CN102350499B - 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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- CN102350499B CN102350499B CN 201110295624 CN201110295624A CN102350499B CN 102350499 B CN102350499 B CN 102350499B CN 201110295624 CN201110295624 CN 201110295624 CN 201110295624 A CN201110295624 A CN 201110295624A CN 102350499 B CN102350499 B CN 102350499B
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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, specifically a kind of take porous C u as core, cube Cu
2O is the Cu/Cu that shell consists of
2O nucleocapsid complex microsphere and preparation method thereof.
Background technology
Core-shell complex microsphere refers to take a size at micron to the spheric granules of nanometer range as core, coats several layers of uniform film on its surface and a kind of compound heterogeneous structure that forms, interconnects by physics or chemical action between this core and shell.The nucleocapsid of broad sense (Core/shell) material not only comprises the composite with nucleocapsid structure that is comprised of identical or different material, also comprises the composite of the special appearances such as hollow microsphere (Hollow sphere), microcapsules (Microcapsule).The nucleocapsid composite generally is divided into the several types such as inorganic-organic, inorganic-inorganic, organic-organic and organic and inorganic.
Design and construct the composite with nucleocapsid structure and become gradually a research field that becomes more and more important in material science.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 class material is used for constructing the extensive favor that the novel capabilities formed material is subject to 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
2The cuprous oxide that O nucleocapsid complex microsphere is less with particle diameter is attached to the larger copper ball carrier surface of particle diameter, thereby has solved well the difficult difficult problem that reclaims of cuprous oxide powder; Simultaneously, the shell of nucleocapsid structure material can be adjusted the surface characteristic of particle, changes its surperficial 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.
At present take Cu as core, 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 isopropyl alcohol, add powder KBH
4Make reducing agent, made take Cu as core, 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 by RF-spray and the RF-PECVD co-electrodeposition method prepare composite, made different Cu content and different Cu nano particle diameter, take copper as core, oxide be distributed in the surface Cu@Cu
2O core-shell nano (Ghodselahi T, Vesaghi M A, Shafiekhani A, et al, XPS study ofthe Cu@Cu
2O core-shell nanoparticles[J]. Applied Surface Science, 2008,255:2730-2734).Wang etc., by heat treatment by electro-deposition method made take Cu as core, Cu
2O is the Cu/Cu of shell
2The Cu of the 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 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, make take Cu as matrix, the Cu-Cu of 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).
The 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 comparison in equipment complexity that the methods such as electro-deposition are used, electrolyte has adverse influence to environment, also is unfavorable for large-scale production.Some methods are also used virose KBF
4And K
2TiF
6, careless slightly may 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: provide a kind of take Cu as core, Cu
2O is the Cu/Cu that shell consists of
2The preparation method of O nucleocapsid complex microsphere namely 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 large to overcome, complex process, contaminated environment, be difficult to large-scale production, particle size were little, be difficult for the defectives such as recovery.
The present invention solves this technical problem the technical scheme that adopts:
A kind of Cu/Cu
2O nucleocapsid complex microsphere, this nucleocapsid complex microsphere be take porous C u as core, the Cu of average grain diameter 200 nanocube shapes
2O is that shell consists of, 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; Separately dodecyl sodium sulfate and reducing agent are dissolved in 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
-4Mole reducing agent; Get 20 parts of copper salt solutions and mix with 30 parts of dodecyl sodium sulfate-reducing agent-ethylene glycol solutions, add in reactor, stir, be made into mantoquita-dodecyl sodium sulfate-reducing agent-ethylene glycol-water mixed liquid;
(2) precipitating reagent is dissolved in water, makes the precipitant solution that concentration is 0.004～0.006 mole of precipitating reagent/ml water, get 10 parts, then add the ethylene glycol of 30～90 parts, be mixed with precipitating reagent-ethylene glycol-water mixed liquid;
(3) under agitation, the mixed liquor of preparation in step (2) is joined in reactor in step (1), under nitrogen protection, be warming up to reflux temperature, back flow reaction 12～48 hours stops stirring and heating;
(4) again with products therefrom of upper step at room temperature standing 0～15 hour, then washing, suction filtration with the products therefrom oven dry, obtains Cu/Cu
2O nucleocapsid complex microsphere.
The umber of said components is volume parts, and in each step, volume unit used is identical.
Mantoquita described in top step (1) is copper chloride, copper sulphate or Schweinfurt green;
Reducing agent described in top step (1) is glucose or sodium sulfite;
Precipitating reagent described in 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 core 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 is that the cuprous oxide that particle diameter is less is attached to the larger copper ball carrier surface of particle diameter, thereby has solved well the difficult difficult problem that reclaims of cuprous oxide powder.
3. simple circumfluence method is adopted in this research, is Cu/Cu
2O nucleocapsid structure material preparation provides a new method.
4. in the inventive method, adopt the low anion surfactant dodecyl sodium sulfate of toxicity, be conducive to 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
The present invention is further described below in conjunction with drawings and Examples.
Fig. 1 is Cu/Cu in embodiment 1
2The XRD spectra of O nucleocapsid complex microsphere.
Fig. 2 is Cu/Cu in embodiment 1
2The XPS spectrum figure on O nucleocapsid complex microsphere surface.
Fig. 3 is Cu/Cu in 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 in 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; Separately 1g dodecyl sodium sulfate and 0.0133 mole of glucose are dissolved in and make dodecyl sodium sulfate-glucose-ethylene glycol solution in 30mL ethylene glycol; Then copper chloride solution is mixed with dodecyl sodium sulfate-glucose-ethylene glycol solution, add in the flask with reflux, stir, be made into copper chloride-dodecyl sodium sulfate-glucose-ethylene glycol-water mixed liquid.
(2) 0.04 molar sodium hydroxide is dissolved in 10mL water, then adds 30mL ethylene glycol, be mixed with NaOH-ethylene glycol-water mixed liquid.
(3) under agitation, the mixed liquor of preparation in step (2) is joined in flask in step (1), under nitrogen protection, be warming up to reflux temperature, back flow reaction 48h stops stirring and heating.
(4) again with products therefrom of upper step standing 15h at room temperature, then with it with deionized water washing three times, then through suction filtration, products therefrom is dried in the vacuum drying chamber of 60 ℃, 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 Emission in Cubic 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 main composition in compound.To Cu/Cu
2XPS analysis is carried out on O nucleocapsid complex microsphere surface, and two peak Cu 2p1/2 and Cu 2p3/2 appear at respectively 952.05 and the 932.26eV place, and take C1s (284.6eV) as with reference to after it is proofreaied and correct, 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 pattern on O nucleocapsid complex microsphere surface changes and inner cross-section morphology.Fig. 3 a is the SEM photo of microballoon before pickling, and Fig. 3 b is the local enlarged photograph of microsphere surface before pickling, and Fig. 3 c is the SEM photo of microballoon after pickling, and Fig. 3 d is the local enlarged photograph of microsphere surface after pickling, Cu/Cu after pickling
2O nucleocapsid complex microsphere surface becomes coarse, and this shell that is the cuprous oxide due to the cube structure of regular compact arranged 200 about nanometers that originally are attached to microsphere surface consists of is dissolved by HCl, exposes the result of copper core.Fig. 4 is the cross-section morphology of microballoon, shows that microballoon inside is to be combined into by some little irregular particulates, and also has some holes between them, and is similar to microsphere surface after pickling, hence one can see that Cu/Cu
2The core of O nucleocapsid complex microsphere is the simple substance Cu of porous.
Change respectively the time of the backflow in step (3) in embodiment 1 into 12h, 24h, 36h, 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 in 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 in embodiment 1
6H
12O
6Consumption change 0.015 mole into, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 7
Change the consumption of step (1) SDS in embodiment 1 into 0.5g, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 8
Change the consumption of step (1) SDS in embodiment 1 into 4g, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 9
Change the consumption of step (2) NaOH in 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; Separately 1g dodecyl sodium sulfate and 0.0133 mole of glucose are dissolved in and make dodecyl sodium sulfate-glucose-ethylene glycol solution in 30mL ethylene glycol; Then copper-bath is mixed with dodecyl sodium sulfate-glucose-ethylene glycol solution, add in the flask with reflux, stir, be made into copper sulphate-dodecyl sodium sulfate-glucose-ethylene glycol-water mixed liquid.
(2) 0.04 mole of KOH is dissolved in 10mL water, then adds 30mL ethylene glycol, be mixed with potassium hydroxide-ethylene glycol-water mixed liquid.
(3) under agitation, the mixed liquor of preparation in step (2) is joined in flask in step (1), under nitrogen protection, be warming up to reflux temperature, back flow reaction 48h stops stirring and heating.
(4) again with products therefrom of upper step standing 15h at room temperature, then with deionized water washing three times, then through suction filtration, products therefrom to be dried in the vacuum drying chamber of 60 ℃, 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 in embodiment 10 into 0.06 mole, other steps obtain product with embodiment 1 with embodiment 11.
Embodiment 12
Change step (1) copper chloride in embodiment 1 into Schweinfurt green, other steps obtain product with embodiment 1 with embodiment 1.
Embodiment 13
Change step (1) glucose and consumption thereof in 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 in 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; Separately 1g dodecyl sodium sulfate and 0.0133 mole of glucose are dissolved in and make dodecyl sodium sulfate-glucose-ethylene glycol solution in 30mL ethylene glycol; Then copper chloride solution is mixed with dodecyl sodium sulfate-glucose-ethylene glycol solution, add in the flask with reflux, stir, be made into copper chloride-dodecyl sodium sulfate-glucose-ethylene glycol-water mixed liquid.
(2) 0.04 molar sodium hydroxide is dissolved in 10mL water, then adds 90mL ethylene glycol, be mixed with NaOH-ethylene glycol-water mixed liquid.
(3) under agitation, the mixed liquor of preparation in step (2) is joined in flask in step (1), under nitrogen protection, be warming up to reflux temperature, back flow reaction 48h stops stirring and heating.
(4) again with products therefrom of upper step standing 0h at room temperature, obtain microballoon of uniform size, then with it with deionized water washing three times, then through suction filtration, thus obtained microsphere is dried in the vacuum drying chamber of 60 ℃, 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; Separately 1g dodecyl sodium sulfate and 0.0133 mole of glucose are dissolved in and make dodecyl sodium sulfate-glucose-ethylene glycol solution in 30mL ethylene glycol; Then copper chloride solution is mixed with dodecyl sodium sulfate-glucose-ethylene glycol solution, add in the flask with reflux, stir, be made into copper chloride-dodecyl sodium sulfate-glucose-ethylene glycol-water mixed liquid.
(2) 0.04 molar sodium hydroxide is dissolved in 10mL water, then adds 30mL ethylene glycol, be mixed with NaOH-ethylene glycol-water mixed liquid.
(3) under agitation, the mixed liquor of preparation in step (2) is joined in flask in step (1), under nitrogen protection, be warming up to reflux temperature, back flow reaction 6h stops stirring and heating.
(4) again with products therefrom of upper step standing 15h at room temperature, then with it with deionized water washing three times, then through suction filtration, the vacuum drying chamber that is placed in 60 ℃ is dried, 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 in 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; Separately 1g dodecyl sodium sulfate and 0.0133 mole of glucose are dissolved in and make dodecyl sodium sulfate-glucose-ethylene glycol solution in 30mL ethylene glycol; Then copper chloride solution is mixed with dodecyl sodium sulfate-glucose-ethylene glycol solution, add in the flask with reflux, stir, be made into copper chloride-dodecyl sodium sulfate-glucose-ethylene glycol-water mixed liquid.
(2) 0.04 molar sodium hydroxide is dissolved in 10mL water, then adds 1mL ethylene glycol, be mixed with NaOH-ethylene glycol-water mixed liquid.
(3) under agitation, the mixed liquor of preparation in step (2) is joined in flask in step (1), under nitrogen protection, be warming up to reflux temperature, back flow reaction 48h stops stirring and heating.
(4) again with products therefrom of upper step standing 15h at room temperature, then with it with deionized water washing three times, then after suction filtration, dry in the vacuum drying chamber of 60 ℃, the time is 2.5h.
That obtain under this condition is Cu and Cu
2The composite powder that O and precursor thereof form.
Comparative Examples 4
(1) the 0.02mol copper chloride is dissolved in the water of 20mL, makes copper chloride solution; Separately 1g dodecyl sodium sulfate and 0.0133 mole of glucose are dissolved in and make dodecyl sodium sulfate-glucose-ethylene glycol solution in 30mL ethylene glycol; Then copper chloride solution is mixed with dodecyl sodium sulfate-glucose-ethylene glycol solution, add in the flask with reflux, stir, be made into copper chloride-dodecyl sodium sulfate-glucose-ethylene glycol-water mixed liquid.
(2) 0.04 molar sodium hydroxide is dissolved in 40mL water, then adds 1mL ethylene glycol, be mixed with NaOH-ethylene glycol-water mixed liquid.
(3) under agitation, the mixed liquor of preparation in step (2) is joined in flask in step (1), under nitrogen protection, be warming up to reflux temperature, back flow reaction 48h stops stirring and heating.
(4) again with products therefrom of upper step standing 15h at room temperature, then with it with deionized water washing three times, then through suction filtration, products therefrom is dried in the vacuum drying chamber of 60 ℃, the time is 2.5h.
That obtain under this condition is Cu and Cu
2The composite powder that O and precursor thereof form.
Analysis and research by means such as SEM, XRD, XPS have characterized this Cu/Cu
2The structure of O nucleocapsid complex microsphere forms, i.e. this Cu/Cu
2O nucleocapsid complex microsphere be take porous C u as core, 200 nanocube shape Cu
2O is the new type structure of hud complex microsphere of about 300～500 microns of the average grain diameter that consists of of shell.The Cu/Cu of this structure
2O nucleocapsid complex microsphere is for being successfully prepared first.Has method simple with regard to preparation, the advantage such as raw material is cheap and easy to get.By 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 (4)
1. Cu/Cu
2The preparation method of O nucleocapsid complex microsphere is characterized by this nucleocapsid complex microsphere and is take porous C u as core, the Cu of average grain diameter 200 nanocube shapes
2O is that shell consists of, and the complex microsphere average grain diameter is 300 ~ 500 microns;
Its step is as follows:
(1) mantoquita is soluble in water, make the copper salt solution that concentration is 0.001 mole of copper ion/ml water; Separately dodecyl sodium sulfate and reducing agent are dissolved in 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
-4Mole reducing agent; Get 20 parts of copper salt solutions and mix with 30 parts of dodecyl sodium sulfate-reducing agent-ethylene glycol solutions, add in reactor, stir, be made into mantoquita-dodecyl sodium sulfate-reducing agent-ethylene glycol-water mixed liquid;
(2) precipitating reagent is dissolved in water, makes the precipitant solution that concentration is 0.004 ~ 0.006 mole of precipitating reagent/ml water, get 10 parts, then add the ethylene glycol of 30 ~ 90 parts, be mixed with precipitating reagent-ethylene glycol-water mixed liquid;
(3) under agitation, the mixed liquor of preparation in step (2) is joined in reactor in step (1), under nitrogen protection, be warming up to reflux temperature, back flow reaction 12 ~ 48 hours stops stirring and heating;
(4) again with products therefrom of upper step at room temperature standing 0 ~ 15 hour, then washing, suction filtration with the products therefrom oven dry, obtains Cu/Cu
2O nucleocapsid complex microsphere;
The umber of said components is volume parts, and in each step, volume unit used is identical.
2. Cu/Cu as claimed in claim 1
2The preparation method of O nucleocapsid complex microsphere, it is characterized by the mantoquita described in step (1) is copper chloride, copper sulphate or Schweinfurt green.
3. Cu/Cu as claimed in claim 1
2The preparation method of O nucleocapsid complex microsphere, it is characterized by the reducing agent described in step (1) is glucose or sodium sulfite.
4. Cu/Cu as claimed in claim 1
2The preparation method of O nucleocapsid complex microsphere, it is characterized by the precipitating reagent described in step (2) is NaOH or potassium hydroxide.
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| CN101717980A (en) * | 2009-12-15 | 2010-06-02 | 天津大学 | Method for preparing cuprous oxide/titanium dioxide core-shell structure array film through AC electro-deposition method |
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| CN102180509A (en) * | 2011-03-28 | 2011-09-14 | 浙江理工大学 | Method for preparing hollow CuO/Cu2O spheres with controllable ingredients |
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| CN1759965A (en) * | 2005-11-04 | 2006-04-19 | 清华大学 | Method for synthesizing Nano balls of cuprous oxide, and application of Nano balls of cuprous oxide |
| KR20110008386A (en) * | 2009-07-20 | 2011-01-27 | 단국대학교 산학협력단 | Preparation method of copper oxide(cu2o) particle with cubic morphology |
| CN101722314A (en) * | 2009-11-20 | 2010-06-09 | 云南大学 | Method for preparing Cu2O-Cu composite microsphere by adopting bean flour as template |
| CN101717980A (en) * | 2009-12-15 | 2010-06-02 | 天津大学 | Method for preparing cuprous oxide/titanium dioxide core-shell structure array film through AC electro-deposition method |
| CN102180509A (en) * | 2011-03-28 | 2011-09-14 | 浙江理工大学 | Method for preparing hollow CuO/Cu2O spheres with controllable ingredients |
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| CN108373164A (en) * | 2018-03-12 | 2018-08-07 | 江苏师范大学 | A kind of C claddings Cu2The synthetic method of O cuboctahedron nucleocapsids |
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