CN113979466B - ZnO@SiO 2 Method for preparing nanocapsules - Google Patents

ZnO@SiO 2 Method for preparing nanocapsules Download PDF

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CN113979466B
CN113979466B CN202111255036.0A CN202111255036A CN113979466B CN 113979466 B CN113979466 B CN 113979466B CN 202111255036 A CN202111255036 A CN 202111255036A CN 113979466 B CN113979466 B CN 113979466B
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nanocapsule
long
sio
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CN113979466A (en
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岳都元
栾奕
贾志忠
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Yantai Jialong Nano Industry Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Abstract

The invention relates to a ZnO@SiO 2 The preparation method of the nanocapsule belongs to the technical field of nanometer materials, and comprises the following steps: step 1, preparing zinc salts of organic acids; step 2, znO@SiO 2 Preparation of nanocomposite materials. The invention relates to ZnO@SiO 2 The preparation method of the nanocapsule comprises the steps of using long-chain carboxylate as a structure guiding agent, tetraethoxysilane and aminosilane as silicon sources, using organic acid zinc salt as a precursor, sequentially carrying out a series of continuous spontaneous reactions in a hydroalcoholic system to obtain an organic-inorganic hybrid nanomaterial, and finally obtaining ZnO@SiOthrough calcination 2 A nanocapsule; the ligand exchange reaction is utilized to connect the zinc salt of the organic acid with the long-chain sodium carboxylate serving as a structure directing agent, so that a large amount of metal ions can be introduced into the silicon dioxide matrix; the preparation method has mild reaction conditions, does not need to add an acid or alkaline catalyst, and can obtain ZnO nano particles with better dispersibility.

Description

ZnO@SiO 2 Method for preparing nanocapsules
Technical Field
The invention relates to a preparation method of nanocapsules, in particular to ZnO@SiO 2 A preparation method of nanocapsules, which belongs to the technical field of nanomaterials.
Background
ZnO nanoparticles have excellent optical characteristics, no toxicity, wide raw materials and the like, and are used as research hot spots in the field of nano science, but the ZnO nanoparticles are extremely easy to agglomerate to cause serious reduction of functionality, so that the ZnO nanoparticles are required to be dispersed in carrier materials to stabilize the performance, and in many carrier materials, siO is used as a material 2 Has the advantages of high stability, ultraviolet permeability, easy preparation, and the like, and has large specific surface area of SiO 2 Composite materials, which are carriers, have become research hot spots in many fields of physics, chemistry, materials, life sciences and the like in recent years, and therefore, are very ideal carrier materials for numerous nanoparticles.
The template method is the currently preferred and mainstream method for preparing the hollow silica-based nanocomposite, but it is difficult to obtain metal nanoparticles with good dispersibility and considerable loading. In addition, the method needs to use strong alkaline substances such as ammonia water, sodium hydroxide and the like as catalysts, so that potential experimental risks exist, metal nano particles are easy to damage, a large amount of the method also causes great harm to the environment, and the synthesis process is complicated. Thus, there is a need for a simple method to obtain silica matrix composite capsules containing a relatively large loading.
Disclosure of Invention
The purpose of the invention is that: in order to overcome the defects in the prior art, a ZnO@SiO is provided 2 The preparation method of the nanocapsule has mild reaction conditions, the reaction is continuously and spontaneously carried out, no additional acid or alkaline catalyst is needed, the complexity of the preparation step is low, and ZnO nanoparticles with better dispersibility can be obtained.
The technical scheme for solving the technical problems is as follows:
ZnO@SiO 2 The preparation method of the nanocapsule comprises the following steps:
step 1, preparation of zinc salt of organic acid: sequentially placing organic carboxylic acid and zinc oxide in 100mL of high-purity water according to a certain proportion, and reacting for 2-24 h in a water bath at 40-90 ℃ to generate zinc salt of organic acid as a metal particle precursor;
step 2, znO@SiO 2 Preparation of nanocomposite: dissolving long-chain sodium carboxylate in high-purity water, carrying out ultrasonic treatment and intense stirring until the long-chain sodium carboxylate is completely dissolved, dissolving the generated zinc salt of the organic acid in a mixed solution of water and absolute ethyl alcohol, dripping the solution into a high-purity water solution containing long-chain sodium carboxylate, and dripping a mixture of tetraethoxysilane and aminosilane into the solution after uniform dispersion; finally, controlling the stirring speed to be 600r/min, reacting for 12-96 h at normal temperature and normal pressure, centrifuging, drying the obtained solid, placing the dried solid in a muffle furnace, calcining in an air atmosphere, heating at a speed of 1-10 ℃/min, and keeping the temperature at 500-660 ℃ for 0.5-4 h to obtain ZnO@SiOj 2 And (5) nanocapsules.
Further, the long-chain carboxylate is a structure directing agent, the tetraethoxysilane and the aminosilane are silicon sources, and the zinc salt of the organic acid is a precursor.
Still further, the organic carboxylic acid is an α -halopropionic acid; the molar ratio of the organic carboxylic acid to the zinc oxide is 2-10:1.
Still further, the long-chain sodium carboxylate is a long-chain sodium salt with sixteen carbons or more.
Still further, the aminosilane is an aminosilane having an amino group; the volume ratio of the tetraethoxysilane to the aminosilane is 1:2 to 4.
Further, the mass concentration of the organic acid zinc salt is 0.025 g/mL-0.5 g/mL.
Further, the volume ratio of the water to the absolute ethyl alcohol is 1-3: 1.
Further, the centrifugal speed in the second step is 4000 r/min-9500 r/min.
The beneficial effects of the invention are as follows: the preparation method uses long-chain carboxylate as a structure guiding agent, tetraethoxysilane and aminosilane as a silicon source, and organic acid zinc salt as a precursor, and sequentially carries out a series of continuous spontaneous reactions in a hydro-alcoholic system to obtain an organic-inorganic hybrid nanomaterial, and finally the organic-inorganic hybrid nanomaterial is calcined to obtain ZnO@SiO 2 A nanocapsule; the ligand exchange reaction is utilized to connect the zinc salt of the organic acid with the long-chain sodium carboxylate serving as a structure directing agent, so that a large amount of metal ions can be introduced into the silicon dioxide matrix; the preparation method has mild reaction conditions, does not need to add an acid or alkaline catalyst, has low complexity of preparation steps, and can obtain ZnO nano particles with better dispersibility.
Drawings
FIG. 1 is a diagram of ZnO@SiO of the present invention 2 SEM image of nanocapsules;
FIG. 2 is a graph of ZnO@SiO in the present invention 2 TEM image of nanocapsules;
FIG. 3 is a graph of ZnO@SiO in the present invention 2 XRD pattern of nanocapsules.
Detailed Description
The principles and features of the present invention are described below with reference to fig. 1 through 3, the examples being provided for illustration only and not for limitation of the scope of the invention.
Example 1
The preparation method of the ZnO@SiO2 nanocapsule comprises the following steps:
step 1, preparation of alpha-bromopropionic acid zinc salt: sequentially placing 0.01mol of zinc oxide and 0.02mol of alpha-bromopropionic acid into a single-neck round-bottom flask filled with 100ml of high-purity water, reacting for 4 hours at a water bath of 60 ℃, filtering to obtain a clear solution, and evaporating the solvent by a rotary evaporator to obtain white solid, namely the alpha-bromopropionic acid zinc salt;
step 2, preparation of ZnO@SiO2 nanocomposite: dissolving 0.5g sodium octadecenoate in 18mL high-purity water, carrying out ultrasonic treatment until the sodium octadecenoate is completely dispersed, dissolving 0.45g of zinc alpha-bromopropionate salt in 6mL water and 6mL absolute ethyl alcohol, dropwise adding the solution into the sodium octadecenoate solution, and uniformly stirring; then 0.6mL of tetraethoxysilane and 1.2mL of 3-aminopropyl triethylsilane are added into the solution, the stirring speed is controlled to be 600r/min, the centrifugation is carried out after the reaction is carried out for 12h at normal temperature and normal pressure, the speed is 8000r/min, the obtained solid is dried and then is put into a muffle furnace to be calcined in air atmosphere, the heating rate is 1 ℃/min, the heat preservation temperature is 600 ℃, the heat preservation time is 4h, and finally the ZnO@SiO is obtained 2 And (5) nanocapsules.
Example 2
The preparation method of the ZnO@SiO2 nanocapsule comprises the following steps:
step 1, preparation of alpha-zinc chloropropionate: sequentially placing 0.01mol of zinc oxide and 0.02mol of alpha-chloropropionic acid into a single-neck round-bottom flask filled with 100ml of high-purity water, reacting for 24 hours at the water bath of 60 ℃, filtering to obtain a clear solution, and evaporating the solvent by a rotary evaporator to obtain white solid, namely the alpha-chloropropionic acid zinc salt;
step 2, znO@SiO 2 Preparation of nanocomposite: dissolving 0.5g of sodium laurate in 18mL of high-purity water, carrying out ultrasonic treatment until the sodium laurate is completely dispersed, dissolving 0.45g of zinc alpha-chloropropionate salt in 6mL of water and 6mL of absolute ethyl alcohol, dripping the solution into the sodium laurate solution, and uniformly stirring; then 0.6mL of ethyl orthosilicate and 1.2mAdding L3-aminopropyl triethylsilane into the solution, controlling the stirring speed to be 600r/min, performing centrifugation after reacting for 12 hours at normal temperature and normal pressure at the speed of 8000r/min, drying the obtained solid, placing the dried solid in a muffle furnace, calcining in air atmosphere at the heating speed of 1 ℃/min, and keeping the temperature at 600 ℃ for 4 hours to finally obtain ZnO@SiOO 2 And (5) nanocapsules.
The two groups of ZnO@SiO are obtained 2 Nanocapsules were collected and analyzed for any of the materials, as shown in fig. 1, 2 and 3:
(1) As can be seen from fig. 1, the resulting material is in the form of regular spheres with an average particle size of about 400nm and an open structure is observed;
(2) As can be seen from fig. 2, the resulting material is hollow structure, and ZnO nanoparticles are dispersed on the silica wall;
(3) As can be seen from fig. 3, a series of diffraction peaks appear at 2θ=31.7 °, 34.6 °, 36.5 °, 47.6 °, 56.5 °, 62.8 °, 68.3 ° and 69.2 °, corresponding to ZnO nanoparticles (100), (002), (101), (102), (110), (103), (112) and (201) crystal planes, respectively, and the resultant ZnO nanoparticles are hexagonal crystal systems with unit cell parameters of a= 3.253, c= 5.209 (JCPDS No. 80-0075) as compared with standard cards.
The preparation method of the ZnO@SiO2 nanocapsule comprises the steps of using long-chain carboxylate as a structure guiding agent, tetraethoxysilane and aminosilane as silicon sources, using organic acid zinc salt as a precursor, sequentially performing a series of continuous spontaneous reactions in a hydroalcoholic system to obtain an organic-inorganic hybrid nanomaterial, and finally calcining to obtain the ZnO@SiO2 nanocapsule 2 A nanocapsule; the ligand exchange reaction is utilized to connect the zinc salt of the organic acid with the long-chain sodium carboxylate serving as a structure directing agent, so that a large amount of metal ions can be introduced into the silicon dioxide matrix; the preparation method has mild reaction conditions, does not need to add an acid or alkaline catalyst, has low complexity of preparation steps, and can obtain ZnO nano particles with better dispersibility.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.

Claims (7)

1. ZnO@SiO 2 The preparation method of the nanocapsule is characterized by comprising the following steps:
step 1, preparation of zinc salt of organic acid: sequentially placing organic carboxylic acid and zinc oxide in 100mL of high-purity water according to a certain proportion, and reacting for 2-24 h in a water bath at 40-90 ℃ to generate zinc salt of organic acid as a metal particle precursor;
step 2, znO@SiO 2 Preparation of nanocomposite: dissolving long-chain sodium carboxylate in high-purity water, carrying out ultrasonic treatment and intense stirring until the long-chain sodium carboxylate is completely dissolved, dissolving the generated zinc salt of the organic acid in a mixed solution of water and absolute ethyl alcohol, dripping the solution into a high-purity water solution containing long-chain sodium carboxylate, and dripping a mixture of tetraethoxysilane and aminosilane into the solution after uniform dispersion; finally, controlling the stirring speed to be 600r/min, reacting for 12-96 h at normal temperature and normal pressure, centrifuging, drying the obtained solid, placing the dried solid in a muffle furnace, calcining in an air atmosphere, heating at a speed of 1-10 ℃/min, and keeping the temperature at 500-660 ℃ for 0.5-4 h to obtain ZnO@SiOj 2 A nanocapsule;
the long-chain carboxylate is a structure guiding agent, the tetraethoxysilane and the aminosilane are silicon sources, and the zinc salt of the organic acid is a precursor.
2. The zno@siox of claim 1 2 The preparation method of the nanocapsule is characterized by comprising the following steps: the organic carboxylic acid is alpha-halopropionic acid; the molar ratio of the organic carboxylic acid to the zinc oxide is 2-10:1.
3. The zno@siox of claim 1 2 The preparation method of the nanocapsule is characterized by comprising the following steps: the long-chain sodium carboxylate is long-chain sodium salt with sixteen carbons or more.
4. The zno@siox of claim 1 2 Preparation method of nanocapsulesThe method is characterized in that: the aminosilane is organosilane with amino; the volume ratio of the tetraethoxysilane to the aminosilane is 1:2 to 4.
5. The zno@siox of claim 1 2 The preparation method of the nanocapsule is characterized by comprising the following steps: the mass concentration of the organic acid zinc salt is 0.025 g/mL-0.5 g/mL.
6. The zno@siox of claim 1 2 The preparation method of the nanocapsule is characterized by comprising the following steps: the volume ratio of the water to the absolute ethyl alcohol is 1-3: 1.
7. The zno@siox of claim 1 2 The preparation method of the nanocapsule is characterized by comprising the following steps: the centrifugal speed in the step 2 is 4000 r/min-9500 r/min.
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JP2001038193A (en) * 1999-07-28 2001-02-13 Nippon Millipore Kk Production of composite silica microcapsule, and method for controlling immobilization and slow releasing action of core substance of composite silica microcapsule
WO2008069561A1 (en) * 2006-12-05 2008-06-12 Seoul National University Industry Foundation Metal oxide hollow nanocapsule and a method for preparing the same
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CN104910901A (en) * 2015-05-26 2015-09-16 哈尔滨工业大学 Method used for preparing ZnO/SiO2 nano composite material
CN110013807A (en) * 2019-04-28 2019-07-16 燕山大学 A kind of preparation method of light-initiated self-repairing microcapsule
CN113042044A (en) * 2021-04-02 2021-06-29 福州大学 TiO doped with ZnO2-SiO2Preparation and application of platinum catalyst as carrier
CN113428867A (en) * 2021-07-15 2021-09-24 深圳先进技术研究院 Hollow silicon dioxide spherical particle and preparation method and application thereof

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EP3124112A1 (en) * 2015-07-30 2017-02-01 DWI - Leibniz-Institut für Interaktive Materialien e.V. Method for the encapsulation of substances in silica-based capsules and the products obtained thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001038193A (en) * 1999-07-28 2001-02-13 Nippon Millipore Kk Production of composite silica microcapsule, and method for controlling immobilization and slow releasing action of core substance of composite silica microcapsule
WO2008069561A1 (en) * 2006-12-05 2008-06-12 Seoul National University Industry Foundation Metal oxide hollow nanocapsule and a method for preparing the same
CN102733005A (en) * 2012-05-16 2012-10-17 青岛科技大学 Preparation method for hollow SiO2/ZnO composite nanofibers
CN104211071A (en) * 2014-09-05 2014-12-17 哈尔滨工业大学 Synthetic method of CdS@SiO2 nano composite material
CN104910901A (en) * 2015-05-26 2015-09-16 哈尔滨工业大学 Method used for preparing ZnO/SiO2 nano composite material
CN110013807A (en) * 2019-04-28 2019-07-16 燕山大学 A kind of preparation method of light-initiated self-repairing microcapsule
CN113042044A (en) * 2021-04-02 2021-06-29 福州大学 TiO doped with ZnO2-SiO2Preparation and application of platinum catalyst as carrier
CN113428867A (en) * 2021-07-15 2021-09-24 深圳先进技术研究院 Hollow silicon dioxide spherical particle and preparation method and application thereof

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