microspheres are controllable.
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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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285678A (en) * | 2011-06-09 | 2011-12-21 | 北京大学 | Method for preparing cerium oxide nano particles and antioxidation use thereof |
| CN102906024A (en) * | 2010-06-04 | 2013-01-30 | 荷兰联合利华有限公司 | Microspheres and photoprotective personal care composition comprising same |
| CN107159182A (en) * | 2017-05-31 | 2017-09-15 | 中盐金坛盐化有限责任公司 | A kind of preparation method of hollow microsphere SCR denitration |
| US20200190331A1 (en) * | 2017-04-10 | 2020-06-18 | Nanophase Technologies Corporation | Coated powders having high photostability |
| CN111601691A (en) * | 2017-09-11 | 2020-08-28 | 哈佛大学 | Microspheres comprising polydisperse polymeric nanospheres and porous metal oxide microspheres |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104001491B (en) * | 2014-05-15 | 2016-12-07 | 上海应用技术学院 | A kind of CeO2/TiO2 nanocomposite hollow sphere catalyst and preparation method thereof |
| CN104176761B (en) * | 2014-08-01 | 2016-03-16 | 长春理工大学 | A kind of preparation method of cerium dioxide porous microspheres |
| CN109663595A (en) * | 2018-12-11 | 2019-04-23 | 中科廊坊过程工程研究院 | A kind of copper based composite metal oxidate hollow microsphere, preparation method and the usage |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102906024A (en) * | 2010-06-04 | 2013-01-30 | 荷兰联合利华有限公司 | Microspheres and photoprotective personal care composition comprising same |
| CN102285678A (en) * | 2011-06-09 | 2011-12-21 | 北京大学 | Method for preparing cerium oxide nano particles and antioxidation use thereof |
| US20200190331A1 (en) * | 2017-04-10 | 2020-06-18 | Nanophase Technologies Corporation | Coated powders having high photostability |
| CN107159182A (en) * | 2017-05-31 | 2017-09-15 | 中盐金坛盐化有限责任公司 | A kind of preparation method of hollow microsphere SCR denitration |
| CN111601691A (en) * | 2017-09-11 | 2020-08-28 | 哈佛大学 | Microspheres comprising polydisperse polymeric nanospheres and porous metal oxide microspheres |
Non-Patent Citations (3)
| Title |
|---|
| A simple method to controlled synthesis of CeO2 hollow microspheres;Zhiyan Guo et al;《Scripta Materialia》;20090731;第61卷;第48-51页 * |
| Strong yellow emission of ZnO hollow nanospheres fabricated using polystyrene spheres as templates;Zhigang Zang et al;《Materials and Design》;20150630;第84卷;第418-421页 * |
| ZnO/CeO2 nanocomposite with low photocatalytic activity as efficient UV filters;Rafid Mueen et al;《Journal of Matertals Sciences》;20200630;第55卷;第6834-6847页 * |
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