CN102350499A - Cu/Cu2O core-shell composite microsphere and preparation method thereof - Google Patents
Cu/Cu2O core-shell composite microsphere and preparation method thereof Download PDFInfo
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- CN102350499A CN102350499A CN2011102956247A CN201110295624A CN102350499A CN 102350499 A CN102350499 A CN 102350499A CN 2011102956247 A CN2011102956247 A CN 2011102956247A CN 201110295624 A CN201110295624 A CN 201110295624A CN 102350499 A CN102350499 A CN 102350499A
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Abstract
The invention relates to a Cu/Cu2O core-shell composite microsphere and a preparation method thereof. The core-shell composite microsphere is composed of a core and a shell and has an average grain size of 300-500 microns, wherein porous Cu is taken as the core and 200-nanometer cubic Cu2O is taken as the shell. The preparation method of the core-shell composite microsphere comprises the following steps: while stirring, adding a mixed solution of precipitant, ethylene glycol and water into a mixed solution of nantokite, sodium dodecyl sulfate, reducing agent, ethylene glycol and water, and performing reflux reaction for 12-48 hours; standing for 0-15 hours at room temperature, and then washing and filtering; and drying an acquired product, thereby acquiring the Cu/Cu2O core-shell composite microsphere. A simple reflux method is adopted to prepare the Cu/Cu2O core-shell composite microsphere and a cuprous oxide in smaller grain size is attached to the surface of a copper sphere carrier in bigger grain size, thereby efficiently solving the difficulty in recycling cuprous oxide powder. Besides, the raw materials are cheap and easily acquired.
Description
Technical field
Technical scheme of the present invention relates to the compound and preparation method thereof of the lower valency oxide of copper and copper, and specifically a kind of is nuclear, cube Cu with porous C u
2O is the Cu/Cu that shell constitutes
2O nucleocapsid complex microsphere and preparation method thereof.
Background technology
Nuclear-shell complex microsphere is meant that be nuclear with a size at the spheric granules of micron to nanometer range, and a kind of compound heterogeneous structure that forms at its surface several layers of uniform films of coating interconnects through physics or chemical action between this nuclear and the shell.The nucleocapsid of broad sense (Core/shell) material not only comprises the composite of being made up of identical or different material with nucleocapsid structure, also comprises the composite of hollow microsphere (Hollow sphere), microcapsules special appearances such as (Microcapsule).That the nucleocapsid composite generally is divided into is inorganic-several types such as organic and inorganic-inorganic, organic-organic and organic and inorganic.
Design and construct composite and become a research field that becomes more and more important in the material science gradually with nucleocapsid structure.The core-shell type complex microsphere integrates many specific physiques; Physicochemical properties with many novelties; For example: the operability of monodispersity, nucleocapsid, stability, Modulatory character, self assembly and relate to the ability of light, electricity, magnetics, catalysis, chemistry and biological respinse; Therefore, this type material is used to construct the extensive favor that the novel capabilities formed material receives the researcher.
Cuprous oxide as rare can be by the semi-conducting material of excited by visible light; Nontoxic, preparation cost is low, can directly utilize the sunshine degradation of organic substances, theoretical utilization ratio is higher; Simultaneously can not produce secondary pollution, be a kind of environmental protection catalyst that has DEVELOPMENT PROSPECT.Though nano level cuprous oxide photocatalysis treatment effect is good, because its particle diameter is little, extremely difficult recycling.Cu/Cu
2O nucleocapsid complex microsphere cuprous oxide that particle diameter is less is attached to the bigger copper ball carrier surface of particle diameter, is difficult for the difficult problem that reclaims thereby solved the cuprous oxide powder well; Simultaneously, the shell of nucleocapsid structure material can be adjusted the surface characteristic of particle, changes its surface electric charge density, surface-active, functional group, reactivity, biocompatibility, stable and dispersed; The gradient-structure that it is special also can be given interior karyomicrosome with the distinctive ultra-hydrophobicity of outer shell particles, catalytic activity, electric property, biological medicine performance, optical property etc.
Be nuclear, Cu at present with Cu
2O is the Cu/Cu of shell
2The preparation method of O nucleocapsid compound has hydro-thermal method, microemulsion method, sedimentation etc.Wang etc. use the polyethylene glycol used as stabilizers in microemulsion system, saturated copper salt solution is scattered in the isopropyl alcohol, add powder KBH
4Make reducing agent, having made with Cu is nuclear, Cu
2O is the Cu/Cu of shell
2O nucleocapsid complex particle (Wang C Y, Zhou Y, Chen Z Y, et al.Preparation of Shell-Core Cu
2O-Cu Nanocomposite Particles and Cu Nanoparticles in a New Microemulsion System[J] .Journal of Colloid and Interface Science, 1999,220:468-470).Ghodselahi etc.; Do electrode with copper sheet and stainless steel; On the C:H film, spray with the RF-PECVD co-electrodeposition method and prepare composite through RF-, made different Cu content and different Cu nano particle diameter, with copper be examine, divided oxide is distributed in surperficial CuCu
2O core-shell nano (Ghodselahi T, Vesaghi M A, Shafiekhani A, et al, XPS study ofthe CuCu
2O core-shell nanoparticles[J] .Applied Surface Science, 2008,255:2730-2734).Wang etc., having been made with Cu by electro-deposition method through heat treatment is nuclear, Cu
2O is the Cu/Cu of shell
2The Cu of dendritic crystal of the nanotrees of O nucleocapsid structure and hollow
2The dendritic crystal of O nanotrees (Wang R C, Li C H.Cu, Cu-Cu
2O core-shell, and hollow Cu
2O nanodendrites:Structural evolution and reverse surface-enhanced Raman scattering[J] .Acta Materialia, 2011,59:822-829).Yu etc. are at ultra-thin CuSO
4On the liquid layer, carry out the electro-deposition experiment, the Cu that makes
2The O crystallite is scattered in sample surfaces, forms the Cu of inferior micro-or nanoscale
2O/Cu interface (Yu G W, Hu X B, Liu D, et al.Electrodeposition of submicron/nanoscale Cu
2O/Cu junctions in an ultrathin CuSO
4Solution layer[J] .Journal of Electroanalytical Chemistry, 2010,638:225-230).Wu etc. add K in the Cu that melts
2TiF
6And KBF
4, making with Cu is the Cu-Cu of matrix, in-situ nano size
2O compound (Wu YY, Liu X F, Zhang J Q, et al.In situ formation of nano-scale Cu-Cu
2O composites[J] .Materials Science and Engineering A, 2010,527:1544-1547).
KBH4 that microemulsion method is used meets naked light, Gao Re or contacts with oxidant, and the danger that causes combustion explosion is arranged; Meeting humid air, water or acid emits inflammable hydrogen and causes burning.The equipment more complicated that methods such as electro-deposition are used, electrolyte has adverse influence to environment, also is unfavorable for large-scale production.The method that has is also used virose KBF
4And K
2TiF
6, careless slightly possibly working the mischief to human body also can be brought negative effect to environment.So we prepare Cu/Cu with a kind of simple, efficient, green method
2O nucleocapsid complex microsphere.
Summary of the invention
Technical problem to be solved by this invention is: providing a kind of is nuclear, Cu with Cu
2O is the Cu/Cu that shell constitutes
2The preparation method of O nucleocapsid complex microsphere promptly adopts reflux technique in ethylene glycol-aqueous systems, with the auxiliary synthetic Cu/Cu of anion surfactant dodecyl sodium sulfate
2O nucleocapsid complex microsphere, the existing raw materials used toxicity of method is big to overcome, complex process, contaminated environment, be difficult to large-scale production, product particle diameter little, be difficult for defectives such as recovery.
The present invention solves this technical problem the technical scheme that is adopted:
A kind of Cu/Cu
2O nucleocapsid complex microsphere, this nucleocapsid complex microsphere are to be the Cu of nuclear, average grain diameter 200 nanocubes shapes with porous C u
2O is that shell constitutes, and the complex microsphere average grain diameter is 300～500 microns.
Described Cu/Cu
2The preparation method of O nucleocapsid complex microsphere the steps include:
(1) mantoquita is soluble in water, make the copper salt solution that concentration is 0.001 mole of copper ion/ml water; In addition dodecyl sodium sulfate and reducing agent are dissolved in the ethylene glycol, make dodecyl sodium sulfate-reducing agent-ethylene glycol solution, its concentration is that every milliliter of ethylene glycol contains 0.017～0.133 gram dodecyl sodium sulfate and 3.33 * 10
-4～5 * 10
-4The mole reducing agent; Get 20 parts of copper salt solutions and mix, add in the reactor, stir, be made into mantoquita-dodecyl sodium sulfate-reducing agent-ethylene glycol-water mixed liquid with 30 parts of dodecyl sodium sulfate-reducing agent-ethylene glycol solutions;
(2) precipitating reagent is dissolved in the water, makes the precipitant solution that concentration is 0.004～0.006 mole of precipitating reagent/ml water, get 10 parts, add 30～90 parts ethylene glycol again, be mixed with precipitating reagent-ethylene glycol-water mixed liquid;
(3) under agitation, liquid mixture prepared in the step (2) is joined in the reactor in the step (1), under the nitrogen protection, be warming up to reflux temperature, back flow reaction 12～48 hours stops to stir and heating;
(4) will go up the step products therefrom again and at room temperature leave standstill 0～15 hour, washing then, suction filtration with the products therefrom oven dry, obtains Cu/Cu
2O nucleocapsid complex microsphere.
The umber of said components is volume parts, and used volume unit is identical in each step.
Mantoquita described in the top step (1) is copper chloride, copper sulphate or Schweinfurt green;
Reducing agent described in the top step (1) is glucose or sodium sulfite;
Precipitating reagent described in the top step (2) is NaOH or potassium hydroxide.
The invention has the beneficial effects as follows:
1. the resulting Cu/Cu of the inventive method
2Its structure of O nucleocapsid complex microsphere is to be assembled and be interconnected to form the Cu nuclear of porous, Cu by the Cu particle
2The O isometric particle is distributed in microsphere surface, forms nucleocapsid structure.
2. the Cu/Cu that makes of this research
2O nucleocapsid complex microsphere be cuprous oxide that particle diameter is less attached to the bigger copper ball carrier surface of particle diameter, be difficult for the difficult problem that reclaims thereby solved the cuprous oxide powder well.
3. simple circumfluence method is adopted in this research, is Cu/Cu
2The preparation of O nucleocapsid structure material provides a new method.
4. in the inventive method, adopt the low anion surfactant dodecyl sodium sulfate of toxicity, help nonhazardous production and environmental protection.
5. the raw material copper chloride, copper sulphate, the Schweinfurt green that adopt of the present invention; Glucose (C
6H
12O
6), sodium sulfite (Na
2SO
3); NaOH (NaOH), potassium hydroxide (KOH); Ethylene glycol; Dodecyl sodium sulfate (SDS) all belongs to general chemistry reagent, and is cheap and easy to get.
Description of drawings
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
Fig. 1 is Cu/Cu among the embodiment 1
2The XRD spectra of O nucleocapsid complex microsphere.
Fig. 2 is Cu/Cu among the embodiment 1
2The XPS spectrum figure on O nucleocapsid complex microsphere surface.
Fig. 3 is Cu/Cu among the embodiment 1
2SEM photo before and after the pickling of O nucleocapsid complex microsphere is before a, b are pickling; After c, d are pickling.
Fig. 4 is Cu/Cu among the embodiment 1
2The cross-section morphology of O nucleocapsid complex microsphere.
The specific embodiment
Embodiment 1
(1) the 0.02mol copper chloride is dissolved in the water of 20mL, makes copper chloride solution; In addition 1g dodecyl sodium sulfate and 0.0133 mole of glucose are dissolved in and make dodecyl sodium sulfate-glucose-ethylene glycol solution in the 30mL ethylene glycol; Then copper chloride solution is mixed with dodecyl sodium sulfate-glucose-ethylene glycol solution, adding has in the flask of reflux, stirs, and is made into copper chloride-dodecyl sodium sulfate-glucose-ethylene glycol-water mixed liquid.
(2) 0.04 molar sodium hydroxide is dissolved in the 10mL water, adds 30mL ethylene glycol again, be mixed with NaOH-ethylene glycol-water mixed liquid.
(3) under agitation, liquid mixture prepared in the step (2) is joined in the flask in the step (1), under the nitrogen protection, be warming up to reflux temperature, back flow reaction 48h stops to stir and heating.
(4) will go up the step products therefrom again and at room temperature leave standstill 15h, and then it washed three times with deionized water, and again through suction filtration, products therefrom dried in 60 ℃ vacuum drying chamber, the time is 2.5h, obtains Cu/Cu
2O nucleocapsid complex microsphere 1.38g, average grain diameter is 430.5 μ m.
Through XRD test, diffraction maximum shows that product is the elemental copper of cube phase to wide-angle part (2 θ=10～80 °), and diffraction maximum is very clear, sharp-pointed, illustrates that copper simple substance degree of crystallinity is fine, is major ingredients in compound.To Cu/Cu
2XPS analysis is carried out on O nucleocapsid complex microsphere surface, two peak Cu 2p1/2 and Cu 2p3/2 appear at respectively 952.05 with 932.26eV place, with C1s (284.6eV) serve as reference to its correction after, these two peaks are corresponding to Cu
2The xps energy spectrum of O learns that thus microsphere surface has cuprous oxide.
Observed pickling front and back Cu/Cu through SEM again
2The morphology change on O nucleocapsid complex microsphere surface and inner cross-section morphology.Fig. 3 a is the SEM photo of microballoon before the pickling, and Fig. 3 b is the local enlarged photograph of microsphere surface before the pickling, and Fig. 3 c is the SEM photo of microballoon after the pickling, and Fig. 3 d is the local enlarged photograph of microsphere surface after the pickling, Cu/Cu after the pickling
2O nucleocapsid complex microsphere surface becomes coarse, and this is owing to originally dissolved by HCl attached to the shell that cuprous oxide constituted of the cube structure about regular compact arranged 200 nanometers of microsphere surface, exposes the result that copper is examined.Fig. 4 is the cross-section morphology of microballoon, shows that microballoon inside is by some little irregular particulate be combined intos, and also has some holes between them, and is similar with microsphere surface after the pickling, hence one can see that Cu/Cu
2The nuclear of O nucleocapsid complex microsphere is the simple substance Cu of porous.
Change the time of the backflow in the step (3) among the embodiment 1 into 12h, 24h, 36h respectively, other operations is all identical with embodiment 1, gained Cu/Cu
2The average grain diameter of O nucleocapsid complex microsphere respectively is 348 μ m, 378 μ m, 400 μ m.
Embodiment 5
With step (1) C among the embodiment 1
6H
12O
6Consumption change 0.01 mole into, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 6
With step (1) C among the embodiment 1
6H
12O
6Consumption change 0.015 mole into, other steps obtain product with embodiment 1 with embodiment 1.
Change the consumption of step (1) SDS among the embodiment 1 into 0.5g, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 8
Change the consumption of step (1) SDS among the embodiment 1 into 4g, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 9
Change the consumption of step (2) NaOH among the embodiment 1 into 0.06 mole, other steps obtain product with embodiment 1 with embodiment 1.
(1) 0.02mol copper sulphate is dissolved in the water of 20mL, makes copper-bath; In addition 1g dodecyl sodium sulfate and 0.0133 mole of glucose are dissolved in and make dodecyl sodium sulfate-glucose-ethylene glycol solution in the 30mL ethylene glycol; Then copper-bath is mixed with dodecyl sodium sulfate-glucose-ethylene glycol solution, adding has in the flask of reflux, stirs, and is made into copper sulphate-dodecyl sodium sulfate-glucose-ethylene glycol-water mixed liquid.
(2) 0.04 mole of KOH is dissolved in the 10mL water, adds 30mL ethylene glycol again, be mixed with potassium hydroxide-ethylene glycol-water mixed liquid.
(3) under agitation, liquid mixture prepared in the step (2) is joined in the flask in the step (1), under the nitrogen protection, be warming up to reflux temperature, back flow reaction 48h stops to stir and heating.
(4) will go up the step products therefrom again and at room temperature leave standstill 15h, and with deionized water washing three times, again through suction filtration, products therefrom dried in 60 ℃ vacuum drying chamber then, the time is 2.5h, obtains Cu/Cu
2The O complex microsphere is with embodiment 1.
Embodiment 11
Change the consumption of step (2) KOH among the embodiment 10 into 0.06 mole, other steps obtain product with embodiment 1 with embodiment 11.
Embodiment 12
Change step (1) copper chloride among the embodiment 1 into Schweinfurt green, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 13
Change step (1) glucose and consumption thereof among the embodiment 1 into 0.01 mole of sodium sulfite, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 14
With step (1) Na among the embodiment 13
2SO
3Consumption change 0.015 mole into, other steps obtain product with embodiment 13 with embodiment 13.
Embodiment 15
(1) the 0.02mol copper chloride is dissolved in the water of 20mL, makes copper chloride solution; In addition 1g dodecyl sodium sulfate and 0.0133 mole of glucose are dissolved in and make dodecyl sodium sulfate-glucose-ethylene glycol solution in the 30mL ethylene glycol; Then copper chloride solution is mixed with dodecyl sodium sulfate-glucose-ethylene glycol solution, adding has in the flask of reflux, stirs, and is made into copper chloride-dodecyl sodium sulfate-glucose-ethylene glycol-water mixed liquid.
(2) 0.04 molar sodium hydroxide is dissolved in the 10mL water, adds 90mL ethylene glycol again, be mixed with NaOH-ethylene glycol-water mixed liquid.
(3) under agitation, liquid mixture prepared in the step (2) is joined in the flask in the step (1), under the nitrogen protection, be warming up to reflux temperature, back flow reaction 48h stops to stir and heating.
(4) will go up the step products therefrom again and at room temperature leave standstill 0h, and obtain microballoon of uniform size, and then it washed three times with deionized water, and again through suction filtration, thus obtained microsphere dried in 60 ℃ vacuum drying chamber, the time is 2.5h, obtains Cu/Cu
2O complex microsphere 1.30g, average grain diameter is 313.5nm.
Comparative Examples
Comparative Examples 1
(1) the 0.02mol copper chloride is dissolved in the water of 20mL, makes copper chloride solution; In addition 1g dodecyl sodium sulfate and 0.0133 mole of glucose are dissolved in and make dodecyl sodium sulfate-glucose-ethylene glycol solution in the 30mL ethylene glycol; Then copper chloride solution is mixed with dodecyl sodium sulfate-glucose-ethylene glycol solution, adding has in the flask of reflux, stirs, and is made into copper chloride-dodecyl sodium sulfate-glucose-ethylene glycol-water mixed liquid.
(2) 0.04 molar sodium hydroxide is dissolved in the 10mL water, adds 30mL ethylene glycol again, be mixed with NaOH-ethylene glycol-water mixed liquid.
(3) under agitation, liquid mixture prepared in the step (2) is joined in the flask in the step (1), under the nitrogen protection, be warming up to reflux temperature, back flow reaction 6h stops to stir and heating.
(4) will go up the step products therefrom again and at room temperature leave standstill 15h, and then it washed three times with deionized water, and again through suction filtration, place 60 ℃ vacuum drying chamber to dry, the time is 2.5h.
Do not obtain microballoon under this condition, that obtain is Cu and Cu
2The powder of O compound.
Comparative Examples 2
Change the consumption of step (1) SDS among the embodiment 1 into 0g, other steps do not obtain microballoon with embodiment 1, and product is Cu and Cu
2The powder of O compound illustrates that SDS has played auxiliary synthesis in the formation of core-shell particles structure.
Comparative Examples 3
(1) the 0.02mol copper chloride is dissolved in the water of 20mL, makes copper chloride solution; In addition 1g dodecyl sodium sulfate and 0.0133 mole of glucose are dissolved in and make dodecyl sodium sulfate-glucose-ethylene glycol solution in the 30mL ethylene glycol; Then copper chloride solution is mixed with dodecyl sodium sulfate-glucose-ethylene glycol solution, adding has in the flask of reflux, stirs, and is made into copper chloride-dodecyl sodium sulfate-glucose-ethylene glycol-water mixed liquid.
(2) 0.04 molar sodium hydroxide is dissolved in the 10mL water, adds 1mL ethylene glycol again, be mixed with NaOH-ethylene glycol-water mixed liquid.
(3) under agitation, liquid mixture prepared in the step (2) is joined in the flask in the step (1), under the nitrogen protection, be warming up to reflux temperature, back flow reaction 48h stops to stir and heating.
(4) will go up the step products therefrom again and at room temperature leave standstill 15h, and then it washed three times with deionized water, and behind suction filtration, in 60 ℃ vacuum drying chamber, dry, the time is 2.5h.
That obtain under this condition is Cu and Cu
2The composite powder that O and precursor thereof are formed.
Comparative Examples 4
(1) the 0.02mol copper chloride is dissolved in the water of 20mL, makes copper chloride solution; In addition 1g dodecyl sodium sulfate and 0.0133 mole of glucose are dissolved in and make dodecyl sodium sulfate-glucose-ethylene glycol solution in the 30mL ethylene glycol; Then copper chloride solution is mixed with dodecyl sodium sulfate-glucose-ethylene glycol solution, adding has in the flask of reflux, stirs, and is made into copper chloride-dodecyl sodium sulfate-glucose-ethylene glycol-water mixed liquid.
(2) 0.04 molar sodium hydroxide is dissolved in the 40mL water, adds 1mL ethylene glycol again, be mixed with NaOH-ethylene glycol-water mixed liquid.
(3) under agitation, liquid mixture prepared in the step (2) is joined in the flask in the step (1), under the nitrogen protection, be warming up to reflux temperature, back flow reaction 48h stops to stir and heating.
(4) will go up the step products therefrom again and at room temperature leave standstill 15h, and then it washed three times with deionized water, and again through suction filtration, products therefrom dried in 60 ℃ vacuum drying chamber, the time is 2.5h.
That obtain under this condition is Cu and Cu
2The composite powder that O and precursor thereof are formed.
Analysis and research through means such as SEM, XRD, XPS have characterized this Cu/Cu
2The structure of O nucleocapsid complex microsphere is formed, i.e. this Cu/Cu
2O nucleocapsid complex microsphere is to be nuclear, 200 nanocubes shape Cu with porous C u
2O is about 300～500 microns new type structure of hud complex microsphere of average grain diameter that shell constitutes.The Cu/Cu of this structure
2O nucleocapsid complex microsphere is for be prepared into merit first.It is simple with regard to preparation, to have method, low in raw material cost advantage such as be easy to get.Through embodiment and Comparative Examples, can clearly show glycol/water volume ratio (2: 1～4: 1); Reflux time (12～48 hours); SDS consumption (every milliliter of ethylene glycol contains 0.017～0.133 gram dodecyl sodium sulfate, as described in claim 1 (1)) is to Cu/Cu
2The formation of O nucleocapsid complex microsphere is most important.
Claims (5)
1. Cu/Cu
2O nucleocapsid complex microsphere, it is characterized by this nucleocapsid complex microsphere is to be the Cu of nuclear, average grain diameter 200 nanocubes shapes with porous C u
2O is that shell constitutes, and the complex microsphere average grain diameter is 300～500 microns.
2. Cu/Cu as claimed in claim 1
2The preparation method of O nucleocapsid complex microsphere, it is following to it is characterized by step:
(1) mantoquita is soluble in water, make the copper salt solution that concentration is 0.001 mole of copper ion/ml water; In addition dodecyl sodium sulfate and reducing agent are dissolved in the ethylene glycol, make dodecyl sodium sulfate-reducing agent-ethylene glycol solution, its concentration is that every milliliter of ethylene glycol contains 0.017～0.133 gram dodecyl sodium sulfate and 3.33 * 10
-4～5 * 10
-4The mole reducing agent; Get 20 parts of copper salt solutions and mix, add in the reactor, stir, be made into mantoquita-dodecyl sodium sulfate-reducing agent-ethylene glycol-water mixed liquid with 30 parts of dodecyl sodium sulfate-reducing agent-ethylene glycol solutions;
(2) precipitating reagent is dissolved in the water, makes the precipitant solution that concentration is 0.004～0.006 mole of precipitating reagent/ml water, get 10 parts, add 30～90 parts ethylene glycol again, be mixed with precipitating reagent-ethylene glycol-water mixed liquid;
(3) under agitation, liquid mixture prepared in the step (2) is joined in the reactor in the step (1), under the nitrogen protection, be warming up to reflux temperature, back flow reaction 12～48 hours stops to stir and heating;
(4) will go up the step products therefrom again and at room temperature leave standstill 0～15 hour, washing then, suction filtration with the products therefrom oven dry, obtains Cu/Cu
2O nucleocapsid complex microsphere;
The umber of said components is volume parts, and used volume unit is identical in each step.
3. Cu/Cu as claimed in claim 2
2The preparation method of O nucleocapsid complex microsphere, it is characterized by the mantoquita described in the step (1) is copper chloride, copper sulphate or Schweinfurt green.
4. Cu/Cu as claimed in claim 1
2The preparation method of O nucleocapsid complex microsphere, it is characterized by the reducing agent described in the step (1) is glucose or sodium sulfite.
5. Cu/Cu as claimed in claim 1
2The preparation method of O nucleocapsid complex microsphere, it is characterized by the precipitating reagent described in the step (2) is NaOH or potassium hydroxide.
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| CN110325303A (en) * | 2017-03-31 | 2019-10-11 | 三井金属矿业株式会社 | Copper particle and its manufacturing method |
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| CN109967077A (en) * | 2019-03-13 | 2019-07-05 | 西安理工大学 | Nano porous copper/cuprous oxide nucleocapsid micro-powder preparation method and application |
| CN110961105A (en) * | 2019-11-27 | 2020-04-07 | 中国石油大学(北京) | Graphene-hollow copper nanosphere composite material and preparation method and application thereof |
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