CN113713725A - Preparation method of hollow core-shell cubic zinc oxide/cobaltosic oxide/zinc oxide nano composite material - Google Patents
Preparation method of hollow core-shell cubic zinc oxide/cobaltosic oxide/zinc oxide nano composite material Download PDFInfo
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 38
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 title claims abstract description 15
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 15
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title abstract description 97
- 239000011787 zinc oxide Substances 0.000 title abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
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- 238000001354 calcination Methods 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000009388 chemical precipitation Methods 0.000 claims abstract description 5
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- 238000001035 drying Methods 0.000 claims abstract description 4
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- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 64
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 30
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 15
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
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- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 11
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 10
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- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
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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
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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
- B01J13/06—Making microcapsules or microballoons by phase separation
Abstract
The invention discloses a preparation method of a hollow core-shell cubic zinc oxide/cobaltosic oxide/zinc oxide nano composite material, which comprises the following steps: (1) preparing a solution containing solid cubic ZIF-8@ ZIF-67@ ZIF-8 nanoparticles at room temperature by adopting a chemical precipitation method; (2) centrifugally separating the precipitate, washing with absolute ethyl alcohol, and drying to obtain solid cubic ZIF-8@ ZIF-67@ ZIF-8 nanoparticles; (3) grinding solid cubic ZIF-8@ ZIF-67@ ZIF-8 nano particles and then calcining at high temperature to obtain hollow core-shell cubic ZnO @ Co3O4@ ZnO nanocomposite. The preparation method is simple and feasible, and the prepared material has regular shape, large specific surface area and a hollow core-shell cubic structure, and the hollow core-shell structure has potential application value in the field of gas sensors.
Description
Technical Field
The invention relates to the technical field of nano material production, in particular to a preparation method of a hollow core-shell cubic zinc oxide/cobaltosic oxide/zinc oxide nano composite material.
Background
Due to the enhancement of the awareness of environmental protection and the concern on the health problems of human beings, the important function of the gas sensor is gradually highlighted, and the research of researchers on improving the performance of the gas sensor is stimulated. For nano materials, the improvement of gas-sensitive performance is generally realized by constructing a heterojunction, doping, regulating and controlling morphology and the like. The p-n nano heterostructure for constructing the hollow core shell not only can furthest enlarge the contact area between two phases or multiple phases and provide more active sites, but also can improve the performance of the gas sensor due to the existence of the p-n heterojunction and the mutual synergistic effect between two or more semiconductor materials.
In recent years, Metal Organic Frameworks (MOFs) with high specific surface area and good pore structure have been demonstrated to be excellent precursor templates for the preparation of novel porous metal oxide nanostructures. By high temperature calcination, the metal ions in the MOFs may be converted to metal oxides, and C and other elements (e.g., N and H) may be oxidized to gases. Also, a porous oxide having interconnected pores is easily obtained due to gas release during calcination. The ZIFs are a branch of MOFs, and ZIF-8 and ZIF-67 have the same topological structure, are easy to carry out multilayer composite epitaxial growth and have better chemical stability and thermal stability. The metal oxide semiconductor nano material prepared by taking the metal oxide semiconductor nano material as a precursor and calcining at high temperature is increasingly applied to the field of gas sensing. For example, Zhang et al synthesized ZnO/Co using a metal organic framework (ZIF-8/ZIF-67) as a sacrificial template3O4Two-phase mixed hollow polyhedron p-n heterojunction nano material. ZnO/Co3O4Compared with ZnO prepared by the same method, the acetone sensing performance of the nano composite material is obviously improved, and the nano composite material has high response, good linearity and short response/recovery time; li et al prepared Co by calcining ZIF-8@ ZIF-673O4A quantum dot/ZnO nanocage heterojunction nano material. Through gas-sensitive test, the gas-sensitive detection reagent has the advantages of high response speed, low detection limit, high stability, high selectivity and the like for trimethylamine gas. Its high sensitivity response can be attributed to the increase of the depletion layer thickness caused by the p-n heterojunction and that each ZnO particle is made of several Co3O4The quantum dots are uniformly modified. However, ZIF-8/ZIF-67 prepared as described above andZIF-8@ ZIF-67 requires recovery of monomer (ZIF-8) nanoparticles for secondary compounding, the steps are complicated, and organic pollutants are generated; the prepared nano material has single appearance and limited regulation and control capability on the appearance of a sample material.
Many researches on preparing p-n heterojunction by taking ZIFs as a sacrificial template have been carried out, but few researches on preparing n-p-n or p-n-p double-heterojunction nano materials by taking ZIFs as a sacrificial template are carried out. The existing reported methods for synthesizing double-heterostructure are all completed by three-step or more reaction and have complex steps.
Disclosure of Invention
The invention aims to provide a preparation method of a hollow core-shell cubic zinc oxide/cobaltosic oxide/zinc oxide nano composite material, the preparation method is simple and feasible, the prepared material is regular in shape, large in specific surface area and of a hollow core-shell cubic structure, and the hollow core-shell structure has potential application value in the field of gas sensors.
The technical scheme adopted by the invention for solving the technical problems is as follows:
hollow core-shell cube ZnO @ Co3O4The preparation method of the @ ZnO nanocomposite comprises the following steps:
(1) preparing a solution containing solid cubic ZIF-8@ ZIF-67@ ZIF-8 nanoparticles at room temperature by adopting a chemical precipitation method;
(2) centrifugally separating the precipitate, washing with absolute ethyl alcohol, and drying to obtain solid cubic ZIF-8@ ZIF-67@ ZIF-8 nanoparticles;
(3) grinding solid cubic ZIF-8@ ZIF-67@ ZIF-8 nano particles and then calcining at high temperature to obtain hollow core-shell cubic ZnO @ Co3O4@ ZnO nanocomposite.
The invention prepares an n-p-n type double-heterojunction structure by taking ZIFs as a sacrificial template, and the advantages of the double-heterojunction structure are mainly reflected in that the charge transfer of electrons and holes is enhanced due to the coupling of a ternary semiconductor, so that the double-heterojunction structure can respond to various gases, wherein the gases comprise reducing gases and oxidizing gases. Second, ZnO @ Co prepared3O4The @ ZnO nano material is composed of three layers of semiconductor nano metal particlesThe assembled hollow core-shell is compact and the structure of a large interface is more beneficial to charge transfer.
The invention has the main innovation that the synthesis of solid cubic ZIF-8@ ZIF-67@ ZIF-8 nano particles, ZIF-8@ ZIF-67@ ZIF-8, and the conventional synthesis method of ZIF-8@ ZIF-67@ ZIF-8 comprises three steps, namely, firstly synthesizing ZIF-8, secondly synthesizing ZIF-8@ ZIF-67, and finally synthesizing ZIF-8@ ZIF-67@ ZIF-8. Therefore, the synthesis steps are complicated, the solvent consumption is large, and the production cost is high. Meanwhile, the conventional synthesis method needs a large amount of organic solvent, and the reaction conditions of high temperature and high pressure for a long time consume energy and time, so that the environmental hazard is large and the production safety is low. The synthesis environment of the invention is carried out at normal temperature and normal pressure, water is used as a solvent system in an open environment, potential environmental hazards caused by using an organic solvent are avoided, high-temperature and high-pressure long-time reaction conditions are also avoided, and the sequence of forming solution and mixing materials in each step is very critical.
In conventional ZnO @ Co3O4In the preparation method, only a preparation step of simply adding ZIF-8 is adopted, and the inventor finds that ZnO @ Co cannot be prepared3O4@ ZnO material, possibly related to the surface properties of ZIF-8 and ZIF-67. Therefore, the inventor improves the synthesis method, and the synthesis method specifically adds Cetyl Trimethyl Ammonium Bromide (CTAB) to adjust the morphology in the synthesis of ZIF-8@ ZIF-67@ ZIF-8, CTAB is used as a capping agent, the long chain of the CTAB can adsorb the surface of a synthesized ZIF material crystal nucleus, only a specific crystal face is exposed, the crystal nucleus grows along the specific crystal face, and ZnO @ Co is obtained by calcination after the morphology is adjusted by the CTAB3O4The @ ZnO composite material well keeps the morphology of the precursor, is regular in morphology and large in specific surface area, and forms a unique hollow core-shell cubic structure. Meanwhile, the appearance is adjusted by CTAB and matched with the aqueous reaction system of the invention, so that the prepared ZnO @ Co3O4@ ZnO is not easily agglomerated. The method is very critical because cetyl trimethyl ammonium bromide is added in the preparation of each metal source solution, dodecahedron appears when CTAB is not added every time, a ZIF-8@ ZIF-67@ ZIF-8 solid cubic structure can be formed only by fully ensuring the existence of CTAB in the solution, and ZnO @ Co-8 solid cubic structure is finally prepared3O4@ ZnO hollow core-shell cubic structure.
Preferably, the specific process of step (1) is as follows:
at room temperature, firstly, respectively preparing an aqueous solution A containing 2-methylimidazole and an aqueous solution B containing hexadecyl trimethyl ammonium bromide and zinc nitrate hexahydrate; quickly pouring the aqueous solution B into the aqueous solution A, and uniformly stirring;
then, preparing an aqueous solution C containing hexadecyl trimethyl ammonium bromide and cobalt nitrate hexahydrate; quickly pouring the aqueous solution C into the aqueous solution A poured with the aqueous solution B, and uniformly stirring;
finally, preparing an aqueous solution D containing hexadecyl trimethyl ammonium bromide and zinc nitrate hexahydrate; quickly pouring the aqueous solution D into the aqueous solution A into which the aqueous solution B and the aqueous solution C are poured, uniformly stirring, and standing and aging.
Preferably, in the aqueous solution A, the mass-volume ratio of the 2-methylimidazole to the deionized water is 4-5 g: 70 mL.
Preferably, in the aqueous solution B, cetyltrimethylammonium bromide: zinc nitrate hexahydrate: deionized water = 4-5 mg: 295-300 mg: 7 mL.
Preferably, in the aqueous solution C, cetyltrimethylammonium bromide: cobalt nitrate hexahydrate: deionized water = 4-5 mg: 289-293 mg: 7 mL.
Preferably, in the aqueous solution D, cetyltrimethylammonium bromide: zinc nitrate hexahydrate: deionized water = 4-5 mg: 295-300 mg: 7 mL.
Preferably, the zinc nitrate hexahydrate in aqueous solution B: cobalt nitrate hexahydrate in aqueous solution C: zinc nitrate hexahydrate in aqueous solution D: the molar ratio of 2-methylimidazole is 1: 1: 1: 54 to 57.
Preferably, the standing and aging time is 5 to 20 hours.
Preferably, in the step (2), the centrifugation is carried out for 3-5 times, the centrifugation rotating speed is 6000-8000 rpm, and the centrifugation is carried out for 5-10 min each time.
Preferably, in the step (3), the high-temperature calcination is carried out at a temperature of 400-450 ℃, a temperature rise rate of 1-10 ℃/min, and the calcination is carried out for 1-2 h.
The invention has the beneficial effects that:
1. synthesizing the n-p-n heterojunction nano material by a simple chemical precipitation method and high-temperature calcination;
2. synthetic ZnO @ Co3O4The @ ZnO nano material is a hollow core-shell hierarchical structure assembled by three layers of nano metal particles;
3. the gas sensor is not easy to agglomerate, has larger specific surface area and higher chemical activity, and has excellent gas-sensitive performance because a large number of surface particles are in surface contact;
4. the method is simple to operate, high-precision instruments and equipment are not needed, and the precursors are not needed to be separated.
5. Synthetic ZnO @ Co3O4The @ ZnO nanomaterial has excellent electron hole mobility.
6. Provides a new idea for preparing multilayer double-heterojunction nano materials.
Drawings
FIG. 1 is a hollow core-shell cube ZnO @ Co prepared in EXAMPLE 13O4Scanning Electron Microscope (SEM) picture of @ ZnO nano material.
FIG. 2 is a hollow core-shell cube ZnO @ Co prepared in EXAMPLE 23O4Scanning Electron Microscope (SEM) picture of @ ZnO nano material.
FIG. 3 is a hollow core-shell cube ZnO @ Co prepared in EXAMPLE 33O4Scanning Electron Microscope (SEM) picture of @ ZnO nano material.
FIG. 4 is a hollow core-shell cube ZnO @ Co prepared in example 43O4Scanning Electron Microscope (SEM) picture of @ ZnO nano material.
FIG. 5 is a hollow core-shell cube ZnO @ Co prepared in example 53O4Scanning Electron Microscope (SEM) picture of @ ZnO nano material.
FIG. 6 is a hollow core-shell cube ZnO @ Co prepared in example 13O4Scanning Transmission Electron Microscope (STEM) photo of @ ZnO nano-material.
FIG. 7 is a hollow core shell cube ZnO @ Co prepared in examples 1-53O4X-ray electron diffraction (XRD) photograph of @ ZnO nano material。
FIG. 8 is a prepared hollow core-shell cube ZnO @ Co3O4Structure schematic diagram of @ ZnO nanomaterial.
FIG. 9 is a hollow core-shell cube ZnO @ Co prepared in example 13O4And a Transmission Electron Microscope (TEM) picture of the @ ZnO nano material.
FIG. 10 is a hollow core-shell cube ZnO @ Co prepared in example 13O4@ ZnO nanomaterial element surface distribution (SED) picture.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
General implementation:
hollow core-shell cube ZnO @ Co3O4The preparation method of the @ ZnO nanocomposite comprises the following steps:
(1) preparing a solution containing solid cubic ZIF-8@ ZIF-67@ ZIF-8 nanoparticles at room temperature by adopting a chemical precipitation method;
the specific process is as follows:
at room temperature, firstly, respectively preparing an aqueous solution A containing 2-methylimidazole and an aqueous solution B containing hexadecyl trimethyl ammonium bromide and zinc nitrate hexahydrate; quickly pouring the aqueous solution B into the aqueous solution A, and uniformly stirring;
then, preparing an aqueous solution C containing hexadecyl trimethyl ammonium bromide and cobalt nitrate hexahydrate; quickly pouring the aqueous solution C into the aqueous solution A poured with the aqueous solution B, and uniformly stirring;
finally, preparing an aqueous solution D containing hexadecyl trimethyl ammonium bromide and zinc nitrate hexahydrate; and quickly pouring the aqueous solution D into the aqueous solution A poured with the aqueous solution B and the aqueous solution C, uniformly stirring, standing and aging for 5-20 hours.
In the aqueous solution A, the mass-to-volume ratio of the 2-methylimidazole to the deionized water is 4-5 g: 70 mL. In aqueous solution B, cetyltrimethylammonium bromide: zinc nitrate hexahydrate: deionized water = 4-5 mg: 295-300 mg: 7 mL. In aqueous solution C, cetyltrimethylammonium bromide: cobalt nitrate hexahydrate: deionized water = 4-5 mg: 289-293 mg: 7 mL. In aqueous solution D, cetyltrimethylammonium bromide: zinc nitrate hexahydrate: deionized water = 4-5 mg: 295-300 mg: 7 mL. Zinc nitrate hexahydrate in aqueous solution B: cobalt nitrate hexahydrate in aqueous solution C: zinc nitrate hexahydrate in aqueous solution D: the molar ratio of 2-methylimidazole is 1: 1: 1: 54 to 57.
(2) Centrifuging for 3-5 times at a rotating speed of 6000-8000 rpm for 5-10 min each time, washing with absolute ethyl alcohol, and drying to obtain solid cubic ZIF-8@ ZIF-67@ ZIF-8 nanoparticles;
(3) grinding solid cube ZIF-8@ ZIF-67@ ZIF-8 nanoparticles, calcining at a high temperature of 400-450 ℃, at a heating rate of 1-10 ℃/min for 1-2 h to obtain hollow core-shell cube ZnO @ Co3O4@ ZnO nanocomposite.
Example 1: hollow core-shell cube ZnO @ Co3O4The preparation method of the @ ZnO nano composite material comprises the following specific steps:
first, 70mL of an aqueous solution A containing 4.6g of 2-methylimidazole (2-MeIM) and 7mL of an aqueous solution B containing 4mg of cetyltrimethylammonium bromide (CTAB) and 297.49mg of zinc nitrate hexahydrate were prepared at room temperature, respectively; after stirring uniformly, the foamy colorless transparent solution B is quickly poured into the solution A, and the solution is fully stirred for 5 hours at the speed of 500 rmp/min. Secondly, preparing 7mL of aqueous solution C containing 4mg of CTAB and 291.03mg of cobalt nitrate hexahydrate; after stirring uniformly, the bubbly pink solution C was quickly poured into the solution A, and stirred well at 500rmp/min for 5 hours. Finally, preparing 7mL of aqueous solution D containing 4mg of CTAB and 297.49mg of zinc nitrate hexahydrate; after stirring evenly, quickly pouring the foamy colorless transparent solution D into the solution A, fully stirring for 5 hours at 500rmp/min, and then standing and aging for 24 hours.
And secondly, centrifuging the purple solution completely reacted for 4 times by using a centrifuge, wherein the centrifugation time is 5min each time, and the rotation speed is 7000 rmp/min. The precipitate was washed with absolute ethanol and then dried in an air-blown dry oven at 60 ℃ for 24 hours.
Thirdly, grinding the completely dried sample, spreading the sample in a porcelain boat for high-temperature calcination, setting the calcination temperature to be 450 ℃, the heating rate to be 5 ℃/min, and calcining for 2 hours to obtain the available ZnO @ Co3O4@ ZnO nanocomposite. Its scanning image (SEM) is shown in FIG. 1; scanning transmission map (STEM) see fig. 6; the X-ray diffraction (XRD) pattern is shown in FIG. 7 (c).
Example 2:
this example differs from example 1 in that: the temperature increase rate set in the third step was 1 ℃/min, and the rest was the same as in example 1. The scanning image is shown in FIG. 2; the X-ray diffraction (XRD) pattern is shown in FIG. 7 (a).
Example 3:
this example differs from examples 1 and 2 in that: the temperature increase rate set in the third step was 2 ℃/min, and the other steps were the same as in examples 1 and 2. The scanning image is shown in FIG. 3; the X-ray diffraction (XRD) pattern is shown in FIG. 7 (b).
Example 4:
this example differs from examples 1 to 3 in that: the temperature increase rate set in the third step was 10 ℃/min, and the others were the same as in examples 1 to 3. The scanning image is shown in FIG. 4; the X-ray diffraction (XRD) pattern is shown in FIG. 7 (d).
Example 5:
this example differs from example 1 in that: the calcination time set in the third step was 1 hour, and the rest was the same as in example 1. The scanning image is shown in FIG. 5; the X-ray diffraction (XRD) pattern is shown in fig. 7 (e).
As can be seen from FIG. 1, the hollow core-shell ZnO @ Co synthesized in example 13O4The @ ZnO nano material perfectly inherits the structural morphology of a precursor ZIF-8@ ZIF-67@ ZIF-8. The size is uniform, and the framework structure is stable; no obvious damage phenomenon. The size of the synthesized hollow cube is about 150 nanometers. From fig. 6, a distinct hollow cubic structure is observed in the scanning electron microscope scan through mode, with a wall thickness of about 40 nm.
Fig. 2 to 5 are respectively alignedExamples 2 to 5 should be used. As can be seen by comparison of scanning pictures, when the heat preservation time is not changed (2 h), under the condition of lower temperature rise rate (1 ℃/min), the synthesized hollow core-shell ZnO @ Co3O4The surface of the @ ZnO nano material has larger pores and the metal oxide particles formed on the surface have larger sizes. This may be due to the relatively extensive calcination caused by the slow rate of temperature rise. In the case of a high temperature rise rate (10 ℃/min), the precursor within the shell structure will have not yet reacted until it is stable due to the rapid temperature rise. Thus, the synthesized hollow core-shell ZnO @ Co3O4@ ZnO nanomaterial is severely damaged. In conclusion, when the heating rate is 5 ℃/min, the synthesized hollow core-shell ZnO @ Co3O4The @ ZnO nano material has the optimal ideal morphology.
Fig. 7 is an X-ray diffraction (XRD) pattern of examples 1 to 5, and (a), (b), (c), (d) and (e) correspond to example 2, example 3, example 1, example 4 and example 5, respectively. The synthesized hollow core-shell ZnO @ Co can be seen from the picture3O4The peak type of @ ZnO nanomaterial is ZnO and Co3O4Superposition of peak patterns, the main crystal structure being formed by cubic Co3O4(JCPDS # 42-1467) and hexagonal phase ZnO (JCPDS # 89-0511).
From fig. 9 and 10 we can see clearly the hollow core-shell structure, the cube is formed by stacking one nanoparticle, the wall thickness is about 30 nm, and there is a distinct core structure inside. Through the element distribution diagram, the structure of the intermediate core can be determined to be ZnO, and the wall layer of the cube is formed by ZnO and Co3O4。
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (10)
1. Hollow core-shell cube ZnO @ Co3O4@ ZnO nanocompositeThe preparation method of the material is characterized by comprising the following steps:
(1) preparing a solution containing solid cubic ZIF-8@ ZIF-67@ ZIF-8 nanoparticles at room temperature by adopting a chemical precipitation method;
(2) centrifugally separating the precipitate, washing with absolute ethyl alcohol, and drying to obtain solid cubic ZIF-8@ ZIF-67@ ZIF-8 nanoparticles;
(3) grinding solid cubic ZIF-8@ ZIF-67@ ZIF-8 nano particles and then calcining at high temperature to obtain hollow core-shell cubic ZnO @ Co3O4@ ZnO nanocomposite.
2. The method according to claim 1, wherein the specific process of step (1) is as follows:
at room temperature, firstly, respectively preparing an aqueous solution A containing 2-methylimidazole and an aqueous solution B containing hexadecyl trimethyl ammonium bromide and zinc nitrate hexahydrate; quickly pouring the aqueous solution B into the aqueous solution A, and uniformly stirring;
then, preparing an aqueous solution C containing hexadecyl trimethyl ammonium bromide and cobalt nitrate hexahydrate; quickly pouring the aqueous solution C into the aqueous solution A poured with the aqueous solution B, and uniformly stirring;
finally, preparing an aqueous solution D containing hexadecyl trimethyl ammonium bromide and zinc nitrate hexahydrate; quickly pouring the aqueous solution D into the aqueous solution A into which the aqueous solution B and the aqueous solution C are poured, uniformly stirring, and standing and aging.
3. The preparation method according to claim 2, wherein the mass-to-volume ratio of the 2-methylimidazole to the deionized water in the aqueous solution A is 4-5 g: 70 mL.
4. The method according to claim 2, wherein, in the aqueous solution B, the ratio of cetyltrimethylammonium bromide: zinc nitrate hexahydrate: deionized water = 4-5 mg: 295-300 mg: 7 mL.
5. The method according to claim 2, wherein, in the aqueous solution C, the ratio of cetyltrimethylammonium bromide: cobalt nitrate hexahydrate: deionized water = 4-5 mg: 289-293 mg: 7 mL.
6. The method according to claim 2, wherein, in the aqueous solution D, the ratio of cetyltrimethylammonium bromide: zinc nitrate hexahydrate: deionized water = 4-5 mg: 295-300 mg: 7 mL.
7. The method of claim 2, wherein the ratio of zinc nitrate hexahydrate in aqueous solution B: cobalt nitrate hexahydrate in aqueous solution C: zinc nitrate hexahydrate in aqueous solution D: the molar ratio of 2-methylimidazole is 1: 1: 1: 54 to 57.
8. The method according to claim 2, wherein the standing and aging time is 5 to 20 hours.
9. The preparation method according to claim 1, wherein in the step (2), the centrifugation is performed 3-5 times at 6000-8000 rpm for 5-10 min.
10. The preparation method according to claim 1, wherein in the step (3), the high-temperature calcination is performed at a temperature of 400 to 450 ℃, at a temperature rise rate of 1 to 10 ℃/min, and for 1 to 2 hours.
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