CN107381659A - The method that template prepares aspherical hollow structure nanocages composite - Google Patents
The method that template prepares aspherical hollow structure nanocages composite Download PDFInfo
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- CN107381659A CN107381659A CN201710504837.3A CN201710504837A CN107381659A CN 107381659 A CN107381659 A CN 107381659A CN 201710504837 A CN201710504837 A CN 201710504837A CN 107381659 A CN107381659 A CN 107381659A
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Cobaltates
- C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
- C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
- C01G51/52—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese of the type [Mn2O4]2-, e.g. Li2(CoxMn2-x)O4, Li2(MyCoxMn2-x-y)O4
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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Abstract
The invention belongs to metal organic composite material technical field, is related to the method that nanocages composite is prepared using zeolite imidazole ester skeleton as template, more particularly to the method for preparing aspherical hollow structure nanocages composite with ZIF 67 for template.The present invention first synthesizes the nanocrystals of ZIF 67, then with ZIF 67 is template, is scattered in the ethanol solution of nitrate, stirring, centrifugation, after drying, with 2 DEG C of min in 300~350 DEG C of air‑1Speed anneal 2~3h be prepared.Operating condition is easily controllable, and equipment is simple, prepares the nanocages composite for the mass ratio synthesis hollow structure that cost is low, by adjusting zinc nitrate and copper nitrate, and obtained product grain is evenly distributed, and Particle dispersity is good, and split reunion degree is smaller, and pattern is preferable.Present invention process is simple, and raw material is readily available, and cost is cheap, of reduced contamination, suitable for industrialized production.
Description
Technical field
The invention belongs to metal organic composite material technical field, is related to and prepares nanometer by template of zeolite imidazole ester skeleton
The method of cage composite, more particularly to prepare using ZIF-67 as template the side of aspherical hollow structure nanocages composite
Method.
Background technology
Metal organic framework (MOFs) be used as a kind of novel organic-inorganic hybrid material, can by metal ion with it is organic
Part assembles in a suitable solvent.In addition, the metallic element and organic matter of composition metal organic framework compound can be one
Metal/metal oxide is converted under conditions of fixed, uniformity and pure property due to MOFs compositions, obtained metal oxidation
Thing has highly uniform structure and composition.
Metal organic framework has very big potentiality in terms of gas storage, catalysis, sensing and drug delivery.In recent years,
Because MOF has higher surface area, good heat endurance and high porosity, therefore as template and precursor synthesis transition gold
The function nano material of category, causes extensive concern.People have been carried out greatly to MOFs size and dimension control synthesis
The experiment of amount, it is already possible to which as template, this expands template for nanometer and minute yardstick MOF of the selection with various species and structure
Selection.But so far, although MOF template-policies achieve lasting progress, because the form of MOF precursors is limited,
Anisotropy hollow-core construction of the production with high degree of symmetry geometry is still relatively fewer, and lacks Morphological Diversity, hinders
MOF and its derivative has been hindered to be more widely used.Therefore, developing a kind of manufacture the simple of the aspherical hollow structure of anisotropy can
The method leaned on is very important, and challenging.
Three-dimensional (3D) hollow structure causes great interest of the people to its interesting architectural feature and enhancing performance, generally system
Three-dimensional (3D) hollow nanostructures made, the surface area of electronics and shorter diffusion path, the aspheric of open report can be increased
The higher curvature face of shape hollow structure and anisotropic morphology have very big influence to its property.However, on aspherical
The synthesis report of the hollow structure of form is still seldom.
Zeolite imidazole vinegar framework compound（ZIFs）It is a kind of crystalline porous MOFs, the structure of ZIFs materials and traditional boiling
Stone molecular sieve is similar, but has difference again on architecture model.ZIFs is to be substituted by transition metal ions such as Zn or Co in zeolite
Si and Al, the bridging oxygen in the derivative substitution zeolite of imidazoles or imidazoles, be connected by the N atoms on imidazole ring to be formed
A species zeolitic material.ZIFs materials have the Common advantages of zeolite and metal organic framework, such as high specific surface area, height
Crystallinity, superior heat endurance and chemical stability.
The functional nano with aspherical hollow structure is obtained using zeolite imidazole ZIF-67 nanocrystals as template
Cage composite, the composite of synthesis have the characteristics of nanocages of different shell compositions.It is a variety of particularly compared with monometallic
Transition metal or various metal oxide hybrid materials usually provide more preferable capacity and cyclical stability, and this is to energy device
Beneficial.
The content of the invention
The purpose of the present invention is to prepare aspherical hollow structure nanocages composite by template of ZIF-67.
The method that template prepares aspherical hollow structure nanocages composite, ZIF-67 nanocrystals are first synthesized, then
Using ZIF-67 as template, it is scattered in the ethanol solution of nitrate, after stirring, centrifugation, drying, in 300~350 DEG C of sky
With 2 DEG C of min in gas-1Speed anneal 2~3h be prepared.
Wherein, the synthesis of the ZIF-67 nanocrystals, including：Weigh cobalt nitrate and 2-methylimidazole is dissolved in first respectively
Solution is stirred evenly into alcohol, the wherein mol ratio of cobalt nitrate and 2-methylimidazole is 1：4.0~16, preferably 1:4, methanol volume is 25
~45mL, solute unit for mM, preferred 25mL methanol；Then 2-methylimidazole solution is poured into rapidly nitre under agitation
In acidic cobalt solution, rear 12~36h of aged at room temperature, preferably 24h are sufficiently stirred, through being collected by centrifugation to obtain violet precipitate and at 60 DEG C
Lower dry 12h obtains ZIF-67 nanocrystals.
In the more excellent disclosed example of the present invention, the nitrate is that both zinc nitrate, copper nitrate or zinc nitrate and copper nitrate are mixed
Compound.
In the more excellent disclosed example of the present invention, the nitrate is six nitric hydrate salt.
The more excellent disclosed example of the present invention, ZnCo is made when the nitrate is zinc nitrate2O4@Co3O4It is aspherical hollow
Structure nano cage, including：ZIF-67 is dispersed in the ethanol solution of zinc nitrate, the ZIF-67：Zinc nitrate：The quality of ethanol
Volume ratio is 40mg：20~80mg：15~35mL, preferably 40mg：80mg：25mL, after persistently stirring 1h, form ZIF-67
/ Zn-Co hydroxide nano cage particles dry 12h, then in 300~350 DEG C of air by centrifuging and collecting at 60 DEG C
In with 2 DEG C of min-1Speed by ZIF-67/Zn-Co hydroxide nano cages particle anneal 2~3h, preferably 350 DEG C, 2h, obtain
ZnCo2O4@Co3O4Aspherical hollow structure nanocages.
The more excellent disclosed example of the present invention, CuO@Co are made when the nitrate is copper nitrate3O4Aspherical hollow structure
Nanocages, including：ZIF-67 is dispersed in the ethanol solution of copper nitrate, the ZIF-67：Copper nitrate：The quality volume of ethanol
Than for 40mg：20~80mg：15~35mL, preferably 40mg：80mg：25mL, after persistently stirring 1h, formation ZIF-67/
Cu-Co hydroxide nano cage particles dry 12h, then in 300~350 DEG C of air by centrifuging and collecting at 60 DEG C
In with 2 DEG C of min-1Speed by ZIF-67/Cu-Co hydroxide nano cages particle anneal 2~3h, preferably 350 DEG C, 2h, obtain
CuO@Co3O4Aspherical hollow structure nanocages.
The more excellent disclosed example of the present invention, the nitrate are that CuO@are made when mixing in zinc nitrate and copper nitrate equal proportion
ZnCo2O4@Co3O4Aspherical hollow structure nanocages：ZIF-67 is dispersed in the ethanol solution of zinc nitrate and copper nitrate, institute
State ZIF-67：Zinc nitrate：Copper nitrate：The mass volume ratio of ethanol is 40mg：10~70mg：10~70mg：15~35mL, it is excellent
Select 40mg：40mg：40mg：25mL, stir 1h after, formed ZIF-67/Cu-Zn-Co hydroxide nano cage particles by from
The heart is simultaneously collected, and 12h is dried at 60 DEG C, then with 2 DEG C of min in 300~350 DEG C of air-1Speed by ZIF-67/ Cu-
Zn-Co hydroxide nano cages particle 2~3h of annealing, 2h, obtains CuO@ZnCo by preferably 350 DEG C2O4@Co3O4It is aspherical hollow
Structure nano cage.
Reagent used in the present invention is all commercially available, and analysis is pure.
Beneficial effect
The present invention is with solvent structure zeolite imidazole ZIF-67 nanocrystals, and using it as template, by adjusting zinc nitrate
The nanocages composite of hollow structure is synthesized with the mass ratio of copper nitrate.Its operating condition is easily controllable, and equipment is simple, prepares
Cost is low, and made product grain is evenly distributed, and Particle dispersity is good, and split reunion degree is smaller, and pattern is preferable, work of the present invention
Skill is simple, and raw material is readily available, and cost is cheap, of reduced contamination, suitable for industrialized production.
Brief description of the drawings
Fig. 1 is the CuO@ZnCo of aspherical hollow structure made from embodiment 12O4@Co3O4The electricity of nanocages composite
The micro- scanning electron microscope (SEM) photograph of son（SEM）
Fig. 2 is the X ray diffracting spectrum of the nanocages composite of obtained aspherical hollow structure（XRD）, wherein a is implementation
CuO@Co made from example 13O4Aspherical hollow structure nanocages, b are ZnCo made from embodiment 12O4@Co3O4It is aspherical hollow
Structure nano cage, c are CuO@ZnCo made from embodiment 12O4@Co3O4Aspherical hollow structure nanocages.
Embodiment
With reference to specific implementation example, the present invention will be further described, so that those skilled in the art more fully understand this hair
It is bright, but the invention is not limited in following examples.
Embodiment 1
Weigh 1.0mmol cobalt nitrates and 4.0mmol 2-methylimidazoles are dissolved in two kinds of solution of formation in 25mL methanol respectively.So
Afterwards, 2-methylimidazole solution is poured into cobalt nitrate solution rapidly under agitation, after stirring 5 minutes, gained mixed solution is in room
The lower aging of temperature 24 hours.Violet precipitate is collected by centrifugation and is dried 12 hours at 60 DEG C and obtains product ZIF-67 nanocrystals.
40mg ZIF-67 are dispersed in the ethanol that 25mL contains 80mg zinc nitrates.After stirring 1h, formation ZIF-67/
Zn-Co hydroxide nano cage particles, centrifuge and collect, and are finally dried 12 hours at 60 DEG C.Then, in 350 DEG C of air
In with 2 DEG C of min-1Speed by ZIF-67/Zn-Co hydroxide nano cages particle anneal 2 hours, obtain ZnCo2O4@Co3O4Aspheric
Shape hollow structure nanocages.
40mg ZIF-67 are dispersed in the ethanol that 25mL contains 80mg copper nitrates.After stirring 1h, formation ZIF-67/
Cu-Co hydroxide nano cage particles, centrifuge and collect, and are finally dried 12 hours at 60 DEG C.Then, in 350 DEG C of air
In with 2 DEG C of min-1Speed by ZIF-67/Cu-Co hydroxide nano cages particle anneal 2 hours, obtain CuO@Co3O4It is aspherical
Hollow structure nanocages.
40mg ZIF-67 are dispersed in the ethanol that 25mL contains 40mg copper nitrates and 40mg zinc nitrates.After stirring 1h, shape
Into ZIF-67/Cu-Zn-Co hydroxide nano cage particles, centrifuge and collect, finally dried 12 hours at 60 DEG C.Then,
With 2 DEG C of min in 350 DEG C of air-1Speed by ZIF-67/ Cu-Zn-Co hydroxide nano cages particle anneal 2 hours,
Obtain CuO@ZnCo2O4@Co3O4Aspherical hollow structure nanocages.
The metal composite oxide synthesized as can be seen from Figure 1 remains in that ZIF-67 hollow polyhedral structure, table
Face becomes coarse so that it has more avtive spot, can preferably with electrolyte contacts, from multiaspect body case it is broken from
It is able to observe that the hollow structure of nanocages inner casing.And nanocages crystalline size difference is little, is advantageous to chemical property
Play.Contrasted from Fig. 2 XRD and standard card, do not detect the signal of other impurity, show that the purity of product is high.
Embodiment 2
Weigh 1.0mmol cobalt nitrates and 4.0mmol 2-methylimidazoles are dissolved in two kinds of solution of formation in 25mL methanol respectively.So
Afterwards, 2-methylimidazole solution is poured into cobalt nitrate solution rapidly under agitation, after stirring 5 minutes, gained mixed solution is in room
The lower aging of temperature 24 hours.Violet precipitate is collected by centrifugation and is dried 12 hours at 60 DEG C and obtains product ZIF-67 nanocrystals.
40mg ZIF-67 are dispersed in the ethanol that 25mL contains 80mg zinc nitrates.After stirring 1h, formation ZIF-67/
Zn-Co hydroxide nano cage particles, centrifuge and collect, and are finally dried 12 hours at 60 DEG C.Then, in 300 DEG C of air
In with 2 DEG C of min-1Speed by ZIF-67/Zn-Co hydroxide nano cages particle anneal 2 hours, obtain ZnCo2O4@Co3O4Aspheric
Shape hollow structure nanocages.
40mg ZIF-67 are dispersed in the ethanol that 25mL contains 80mg copper nitrates.After stirring 1h, formation ZIF-67/
Cu-Co hydroxide nano cage particles, centrifuge and collect, and are finally dried 12 hours at 60 DEG C.Then, in 300 DEG C of air
In with 2 DEG C of min-1Speed by ZIF-67/Cu-Co hydroxide nano cages particle anneal 2 hours, obtain CuO@Co3O4It is aspherical
Hollow structure nanocages.
40mg ZIF-67 are dispersed in the ethanol that 25mL contains 40mg copper nitrates and 40mg zinc nitrates.After stirring 1h,
ZIF-67/Cu-Zn-Co hydroxide nano cage particles are formed, centrifuges and collects, are finally dried 12 hours at 60 DEG C.So
Afterwards, with 2 DEG C of min in 300 DEG C of air-1Speed the annealing of ZIF-67/ Cu-Zn-Co hydroxide nano cages particle is 2 small
When, obtain CuO@ZnCo2O4@Co3O4Aspherical hollow structure nanocages.
Embodiment 3
Weigh 1.0mmol cobalt nitrates and 16.0mmol 2-methylimidazoles are dissolved in two kinds of solution of formation in 45mL methanol respectively.So
Afterwards, 2-methylimidazole solution is poured into cobalt nitrate solution rapidly under agitation, after stirring 5 minutes, gained mixed solution is in room
The lower aging of temperature 36 hours.Violet precipitate is collected by centrifugation and is dried 12 hours at 60 DEG C and obtains product ZIF-67 nanocrystals.
40mg ZIF-67 are dispersed in the ethanol that 25mL contains 80mg zinc nitrates.After stirring 1h, formation ZIF-67/
Zn-Co hydroxide nano cage particles, centrifuge and collect, and are finally dried 12 hours at 60 DEG C.Then, in 350 DEG C of air
In with 2 DEG C of min-1Speed by ZIF-67/Zn-Co hydroxide nano cages particle anneal 2 hours, obtain ZnCo2O4@Co3O4Aspheric
Shape hollow structure nanocages.
40mg ZIF-67 are dispersed in the ethanol that 25mL contains 80mg copper nitrates.After stirring 1h, formation ZIF-67/
Cu-Co hydroxide nano cage particles, centrifuge and collect, and are finally dried 12 hours at 60 DEG C.Then, in 350 DEG C of air
In with 2 DEG C of min-1Speed by ZIF-67/Cu-Co hydroxide nano cages particle anneal 2 hours, obtain CuO@Co3O4It is aspherical
Hollow structure nanocages.
40mg ZIF-67 are dispersed in the ethanol that 25mL contains 40mg copper nitrates and 40mg zinc nitrates.After stirring 1h, shape
Into ZIF-67/Cu-Zn-Co hydroxide nano cage particles, centrifuge and collect, finally dried 12 hours at 60 DEG C.Then,
With 2 DEG C of min in 350 DEG C of air-1Speed by ZIF-67/ Cu-Zn-Co hydroxide nano cages particle anneal 2 hours,
Obtain CuO@ZnCo2O4@Co3O4Aspherical hollow structure nanocages.
Embodiment 4
Weigh 1.0mmol cobalt nitrates and 4.0mmol 2-methylimidazoles are dissolved in two kinds of solution of formation in 25mL methanol respectively.So
Afterwards, 2-methylimidazole solution is poured into cobalt nitrate solution rapidly under agitation, after stirring 5 minutes, gained mixed solution is in room
The lower aging of temperature 12 hours.Violet precipitate is collected by centrifugation and is dried 12 hours at 60 DEG C and obtains product ZIF-67 nanocrystals.
40mg ZIF-67 are dispersed in the ethanol that 25mL contains 80mg zinc nitrates.After stirring 1h, formation ZIF-67/
Zn-Co hydroxide nano cage particles, centrifuge and collect, and are finally dried 12 hours at 60 DEG C.Then, in 350 DEG C of air
In with 2 DEG C of min-1Speed by ZIF-67/Zn-Co hydroxide nano cages particle anneal 2 hours, obtain ZnCo2O4@Co3O4Aspheric
Shape hollow structure nanocages.
40mg ZIF-67 are dispersed in the ethanol that 25mL contains 80mg copper nitrates.After stirring 1h, formation ZIF-67/
Cu-Co hydroxide nano cage particles, centrifuge and collect, and are finally dried 12 hours at 60 DEG C.Then, in 350 DEG C of air
In with 2 DEG C of min-1Speed by ZIF-67/Cu-Co hydroxide nano cages particle anneal 2 hours, obtain CuO@Co3O4It is aspherical
Hollow structure nanocages.
40mg ZIF-67 are dispersed in the ethanol that 25mL contains 40mg copper nitrates and 40mg zinc nitrates.After stirring 1h, shape
Into ZIF-67/Cu-Zn-Co hydroxide nano cage particles, centrifuge and collect, finally dried 12 hours at 60 DEG C.Then,
With 2 DEG C of min in 350 DEG C of air-1Speed by ZIF-67/ Cu-Zn-Co hydroxide nano cages particle anneal 2 hours,
Obtain CuO@ZnCo2O4@Co3O4Aspherical hollow structure nanocages.
Embodiment 5
Weigh 1.0mmol cobalt nitrates and 4.0mmol 2-methylimidazoles are dissolved in two kinds of solution of formation in 25mL methanol respectively.So
Afterwards, 2-methylimidazole solution is poured into cobalt nitrate solution rapidly under agitation, after stirring 5 minutes, gained mixed solution is in room
The lower aging of temperature 24 hours.Violet precipitate is collected by centrifugation and is dried 12 hours at 60 DEG C and obtains product ZIF-67 nanocrystals.
40mg ZIF-67 are dispersed in the ethanol that 15mL contains 20mg zinc nitrates.After stirring 1h, formation ZIF-67/
Zn-Co hydroxide nano cage particles, centrifuge and collect, and are finally dried 12 hours at 60 DEG C.Then in 350 DEG C of air
With 2 DEG C of min-1Speed by ZIF-67/Zn-Co hydroxide nano cages particle anneal 2 hours, obtain ZnCo2O4@Co3O4It is aspherical
Hollow structure nanocages.
40mg ZIF-67 are dispersed in the ethanol that 15mL contains 20mg copper nitrates.After stirring 1h, formation ZIF-67/
Cu-Co hydroxide nano cage particles, centrifuge and collect, and are finally dried 12 hours at 60 DEG C.Then, in 350 DEG C of air
In with 2 DEG C of min-1Speed by ZIF-67/Cu-Co hydroxide nano cages particle anneal 2 hours, obtain CuO@Co3O4It is aspherical
Hollow structure nanocages.
40mg ZIF-67 are dispersed in the ethanol that 15mL contains 10mg copper nitrates and 10mg zinc nitrates.After stirring 1h, shape
Into ZIF-67/Cu-Zn-Co hydroxide nano cage particles, centrifuge and collect, finally dried 12 hours at 60 DEG C.Then,
With 2 DEG C of min in 350 DEG C of air-1Speed by ZIF-67/ Cu-Zn-Co hydroxide nano cages particle anneal 2 hours,
Obtain CuO@ZnCo2O4@Co3O4Aspherical hollow structure nanocages.
Embodiment 6
Weigh 1.0mmol cobalt nitrates and 4.0mmol 2-methylimidazoles are dissolved in two kinds of solution of formation in 25mL methanol respectively.So
Afterwards, 2-methylimidazole solution is poured into cobalt nitrate solution rapidly under agitation, after stirring 5 minutes, gained mixed solution is in room
The lower aging of temperature 24 hours.Violet precipitate is collected by centrifugation and is dried 12 hours at 60 DEG C and obtains product ZIF-67 nanocrystals.
40mg ZIF-67 are dispersed in the ethanol that 35mL contains 80mg zinc nitrates.After stirring 1h, formation ZIF-67/
Zn-Co hydroxide nano cage particles, centrifuge and collect, and are finally dried 12 hours at 60 DEG C.Then in 350 DEG C of air
With 2 DEG C of min-1Speed by ZIF-67/Zn-Co hydroxide nano cages particle anneal 2 hours, obtain ZnCo2O4@Co3O4It is aspherical
Hollow structure nanocages.
40mg ZIF-67 are dispersed in the ethanol that 35mL contains 80mg copper nitrates.After stirring 1h, formation ZIF-67/
Cu-Co hydroxide nano cage particles, centrifuge and collect, and are finally dried 12 hours at 60 DEG C.Then, in 350 DEG C of air
In with 2 DEG C of min-1Speed by ZIF-67/Cu-Co hydroxide nano cages particle anneal 2 hours, obtain CuO@Co3O4It is aspherical
Hollow structure nanocages.
40mg ZIF-67 are dispersed in the ethanol that 35mL contains 10mg copper nitrates and 70mg zinc nitrates.After stirring 1h, shape
Into ZIF-67/Cu-Zn-Co hydroxide nano cage particles, centrifuge and collect, finally dried 12 hours at 60 DEG C.Then,
With 2 DEG C of min in 350 DEG C of air-1Speed by ZIF-67/ Cu-Zn-Co hydroxide nano cages particle anneal 2 hours,
Obtain CuO@ZnCo2O4@Co3O4Aspherical hollow structure nanocages.
Embodiment 7
Weigh 1.0mmol cobalt nitrates and 4.0mmol 2-methylimidazoles are dissolved in two kinds of solution of formation in 25mL methanol respectively.So
Afterwards, 2-methylimidazole solution is poured into cobalt nitrate solution rapidly under agitation, after stirring 5 minutes, gained mixed solution is in room
The lower aging of temperature 24 hours.Violet precipitate is collected by centrifugation and is dried 12 hours at 60 DEG C and obtains product ZIF-67 nanocrystals.
40mg ZIF-67 are dispersed in the ethanol that 35mL contains 80mg zinc nitrates.After stirring 1h, formation ZIF-67/
Zn-Co hydroxide nano cage particles, centrifuge and collect, and are finally dried 12 hours at 60 DEG C.Then, in 350 DEG C of air
In with 2 DEG C of min-1Speed by ZIF-67/Zn-Co hydroxide nano cages particle anneal 2 hours, obtain ZnCo2O4@Co3O4Aspheric
Shape hollow structure nanocages.
40mg ZIF-67 are dispersed in the ethanol that 35mL contains 80mg copper nitrates.After stirring 1h, formation ZIF-67/
Cu-Co hydroxide nano cage particles, centrifuge and collect, and are finally dried 12 hours at 60 DEG C.Then, in 350 DEG C of air
In with 2 DEG C of min-1Speed by ZIF-67/Cu-Co hydroxide nano cages particle anneal 2 hours, obtain CuO@Co3O4It is aspherical
Hollow structure nanocages.
40mg ZIF-67 are dispersed in the ethanol that 35mL contains 70mg copper nitrates and 10mg zinc nitrates.After stirring 1h, shape
Into ZIF-67/Cu-Zn-Co hydroxide nano cage particles, centrifuge and collect, finally dried 12 hours at 60 DEG C.Then,
With 2 DEG C of min in 350 DEG C of air-1Speed by ZIF-67/ Cu-Zn-Co hydroxide nano cages particle anneal 2 hours,
Obtain CuO@ZnCo2O4@Co3O4Aspherical hollow structure nanocages.
Embodiment 8
Weigh 1.0mmol cobalt nitrates and 4.0mmol 2-methylimidazoles are dissolved in two kinds of solution of formation in 25mL methanol respectively.So
Afterwards, 2-methylimidazole solution is poured into cobalt nitrate solution rapidly under agitation, after stirring 5 minutes, gained mixed solution is in room
The lower aging of temperature 24 hours.Violet precipitate is collected by centrifugation and is dried 12 hours at 60 DEG C and obtains product ZIF-67 nanocrystals.
40mg ZIF-67 are dispersed in the ethanol that 25mL contains 80mg zinc nitrates.After stirring 1h, formation ZIF-67/
Zn-Co hydroxide nano cage particles, centrifuge and collect, and are finally dried 12 hours at 60 DEG C.Then, in 350 DEG C of air
In with 2 DEG C of min-1Speed by ZIF-67/Zn-Co hydroxide nano cages particle anneal 3 hours, obtain ZnCo2O4@Co3O4Aspheric
Shape hollow structure nanocages.
40mg ZIF-67 are dispersed in the ethanol that 25mL contains 80mg copper nitrates.After stirring 1h, formation ZIF-67/
Cu-Co hydroxide nano cage particles, centrifuge and collect, and are finally dried 12 hours at 60 DEG C.Then, in 350 DEG C of air
In with 2 DEG C of min-1Speed by ZIF-67/Cu-Co hydroxide nano cages particle anneal 3 hours, obtain CuO@Co3O4It is aspherical
Hollow structure nanocages.
40mg ZIF-67 are dispersed in the ethanol that 25mL contains 40mg copper nitrates and 40mg zinc nitrates.After stirring 1h, shape
Into ZIF-67/Cu-Zn-Co hydroxide nano cage particles, centrifuge and collect, finally dried 12 hours at 60 DEG C.Then,
With 2 DEG C of min in 350 DEG C of air-1Speed by ZIF-67/ Cu-Zn-Co hydroxide nano cages particle anneal 3 hours,
Obtain CuO@ZnCo2O4@Co3O4Aspherical hollow structure nanocages.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
The equivalent structure or equivalent flow conversion that bright specification is made, or other related technical areas are directly or indirectly used in,
Similarly it is included within the scope of the present invention.
Claims (9)
1. template prepares aspherical hollow structure nanocages composite, it is characterised in that：ZIF-67 nanocrystals are first synthesized,
Again using ZIF-67 as template, it is scattered in the ethanol solution of nitrate, after stirring, centrifugation, drying, at 300~350 DEG C
With 2 DEG C of min in air-1Speed anneal 2~3h be prepared.
2. template prepares aspherical hollow structure nanocages composite according to claim 1, it is characterised in that described
The synthesis of ZIF-67 nanocrystals, including：Weigh cobalt nitrate and 2-methylimidazole dissolves stir evenly into solution in methyl alcohol respectively, its
The mol ratio of middle cobalt nitrate and 2-methylimidazole is 1：4.0~16, solute unit for mM, methanol volume is 25~45mL；
Then 2-methylimidazole solution is poured into cobalt nitrate solution rapidly under agitation, is sufficiently stirred rear 12~36h of aged at room temperature, passed through
It is collected by centrifugation to obtain violet precipitate and dry 12h at 60 DEG C to obtain ZIF-67 nanocrystals.
3. template prepares aspherical hollow structure nanocages composite according to claim 1, it is characterised in that：It is described
Nitrate is both zinc nitrate, copper nitrate or zinc nitrate and copper nitrate mixture.
4. template prepares aspherical hollow structure nanocages composite according to claim 2, it is characterised in that：Institute
The mol ratio for stating cobalt nitrate and 2-methylimidazole is 1:4, solute unit for mM, methanol volume is 25mL.
5. template prepares aspherical hollow structure nanocages composite according to claim 2, it is characterised in that：By 2-
Methyl imidazole solution is poured into cobalt nitrate solution rapidly under agitation, is sufficiently stirred rear aged at room temperature 24h.
6. template prepares aspherical hollow structure nanocages composite according to claim 3, it is characterised in that：Institute
State and ZnCo is made when nitrate is zinc nitrate2O4@Co3O4Aspherical hollow structure nanocages, including：ZIF-67 is dispersed in nitre
In the ethanol solution of sour zinc, the ZIF-67：Zinc nitrate：The mass volume ratio of ethanol is 40mg：20~80mg：15~
35mL, preferably 40mg：80mg：25mL, after persistently stirring 1h, form ZIF-67/Zn-Co hydroxide nano cage particles and lead to
Cross and centrifuge and collect, 12h is dried at 60 DEG C, then with 2 DEG C of min in 300~350 DEG C of air-1Speed by ZIF-67/
Zn-Co hydroxide nano cages particle 2~3h of annealing, 2h, obtains ZnCo by preferably 350 DEG C2O4@Co3O4Aspherical hollow structure
Nanocages.
7. template prepares aspherical hollow structure nanocages composite according to claim 3, it is characterised in that：Institute
State and CuO@Co are made when nitrate is copper nitrate3O4Aspherical hollow structure nanocages, including：ZIF-67 is dispersed in copper nitrate
Ethanol solution in, the ZIF-67：Copper nitrate：The mass volume ratio of ethanol is 40mg：20~80mg：15~35mL, it is excellent
Select 40mg：80mg：25mL, after persistently stirring 1h, form ZIF-67/Cu-Co hydroxide nano cage particles and pass through centrifugation
And collect, 12h is dried at 60 DEG C, then with 2 DEG C of min in 300~350 DEG C of air-1Speed by ZIF-67/Cu-Co
Hydroxide nano cage particle 2~3h of annealing, 2h, obtains CuO@Co by preferably 350 DEG C3O4Aspherical hollow structure nanocages.
8. template prepares aspherical hollow structure nanocages composite according to claim 3, it is characterised in that：Institute
Nitrate is stated as CuO@ZnCo are made when zinc nitrate and the mixing of copper nitrate equal proportion2O4@Co3O4Aspherical hollow structure nanometer
Cage：ZIF-67 is dispersed in the ethanol solution of zinc nitrate and copper nitrate, the ZIF-67：Zinc nitrate：Copper nitrate：The matter of ethanol
Amount volume ratio is 40mg：10~70mg：10~70mg：15~35mL, preferably 40mg：40mg：40mg：25mL, stir 1h
Afterwards, ZIF-67/Cu-Zn-Co hydroxide nano cage particles are formed by centrifuging and collecting, 12h are dried at 60 DEG C, then
With 2 DEG C of min in 300~350 DEG C of air-1Speed by ZIF-67/ Cu-Zn-Co hydroxide nano cages particle anneal 2
~3h, preferably 350 DEG C, 2h, obtain CuO@ZnCo2O4@Co3O4Aspherical hollow structure nanocages.
9. the aspherical hollow structure nanocages composite according to made from any methods describeds of claim 1-8.
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