CN107020055B - SiO (silicon dioxide)2Preparation method and application of @ ZnO core-shell structure multi-legged pellet nanocomposite - Google Patents
SiO (silicon dioxide)2Preparation method and application of @ ZnO core-shell structure multi-legged pellet nanocomposite Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 47
- 239000011258 core-shell material Substances 0.000 title claims abstract description 39
- 239000008188 pellet Substances 0.000 title claims abstract description 34
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 12
- 235000012239 silicon dioxide Nutrition 0.000 title claims description 7
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 44
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 44
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 44
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 44
- 239000013078 crystal Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 25
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 11
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 239000011324 bead Substances 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 5
- 238000005229 chemical vapour deposition Methods 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 130
- 239000011787 zinc oxide Substances 0.000 description 54
- 239000002073 nanorod Substances 0.000 description 15
- 238000001878 scanning electron micrograph Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 8
- 229960004011 methenamine Drugs 0.000 description 7
- 239000002086 nanomaterial Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- 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
- B01J13/20—After-treatment of capsule walls, e.g. hardening
- B01J13/22—Coating
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- C—CHEMISTRY; METALLURGY
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Abstract
The invention discloses a SiO2A @ ZnO core-shell structure polypod-bead nano composite material is prepared from SiO through preparing the SiO layer by chemical vapor deposition method2Growing ZnO seed crystal on the surface of the pellet in situ, ultrasonically crushing the seed crystal in a growth solution, standing, separating, washing and drying to obtain SiO2The @ ZnO core-shell structure polypod ball nano composite material. The ultrasonic crushing is adopted, an in-situ growth method is applied, the preparation condition is mild, the process is simple, and the method is suitable for large-area production. SiO prepared by the invention2The @ ZnO core-shell multi-legged pellet composite material has the advantages of uniform size, good dispersibility and controllable components, and is expected to be applied to photoelectric materials or photocatalytic materials and the like.
Description
Technical Field
The invention belongs to the technical field of new nano composite materials, and particularly relates to SiO2A preparation method and application of a @ ZnO core-shell structure polypod-bead nanocomposite material.
Background
ZnO is a typical wide-bandgap direct band-gap semiconductor material, has good biocompatibility and environmental safety, and is widely concerned by researchers as a promising photocatalytic material in recent years. It is well known that the structure, morphology, surface state, etc. of the photocatalyst directly affect its performance and application. By controlling the preparation process and conditions, ZnO nano materials with various sizes and shapes are obtained, and the photocatalytic activity of the ZnO nano materials is greatly improved. In practical application, the ZnO nano material has the defects of easy agglomeration of nano-sized materials, poor organic matter adsorption performance, low quantum yield and the like, which greatly limits the improvement of ZnO photocatalytic activity and application thereof. Based on the above, some ZnO/semiconductor heterojunction composite materials appear, and the preparation methods thereof are mostly hydrothermal/solvothermal. For example, SiO2 is compounded with ZnO, and the structure of the composite is mostly simple nanoparticles or spherical nanoparticles formed by taking ZnO as a core and SiO2 colloid as a shell. After SiO2 is compounded with ZnO, some properties such as photoluminescence property are improved. The hydrothermal/solvothermal method requires a closed high-temperature high-pressure environment and is not suitable for large-scale production. The ultrasonic crushing preparation material has the advantages of simplicity, convenience, rapidness, suitability for large-area preparation and the like. At present, ZnO nanorods are obtained by adopting ultrasonic crushing energy, but the composite material thereof has great difficulty in preparation and separation.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides SiO2A preparation method and application of a @ ZnO multi-legged pellet nano composite material with a core-shell structure aim to obtain the nano composite material with improved photocatalytic activity through a simple preparation process with mild conditions.
In order to achieve the purpose, the invention adopts the technical scheme that:
SiO (silicon dioxide)2A @ ZnO core-shell structure polypod-bead nano composite material is prepared from SiO2Growing ZnO seed crystal on the surface of the pellet in situ, ultrasonically crushing the seed crystal in a growth solution, standing, separating, washing and drying to obtain SiO2The @ ZnO core-shell structure polypod ball nano composite material.
The preparation method specifically comprises the following steps:
step one, SiO with negative electricity2Adding the small balls into a ZnO seed crystal solution with positive electricity, and oscillating and filtering to obtain SiO with ZnO seed crystals2A pellet;
step two, SiO with ZnO seed crystal2Adding the pellets into a mixed aqueous solution of hexamethylenetetramine and zinc nitrate;
step three, SiO with ZnO seed crystal2Ultrasonic pulverizing the mixed water solution of the small balls at 60-80 deg.C, standing for separation, washing and dryingDrying to obtain SiO2The @ ZnO core-shell structure polypod pellet.
The SiO2The ZnO seed crystal grown on the surface of the small ball in situ is formed by adding SiO with negative electricity2Adding the small balls into a ZnO seed crystal solution with positive electricity, and oscillating and filtering to obtain SiO with ZnO seed crystals2And (4) a small ball. SiO22The ZnO seed crystal is obtained on the surface of the small ball through electrostatic adsorption, so that the ZnO seed crystal and the ZnO seed crystal are conveniently adsorbed and combined, and the method is simple and efficient.
The SiO2The mass concentration ratio of the pellets to the ZnO seed crystal solution is 0.01g to 0.2-1.0 g/L. By adding the mass concentration ratio, SiO with ZnO seed crystal with better form can be obtained2Small balls of SiO2The ZnO seed crystals on the surfaces of the small balls are distributed more uniformly. If the seed concentration is too low, SiO2ZnO nanorods growing on the surfaces of the small spheres are rare, and a core-shell structure cannot be formed; if the seed concentration is too high, SiO2The ZnO nano-rod growing on the surface of the small ball is easy to fall off.
The growth solution adopts a mixed aqueous solution of hexamethylenetetramine and zinc nitrate, so that polypod globules with a core-shell structure can be generated conveniently, and other interference impurities are not easy to generate. The zinc nitrate can be Zn (NO)3)2●6H2O。
The molar ratio of the hexamethylene tetramine to the zinc nitrate is 1: 1. The growth solution with the molar ratio is convenient for SiO2The production of multi-legged globules with the @ ZnO core-shell structure and good particle crystallization.
The molar concentration of the hexamethylene tetramine and the zinc nitrate is 0.5-1.0 mmol/L. The adoption of the molar concentration range facilitates the obtainment of SiO with good form2The @ ZnO core-shell structure polypod pellet.
The temperature of ultrasonic pulverization in the growth solution is 60-80 ℃, and the time of ultrasonic pulverization is 1-4 h. Too low a crushing temperature of SiO2ZnO nano-rods are difficult to grow on the surfaces of the small spheres; the crushing time is less than 1h, the reaction time in the solution is short, the ZnO nano-rod does not grow completely, and the shape is irregular; the reaction mass in the solution was substantially exhausted in about 4h and the reaction was terminated.
The invention uses commercial SiO2The pellets are used as cores, ZnO nano-rods are deposited on the surfaces of the pellets,obtaining SiO2The @ ZnO core-shell structure polypod ball nano composite material. The multi-legged small ball nano structure ensures that the nano-legged small ball nano structure is stable in dispersion in a solution and not easy to settle, and particles do not agglomerate, so that the contact among nano-rods is reduced, and the reactive active sites in the catalytic reaction are increased, thereby improving the photocatalytic activity of the nano-legged small ball nano structure.
The invention has the beneficial effects that:
(1) the ultrasonic crushing is adopted, an in-situ growth method is applied, the preparation condition is mild, the process is simple, and the method is suitable for large-area production;
(2) the novel SiO prepared by the preparation method of the invention2The multi-legged ball nano composite material with the @ ZnO core-shell structure increases the reactive active sites in the catalytic reaction and improves the photocatalytic activity.
(3) SiO prepared by the invention2The @ ZnO core-shell structure polypod pellet composite material is uniform in size, good in dispersity and controllable in components.
(4) The novel SiO prepared by the preparation method of the invention2The @ ZnO multi-legged ball nano composite material with the core-shell structure has great application potential in the fields of adsorption and catalysis of organic matters in gas, sewage or wastewater and the like.
Drawings
The description includes the following figures, the contents shown are respectively:
FIG. 1 is an XRD pattern of a product prepared according to example 1 of the present invention;
FIG. 2 is an SEM image of a product prepared according to example 1 of the present invention;
wherein (a) SiO2Pellets, (b) SiO with ZnO seed2Pellets, (c) SiO prepared by (d)2@ ZnO multi-legged pellets of core-shell structure;
FIG. 3 is an SEM image of a product prepared according to example 2 of the present invention; wherein (a) the SEM of the sample obtained; (b) single SiO2SEM picture of @ ZnO core-shell structure pellet;
FIG. 4 is an SEM image of a product prepared according to example 3 of the present invention; wherein (a) the SEM of the sample obtained; (b) single SiO2SEM picture of @ ZnO core-shell structure pellet;
FIG. 5 is an SEM image of a product prepared according to example 4 of the present invention;
FIG. 6 is an SEM image of a product made according to example 5 of the present invention;
FIG. 7 is an SEM image of a comparative example 1 product of the present invention;
FIG. 8 is an SEM image of a comparative example 2 product of the present invention.
Detailed Description
The following detailed description of the embodiments of the present invention will be given with reference to the accompanying drawings for a purpose of helping those skilled in the art to more fully, accurately and deeply understand the concept and technical solution of the present invention and to facilitate its implementation.
The invention provides SiO2The preparation method of the @ ZnO multi-legged pellet with the core-shell structure comprises the step of preparing SiO2Growing ZnO seed crystal on the surface of the pellet in situ, ultrasonically crushing the seed crystal in a growth solution, standing, separating, washing and drying to obtain SiO2The @ ZnO core-shell structure polypod pellet.
The following is a detailed description of specific examples.
Example 1
(1) First 0.01g SiO2Adding the small ball into 0.5g/L ZnO seed crystal solution, oscillating for 24h, and filtering to obtain SiO with ZnO seed crystal2A pellet;
(2) preparing a mixed aqueous solution from 20mL of 0.625mmol/L Hexamethylenetetramine (HMT) and 20mL of 0.625mmol/L zinc nitrate, and inoculating the SiO seed crystal with the ZnO2Adding the small balls into the mixed aqueous solution;
(3) heating the mixed solution on an electric furnace to enable the temperature of the mixed solution to be 70 ℃, putting a probe of an ultrasonic crusher into the mixed solution, ultrasonically crushing for 4 hours, standing, settling, separating, washing and drying to obtain SiO2The @ ZnO core-shell structure polypod ball nano composite material.
The product was analyzed by X-ray light diffraction (XRD) and Scanning Electron Microscope (SEM).
Referring to FIG. 1, SiO with ZnO seed prepared in example 1 is shown2Pellets and SiO2XRD pattern of @ ZnO compositeFor comparison, commercial SiO is also given2XRD pattern of the pellet.
The result shows that the product of the embodiment contains crystallized ZnO, and the diffraction peak of ZnO is sharper, which indicates that the prepared ZnO particles are well crystallized.
FIG. 2 shows SiO used in the production of the product of example 12Pellets and production of SiO with seed2Pellets and prepared SiO2SEM picture of @ ZnO core-shell structure polypod beads. As can be seen from the figure, commercial SiO2The small spheres have smooth surfaces and uniform sizes and have diameters of about 800 nm. After oscillation treatment in ZnO seed crystal solution, SiO2The surface of the small ball is coarsened, and a plurality of attached particles appear on the surface.
Example 2
The present embodiment is different from embodiment 1 in that: the concentration of the ZnO seed crystal was 0.2 g/L. The product obtained is essentially identical to that of example 1, except that SiO is present due to the relatively low solubility of the seed crystals2The ZnO nanorods on the beads were not dense, and the scanning electron micrograph thereof is shown in FIG. 3. FIG. 3 (a) is an SEM image of a sample prepared so that SiO is present in the sample2The particles with the @ ZnO core-shell structure and the ZnO nanorods are difficult to separate, so a large number of ZnO nanorods can be seen simultaneously in the figure. (b) Is one SiO in the sample2SEM image of @ ZnO core-shell structure particle, from which obvious ZnO seed crystal particle, SiO2The ZnO nano-rods on the surfaces of the small spheres have uneven sizes.
Example 3
The present embodiment is different from embodiment 1 in that: the concentration of the ZnO seed crystal was 1.0 g/L. The scanning electron micrograph of the obtained product is substantially the same as that of example 1, and is shown in FIG. 4. Wherein (a) is an SEM image of a prepared sample and (b) is a single SiO2SEM image of @ ZnO core-shell structure particle. As can be seen from (a), the prepared sample was made of uniform SiO2The material is composed of @ ZnO core-shell structure particles, and ZnO nanorods are basically not found; as can be seen from (b), SiO2The surface is completely covered by ZnO nano-rods to form complete SiO2@ ZnO core-shell structure.
Example 4
The present embodiment is different from embodiment 1 in that: zinc nitrate is Zn (NO)3)2●6H2O，Zn(NO3)2●6H2The molar concentrations of O and hexamethylenetetramine are both 0.5 mol/L.
The product obtained in this example is substantially the same as that of example 1, and the diameter of the zinc oxide foot stick is slightly smaller, and its scanning electron microscope image is shown in fig. 5.
Example 5
The present embodiment is different from embodiment 1 in that: zinc nitrate is Zn (NO)3)2●6H2O， Zn(NO3)2●6H2O，Zn(NO3)2●6H2The molar concentration of O and hexamethylenetetramine is 1.0 mol/L.
The product obtained in this example is substantially the same as that of example 1, the diameter of the zinc oxide foot rod is large, and the scanning electron microscope image thereof is shown in fig. 6.
Comparative example 1
The present embodiment is different from embodiment 1 in that: preparation of SiO2In the case of the @ ZnO core-shell structure, SiO2The pellets were not treated with ZnO seed crystals.
The SEM spectrum of the product of this example is shown in FIG. 7. As can be seen from the figure, the product is made of SiO2Balls and ZnO nano-rods.
Comparative example 2
The present embodiment is different from embodiment 1 in that: and (3) heating the mixed solution on an electric furnace to ensure that the temperature of the mixed solution is 80 ℃, reacting for 2 hours without ultrasonic crushing, and then performing settling separation, washing and drying. The scanning electron microscope picture of the product is shown in FIG. 8, SiO2The surface of the small ball is basically not provided with ZnO nanorods, and only a few ZnO seed crystal nanoparticles are arranged.
The invention is described above with reference to the accompanying drawings. It is to be understood that the specific implementations of the invention are not limited in this respect. Various insubstantial improvements are made by adopting the method conception and the technical scheme of the invention; the present invention is not limited to the above embodiments, and can be modified in various ways.
Claims (7)
1. SiO (silicon dioxide)2The preparation method of the @ ZnO multi-legged pellet nanocomposite material with the core-shell structure is characterized in that the method is implemented by preparing SiO2Growing ZnO seed crystal on the surface of the pellet in situ, ultrasonically crushing the seed crystal in a growth solution, standing, separating, washing and drying to obtain SiO2@ ZnO core-shell structure polypod globule nanocomposite, SiO2The ZnO seed crystal grown on the surface of the small ball in situ is formed by adding SiO with negative electricity2Adding the small balls into a ZnO seed crystal solution with positive electricity, and oscillating and filtering to obtain SiO with ZnO seed crystals2And (4) a small ball.
2. SiO as in claim 12The preparation method of the @ ZnO multi-legged pellet nanocomposite material with the core-shell structure is characterized in that SiO2The mass concentration ratio of the pellets to the ZnO seed crystal solution is 0.01g to 0.2-1.0 g/L.
3. SiO as in claim 12The preparation method of the @ ZnO multi-legged ball nanocomposite with the core-shell structure is characterized in that the growth solution is a mixed aqueous solution of hexamethylenetetramine and zinc nitrate.
4. SiO according to claim 32The preparation method of the @ ZnO multi-legged ball nanocomposite with the core-shell structure is characterized in that the molar ratio of the hexamethylenetetramine to the zinc nitrate is 1: 1.
5. SiO according to claim 32The preparation method of the @ ZnO multi-legged pellet nanocomposite with the core-shell structure is characterized in that the molar concentrations of the hexamethylenetetramine and the zinc nitrate are 0.5-1.0mmol/L respectively.
6. SiO as in claim 12The preparation method of the @ ZnO multi-legged ball nano composite material with the core-shell structure is characterized in that the temperature of ultrasonic grinding in a growth solution is 60-80 DEG CThe ultrasonic pulverization time is 1-4 h.
7. SiO produced by the production method according to any one of claims 1 to 62The application of the @ ZnO core-shell structure polypod pellet nanocomposite in the adsorption of organic matters in gas or wastewater.
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| CN109428065A (en) * | 2017-08-28 | 2019-03-05 | 内蒙古欣蒙碳纳米科技有限公司 | A kind of preparation method of nanometer rods composite negative pole material |
| CN110124739B (en) * | 2019-06-03 | 2020-07-03 | 江南大学 | Nano-photocatalyst-loaded cross-linked CD-MOF composite material and preparation method thereof |
| CN111659374B (en) * | 2020-06-10 | 2023-07-14 | 江苏扬农化工集团有限公司 | Catalyst, preparation method thereof and method for synthesizing hexamethylenediamine intermediate |
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| CN104107689B (en) * | 2013-04-18 | 2016-06-29 | 宁波大学 | A kind of large aperture nano composite material and preparation method thereof |
| CN103480373B (en) * | 2013-09-05 | 2016-03-02 | 同济大学 | The preparation method of dandelion shape nucleocapsid structure AuZnO heterojunction photocatalyst |
| CN103816885B (en) * | 2014-02-20 | 2015-11-11 | 阜阳师范学院 | A kind of preparations and applicatio of nano zinc oxide photocatalyst |
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| CN104961151B (en) * | 2015-07-10 | 2017-03-08 | 中国科学院上海硅酸盐研究所 | A kind of Herba Taraxaci shape composite oxides nano-particle and its preparation method and application |
| CN105381802B (en) * | 2015-12-23 | 2018-10-02 | 哈尔滨工业大学 | One kind preparing dandelion shape Fe based on heterogeneous nucleation means3O4The methods and applications of@ZnO nucleocapsid compounds |
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