CN107473258B - A kind of cuprous oxide polycrystalline microballoon and preparation method thereof - Google Patents
A kind of cuprous oxide polycrystalline microballoon and preparation method thereof Download PDFInfo
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- CN107473258B CN107473258B CN201610398393.5A CN201610398393A CN107473258B CN 107473258 B CN107473258 B CN 107473258B CN 201610398393 A CN201610398393 A CN 201610398393A CN 107473258 B CN107473258 B CN 107473258B
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The invention discloses a kind of cuprous oxide polycrystalline microballoons and preparation method thereof, the described method comprises the following steps: tannic acid being added in Kocide SD dispersion liquid, forms Kocide SD-tannic acid composite precursor；Reducing agent is added, obtains the cuprous oxide polycrystalline microballoon assembled by cuprous nano crystalline substance.The preparation method can obtain under higher precursor concentration close to grade cuprous oxide particle, and yield extends in industrial mass production up to 90% or more.The present invention provides a kind of methods that quick, easy, green prepares cuprous oxide polycrystalline microballoon.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of cuprous oxide polycrystalline microballoon and preparation method thereof.
Background technique
Cuprous oxide is a kind of important semiconductor material, forbidden bandwidth 2.17eV, therefore in photocatalysis and photovoltaic material
Middle extensive application.Cuprous oxide crystal is also used as a kind of good gas sensor.In addition, cuprous oxide is as one
Kind conventional antifouling agents, there is irreplaceable status in marine anti-pollution field.In the application of cuprous oxide, particle size,
Pattern can all have an important influence on final service performance, especially the nano cuprous oxide of morphology controllable, since nanometer is imitated
The generation answered will bring the tremendous increase of performance in the application.Industrially there is very big demand to nano cuprous oxide every year, such as
What just becomes the heat of research using the controllable nano cuprous oxide of method large scale preparation pattern simple, quickly, green, size
Point and difficult point.
The industrial production of cuprous oxide is mainly using the method for electrolysis at present.Usually existed with cuprous oxide prepared by electrolysis method
It is all difficult to control on partial size, pattern.It is a kind of regulation cuprous oxide crystal particle size and shape that wet chemistry, which prepares cuprous oxide,
The effective ways of looks, but a large amount of pattern controlling agent of addition is usually required, and in order to have to product morphology and size
Effect control, generally requires the concentration that lower presoma is kept in strict control reaction system, thus reaction efficiency is lower, it is difficult to real
Now it is mass produced.
When reaction system meets your moral cooking conditions of Oswald, cuprous oxide tends to form the assembling of nano crystal particle
Body microballoon, with the progress of maturing process, often will form hollow ball structure (Zhang L, Wang H, Acs Nano, 2011,
5,3257-3267).Patent 200880100355.0 discloses a kind of method for preparing cuprous oxide spherical assembly particle, is obtained
The assembling particle obtained had not only had due to nano-scale bring low melting point, but also had good processability, but its method needs
Exhibiting high surface activating agent is added to guarantee dimensional homogeneity.
It is easy to happen coordination between biomass polyphenols and metal, and there is certain reproducibility, it is heavier
It wants, this kind of material is environmentally friendly, belongs to green reagent, therefore be directed into the preparation of nano material.Patent
201410660207.1 disclose a kind of method for preparing nano cuprous oxide wire using plant phenolic acid for reducing agent, obtain
Product is monocrystalline cuprous oxide.
Summary of the invention
The present invention is intended to provide a kind of cuprous oxide polycrystalline microballoon and preparation method thereof, the preparation method is by introducing biology
Matter polyphenol --- tannic acid, can be as adjuvant (being both used as a kind of nucleating agent, the inducer also assembled as nano crystal)
It is micro- that the polycrystalline being assembled by cuprous nano crystalline substance is obtained under suitable Kocide SD-tannic acid composite precursor reaction density
Ball, and since the presence of tannic acid improves the storage stability of final product.
To achieve the goals above, one aspect of the present invention provides a kind of preparation method of cuprous oxide polycrystalline microballoon,
The following steps are included: tannic acid is added in Kocide SD dispersion liquid, Kocide SD-tannic acid composite precursor is formed；It is added
Reducing agent obtains the cuprous oxide polycrystalline microballoon assembled by cuprous nano crystalline substance.
According to the present invention, the Kocide SD dispersion liquid is formed by following steps: strong base solution is added drop-wise to cupric
In saline solution, it is stirred to react to obtain suspension, is centrifugated, washing obtains Kocide SD；By shape after Kocide SD dispersion
At Kocide SD dispersion liquid.
Preferably, the cupric salt is copper sulphate or its hydrate, copper nitrate or its hydrate, copper chloride or its hydration
Object and one of copper acetate or its hydrate are a variety of；It such as can be Copper dichloride dihydrate, anhydrous cupric sulfate, anhydrous nitric acid
Copper or copper acetate monohydrate.
It is further preferred that the molar concentration of the cupric salt aqueous solution is 0.001~1M；Preferably 0.01~
0.5M；It such as can be 0.1M.
Preferably, the strong base solution is sodium hydroxide and/or potassium hydroxide solution；The molar concentration of the strong base solution
For 0.1~10M, preferably 1~5M；It such as can be 2M, 3M, 4M or 5M.
It is further preferred that in the cupric salt aqueous solution and strong base solution the molar ratio of solute be (1:2)~(1:
20)；Preferably (1:3)~(1:16)；It such as can be 1:4.
It is further preferred that the time being stirred to react formed in Kocide SD dispersion liquid is 5~240 minutes；Preferably
15-120 minutes, such as can be 20 minutes, 30 minutes, 45 minutes or 60 minutes.
According to the present invention, the tannic acid is added in the form of a solution.The mass ratio of the tannic acid and the Kocide SD
For (1:2.5)~(1:125), preferably (1:12.5)~(1:50).
According to the present invention, the step of formation Kocide SD-tannic acid composite precursor specifically: in Kocide SD point
Tannic acid solution is added in dispersion liquid, is stirred to react to obtain suspension, be centrifugated, washing, obtain Kocide SD-tannic acid it is compound before
Drive body.
Preferably, the time being stirred to react in the step of forming Kocide SD-tannic acid composite precursor is 5~240
Minute；Preferably 2~120 minutes, such as can be 20 minutes, 30 minutes, 45 minutes or 60 minutes.
According to the present invention, the reducing agent is added in the form of a solution.Preferably, the molar concentration of the reducing agent solution is
0.01~5M；It is preferred that 0.1~1M.It is further preferred that the reducing agent is selected from hydrazine hydrate, sodium borohydride, sodium sulfite, grape
One of sugar, fructose, maltose, diol compound, formaldehyde, ascorbic acid and sodium hypophosphite are a variety of；Preferably, described
Reducing agent can be ascorbic acid, glucose or sodium sulfite.Preferably, the solvent in the reducing agent solution is water.
According to the present invention, the step of addition reducing agent obtains polycrystalline microballoon specifically: by the Kocide SD-tannin
Sour composite precursor dispersion, forms Kocide SD-tannic acid dispersion liquid, is added dropwise in Xiang Suoshu Kocide SD-tannic acid dispersion liquid
Reducing agent solution is stirred to react, and is centrifugated, and is washed, and freeze-drying obtains final product cuprous oxide polycrystalline microballoon.
Preferably, the temperature being stirred to react being added in the step of reducing agent obtains polycrystalline microballoon is 10~70 DEG C,
It such as can be room temperature；The time being stirred to react is 0.5~24 hour；It is preferred that 1~8 hour.
Preferably, the reducing agent drips in 10~30 minutes.
The present invention also provides a kind of cuprous oxide polycrystalline microballoon, be using any of the above-described kind preparation method preparation and
At.Preferably, the partial size of the cuprous oxide polycrystalline microballoon is 100~800nm.
According to the present invention, the cuprous oxide polycrystalline microballoon is by brilliant (size the is about 10nm~20nm) group of cuprous nano
It fills.
Beneficial effects of the present invention:
It applies the technical scheme of the present invention, it is more by introducing biomass in the preparation process of cuprous oxide polycrystalline microballoon
Kocide SD-tannic acid composite precursor is first made as adjuvant in phenol --- tannic acid, later will be described multiple using reducing agent
It closes presoma and is reduced into cuprous oxide.Kocide SD-tannic acid composite precursor in this method provides cuprous nano
The nucleating point that crystalline substance generates, and under the action of tannic acid, can under suitable composite precursor reaction density (such as 0.01-
The polycrystalline microballoon being assembled by cuprous nano crystalline substance 0.2M) is obtained, the storage that the presence of tannic acid improves final product is steady
It is qualitative；As it can be seen that the tannic acid serves not only as a kind of nucleating agent, the inducer also assembled as monocrystalline, and can also improve most
The storage stability of final product.The partial size for the cuprous oxide polycrystalline microballoon that the present invention assembles is 100~800nm.
In addition, it also have the advantage that
1) raw material is easy to get and cheap；2) biological material tannic acid is introduced, preparation method is environmentally protective, tannic acid
Addition to the control of final product pattern and nanocrystalline stabilization and assembling all play an important role；3) this method obtains
Product is the microballoon assembled by cuprous nano crystalline substance, has not only obtained the cuprous oxide particle of stable dispersion, but also is maintained
Microcosmic nanocrystalline rock-steady structure；4) preparation method (such as 0.01-0.2M) can be approached under suitable precursor concentration
Grade cuprous oxide particle, and yield extends in industrial mass production up to 90% or more.Therefore, the present invention mentions
A kind of method that quick, easy, green prepares cuprous oxide polycrystalline microballoon is supplied.
Detailed description of the invention
Fig. 1 is preparation process intermediate product Kocide SD (a) of the present invention and Kocide SD-tannic acid (b) transmission electron microscope
Photo；
Fig. 2 is the stereoscan photograph of cuprous oxide polycrystalline microballoon prepared by the present invention, wherein the enlargement ratio of Fig. 2 (a)
It is 25,000 times, the enlargement ratio of Fig. 2 (b) is 100,000 times；
Fig. 3 is the transmission electron microscope photo of cuprous oxide polycrystalline microballoon prepared by the present invention, wherein the enlargement ratio of Fig. 3 (a)
It is 60,000 times, the enlargement ratio of Fig. 3 (b) is 120,000 times；
Fig. 4 is the high-resolution-ration transmission electric-lens photo and selection electronic diffraction of cuprous oxide polycrystalline microballoon prepared by the present invention
Pattern (illustration)；
Fig. 5 is the X-ray diffraction spectrogram of cuprous oxide polycrystalline microballoon prepared by the present invention.
Specific embodiment
It is by hydroxide as previously mentioned, the present invention provides a kind of preparation method of cuprous oxide polycrystalline microballoon
Tannic acid is introduced in copper dispersion liquid, forms Kocide SD-tannic acid composite precursor, is obtained after reducing agent restores sub- by oxidation
The cuprous oxide polycrystalline microballoon that copper nanocrystallite assembles.The tannic acid of introducing is as adjuvant, for inducing nanocrystalline assembling
At microballoon；Its Kocide SD-tannic acid composite precursor formed with Kocide SD provides the generation of cuprous nano crystalline substance
Nucleating point, and under the action of tannic acid, it can be obtained under suitable composite precursor reaction density (such as 0.01M~0.2M)
The presence of the polycrystalline microballoon being assembled by cuprous nano crystalline substance, tannic acid improves the storage stability of final product.
In a preferred embodiment of the present invention, the preparation method of cuprous oxide polycrystalline microballoon includes following preparing hydrogen
The step of copper oxide disperses liquid: strong base solution being added drop-wise in cupric salt aqueous solution, is stirred to react, and gained suspension is centrifuged
Separation, washing, obtains Kocide SD；Kocide SD dispersion liquid will be formed after Kocide SD dispersion.At of the invention one
In specific embodiment, Kocide SD is dispersed in water, since Kocide SD is not soluble in water, forms blue floccule, i.e., it is described
Kocide SD dispersion liquid.
The molar concentration of the cupric salt aqueous solution is 0.001~1M.Preferably 0.01~0.5M.Such as cupric salt
The molar concentration of aqueous solution can be 0.1M.The present invention by the molar concentration of cupric salt aqueous solution limit within the above range its
Purpose is to take into account reaction efficiency and process implementing complexity (concentration too low reaction low efficiency, the hydrogen-oxygen that excessive concentration is then formed
It is excessively high to change copper dispersion viscosity).
Wherein, the molar ratio of cupric salt aqueous solution and solute in strong base solution is (1:2)~(1:20)；Preferably (1:
4)~(1:16)；It such as can be 1:4.The molar ratio of solute in cupric salt aqueous solution and strong base solution is limited to above-mentioned model
In enclosing, abundant reaction is advantageously ensured that.
Wherein, the time being stirred to react is 5~240 minutes；It is preferred that 20~120 minutes.
In a preferred embodiment of the present invention, the Kocide SD-tannic acid composite precursor formation includes
Following steps: being added tannic acid solution in the Kocide SD dispersion liquid, be stirred to react, gained suspension is centrifugated,
Washing, obtains Kocide SD-tannic acid composite precursor.In the present invention, since tannic acid has polyphenol structure, it is easy to and metal
Ion is complexed, to form composite precursor with Kocide SD.
Wherein, the mass ratio of the tannic acid and the Kocide SD is (1:2.5)~(1:125), preferably (1:12.5)
~(1:50).In the range by the ratio control of the two, purpose guarantees that enough tannic acid participate in complexing, while ensuring hydrogen
The decline of bring pH value, which will not be added, in copper oxide because of excessive tannic acid causes to decompose.
The time being stirred to react control is 5~240 minutes by the present invention, is conducive to sufficiently react.It is preferred that be stirred to react
Time is 2~120 minutes, such as can be 30 minutes.
In a preferred embodiment of the present invention, it is specific as follows that the step of reducing agent obtains final product is added: will
Kocide SD-tannic acid composite precursor dispersion, forms Kocide SD-tannic acid dispersion liquid, Xiang Suoshu Kocide SD-tannic acid
Reducing agent solution is added dropwise in dispersion liquid, is stirred to react, is centrifugated, washs, it is more to obtain final product cuprous oxide for freeze-drying
Brilliant microballoon.
According to the present invention, the purpose for adding reducing agent is that Kocide SD-tannic acid composite precursor is reduced into cuprous oxide,
The nucleating point that Kocide SD-tannic acid provides the generation of cuprous nano crystalline substance is further assembled under the action of tannic acid
Cuprous oxide polycrystalline microballoon (100~800nm).
Wherein, the reducing agent solution is selected from hydrazine hydrate, sodium borohydride, sodium sulfite, glucose, fructose, maltose, two
One of alcoholic compound, formaldehyde, ascorbic acid and ortho phosphorous acid sodium solution are a variety of.To guarantee green and highly effective reaction, also
Former agent solution is preferably aqueous ascorbic acid.In addition, reducing agent solution for example can also be glucose solution or sulfurous acid
Sodium water solution.
Preferably, the molar concentration of the reducing agent solution is 0.01~5M；It is preferred that 0.1~1M；Such as can be
0.25M, 0.5M, 0.6M or 1M.The concentration of reducing agent is limited in the present invention, the purpose is to guarantee certain time for adding, favorably
In control cuprous oxide nucleation process.
The dosage of reducing agent is adjusted according to its type and mantoquita type, dosage, optimizes to drop rate, excellent
Choosing is so that reducing agent is added dropwise to complete in 10~30 minutes.
It in accordance with the present invention it is preferred that the temperature being stirred to react is 10~70 DEG C, such as can be room temperature.If reaction
The too high Kocide SD of temperature can decompose rapidly；On the contrary, reaction rate is too slow if the temperature of reaction is too low.Reaction time
It is 0.5~24 hour, preferably 1~8 hour.
According to another aspect of the present invention, a kind of cuprous oxide polycrystalline microballoon is additionally provided, is using any of the above-described kind
Preparation method be prepared.Preferably, the partial size of the cuprous oxide polycrystalline microballoon is 100~800nm.
Beneficial effects of the present invention are further illustrated below with reference to more specific embodiment.
Embodiment 1
1) Kocide SD is synthesized
1.7048g Copper dichloride dihydrate is added in 150mL single port bottle, and with 80mL deionized water stirring and dissolving, wherein
The molar concentration of copper chloride solution is 0.1M.After solution clarification blue, it is added dropwise with 4mL/ minutes rates into solution
20mL 2M sodium hydroxide solution continues to be stirred to react 30 minutes, 10000r/ minutes lower centrifuge separation gained navy blue suspensions,
And separation solid matter with deionized water washed once.Wherein, Copper dichloride dihydrate rubs with solute in sodium hydroxide solution
You are than being 1:4.
2) Kocide SD-tannic acid is synthesized
Again it disperses Kocide SD obtained in step 1) in 100mL deionized water, obtains dispersion liquid.Under stirring,
It is directly added into the tannin aqueous acid that 1mL concentration is 40mg/mL into above-mentioned dispersion liquid, continues to be stirred to react 30 minutes,
The 10000r/ minutes blackish green suspensions of lower centrifuge separation gained, and separating obtained solid matter with deionized water washed once.
3) reduction reaction
Again it disperses Kocide SD-tannic acid obtained in step 2) in 80mL deionized water, forms dispersion liquid,
Under stirring, the reducing agent aqueous ascorbic acid of 20mL 1M is added dropwise with 2mL/ minutes rates into dispersion liquid, stirs at room temperature
The reaction was continued 1 hour, 12000r/ minutes lower centrifuge separation gained orange suspensions, and separation product 3 is washed with deionized
It is secondary, it is collected after sediment is freeze-dried, the polycrystalline microballoon 0.65 that final product, i.e. monocrystalline cuprous nano crystalline substance are assembled into
~0.68g.
Fig. 1 is the intermediate product Kocide SD (Fig. 1 a) and hydrogen prepared during cuprous oxide polycrystalline microballoon in embodiment 1
Copper oxide-tannic acid (Fig. 1 b) transmission electron microscope photo.As can be seen that Kocide SD fiber attenuates after tannic acid is added, and
It is in situ to generate nano particle.
Fig. 2 and Fig. 3 is respectively that the stereoscan photograph of cuprous oxide polycrystalline microballoon prepared by the present invention and transmission electron microscope shine
Piece illustrates that microballoon is received by smaller as can be seen that the microsphere surface of preparation is coarse and internal structure is loose from Fig. 2 and Fig. 3
Rice grain accumulation assembles.
Fig. 4 is the high-resolution photo of product cuprous oxide polycrystalline microballoon prepared in embodiment 1, and selective electron diffraction figure
Case also demonstrates its structure that polycrystalline microballoon is made of monocrystalline cuprous nano crystalline substance.Wherein lattice fringe spacing 0.22nm and oxygen
Change cuprous (200) interplanar distance to be consistent.
The XRD spectra of product cuprous oxide polycrystalline microballoon in embodiment 1 is as shown in Figure 5, it can be seen that prepared answers
It is corresponding with the standard diffraction peak of cuprous oxide to close the diffraction maximum that object generates, and does not find the miscellaneous peak of other products, according to
The size of Scherrer formula calculated single crystal cuprous nano crystalline substance is 10.7nm, and the partial size of cuprous oxide polycrystalline microballoon is 200-
300nm。
Embodiment 2
1) Kocide SD is synthesized
19.2000g anhydrous cupric sulfate is added in 1L single port bottle, and with 504mL deionized water stirring and dissolving, is in solution
After blue clarification, 96mL 5M sodium hydroxide solution is added dropwise into solution with 6mL/ minutes rates, continues to be stirred to react 60 points
Clock, 10000r/ minutes lower centrifuge separation gained navy blue suspensions, and washed once with deionized water by solid product is separated.
2) Kocide SD-tannic acid is synthesized
Again it disperses Kocide SD obtained in step 1) in 588mL deionized water, obtains dispersion liquid.Under stirring,
It is directly added into the tannin aqueous acid that 12mL concentration is 40mg/mL into above-mentioned dispersion liquid, continues to be stirred to react 60 minutes,
The 10000r/ minutes blackish green suspensions of lower centrifuge separation gained, and separating obtained solid matter with deionized water washed once.
3) reduction reaction
Again it disperses Kocide SD-tannic acid obtained in step 2) in 80mL deionized water, forms dispersion liquid,
Under stirring, the reducing agent aqueous ascorbic acid of 120mL 0.5M was added dropwise with 5mL/ minutes rates into dispersion liquid, is stirred at room temperature
It mixes under the reaction was continued 2 hours, 12000r/ minutes and is centrifugated gained orange suspension, and separation product 3 is washed with deionized
It is secondary, collected after sediment is freeze-dried, finally obtain polycrystalline microballoon 7.30 that product cuprous nano crystalline substance is assembled into~
8.10g。
It is 11.5nm, cuprous oxide polycrystalline microballoon according to the size of Scherrer formula calculated single crystal cuprous nano crystalline substance
Partial size be 150-250nm.
The XRD spectra of prepared cuprous oxide polycrystalline microballoon is similar to embodiment 1 in embodiment 2.
Embodiment 3
1) Kocide SD is synthesized
0.4689g anhydrous nitric acid copper is added in 100mL single port bottle, and with 45mL deionized water stirring and dissolving, to solution
After clarification blue, 5mL 3M sodium hydroxide solution is added dropwise with 0.5mL/min rate, continues to be stirred to react 20min, 10000r/
Centrifugation gained navy blue suspension under min, and be washed with deionized primary.
2) Kocide SD-tannic acid is synthesized
Again it disperses Kocide SD obtained in step 1) in 50mL deionized water, obtains dispersion liquid.Under stirring, to
It is directly added into the tannin aqueous acid that 0.5mL concentration is 40mg/mL in the dispersion liquid, continues to be stirred to react 20 minutes, 10000r/
The blackish green suspension of centrifugation gained under minute, and washed once with deionized water by solid product is separated.
3) reduction reaction
Again it disperses Kocide SD-tannic acid obtained in step 2) in 40mL deionized water, forms dispersion liquid, stir
It mixes down, the reducing agent glucose solution of 10mL 0.25M is added dropwise in Xiang Shangshu dispersion liquid with the rate of 0.5mL/min, at 60 DEG C
Under, the reaction was continued 4 hours for stirring, 12000r/ minutes lower centrifuge separation gained orange suspensions, and separation is washed with deionized
It product 3 times, is collected after sediment is freeze-dried, finally obtains the polycrystalline microballoon 0.13 that product cuprous nano crystalline substance is assembled into
~0.17g.
It is 15.2nm, cuprous oxide polycrystalline microballoon according to the size of Scherrer formula calculated single crystal cuprous nano crystalline substance
Partial size be 100-800nm.
Prepared cuprous oxide polycrystalline microballoon XRD spectra is similar to Example 1 in embodiment 3.
Embodiment 4
1) Kocide SD is synthesized
0.4991g copper acetate monohydrate is added in 50mL single port bottle, and with 20mL deionized water stirring and dissolving, to solution
After green clarification, 5mL 4M potassium hydroxide solution was added dropwise with 0.5mL/ minutes rates, continues to be stirred to react 45 minutes,
10000r/ minutes lower centrifuge separation gained navy blue suspensions, and separation solid matter with deionized water washed once.
2) Kocide SD-tannic acid is synthesized
Again it disperses Kocide SD obtained in step 1) in 25mL deionized water, obtains dispersion liquid.Under stirring, to
It is directly added into the tannin aqueous acid that 0.25mL concentration is 40mg/ml in above-mentioned dispersion liquid, continues to be stirred to react 45 minutes,
The 10000r/ minutes blackish green suspensions of lower centrifuge separation gained, and washed once separating obtained solid product with deionized water.
3) reduction reaction
Again it disperses Kocide SD-tannic acid obtained in step 2) in 20mL deionized water, forms dispersion liquid,
Under stirring, the reducing agent sodium sulfite aqueous solution of 5mL 0.5M is added dropwise with 0.2mL/ minutes rates into dispersion liquid, in room temperature
The reaction was continued 1 hour for lower stirring, 12000r/ minutes lower centrifuge separation gained orange suspensions, and is washed with deionized 3 times,
It is collected after sediment is freeze-dried, finally obtains 0.12~0.16g of polycrystalline microballoon that product cuprous nano crystalline substance is assembled into.
It is 14.2nm, cuprous oxide polycrystalline microballoon according to the size of Scherrer formula calculated single crystal cuprous nano crystalline substance
Partial size be 100-400nm.
The XRD spectra of prepared cuprous oxide polycrystalline microballoon is similar to Example 1 in embodiment 4.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (24)
1. a kind of preparation method of cuprous oxide polycrystalline microballoon, which is characterized in that the described method comprises the following steps: Kocide SD
Tannic acid is added in dispersion liquid, forms Kocide SD-tannic acid composite precursor, wherein the tannic acid and the hydroxide
The mass ratio of copper is (1:2.5)~(1:125)；Reducing agent is added, obtains the oxidation assembled by cuprous nano crystalline substance Asia
Copper polycrystalline microballoon；
Wherein, the reducing agent is selected from hydrazine hydrate, sodium borohydride, sodium sulfite, glucose, fructose, maltose, glycol chemical combination
One of object, formaldehyde, ascorbic acid and sodium hypophosphite are a variety of.
2. preparation method according to claim 1, which is characterized in that the Kocide SD dispersion liquid passes through following steps shape
At: strong base solution is added drop-wise in cupric salt aqueous solution, suspension is stirred to react to obtain, is centrifugated, washing obtains hydroxide
Copper；Kocide SD dispersion liquid will be formed after Kocide SD dispersion.
3. preparation method according to claim 2, wherein the cupric salt is copper sulphate or its hydrate, copper nitrate
Or its hydrate, copper chloride or its hydrate and one of copper acetate or its hydrate or a variety of.
4. preparation method according to claim 3, wherein the cupric salt be Copper dichloride dihydrate, anhydrous cupric sulfate,
Anhydrous nitric acid copper or copper acetate monohydrate.
5. according to the described in any item preparation methods of claim 2-4, wherein the molar concentration of the cupric salt aqueous solution is
0.001~1M.
6. preparation method according to claim 5, wherein the molar concentration of the cupric salt aqueous solution be 0.01~
0.5M。
7. preparation method according to claim 2, wherein the strong base solution is that sodium hydroxide and/or potassium hydroxide are molten
Liquid；The molar concentration of the strong base solution is 0.1~10M.
8. preparation method according to claim 2, wherein the cupric salt aqueous solution rubs with solute in strong base solution
You are than being (1:2)~(1:20).
9. preparation method according to claim 2, wherein formed Kocide SD dispersion liquid in the time being stirred to react be
5~240 minutes.
10. preparation method according to claim 1, which is characterized in that the tannic acid is added in the form of a solution.
11. preparation method according to claim 1, wherein the mass ratio of the tannic acid and the Kocide SD be (1:
12.5)~(1:50).
12. preparation method according to claim 10, which is characterized in that before the formation Kocide SD-tannic acid is compound
The step of driving body specifically: tannic acid solution is added in Kocide SD dispersion liquid, is stirred to react to obtain suspension, is centrifugated,
Washing, obtains Kocide SD-tannic acid composite precursor.
13. preparation method according to claim 12, wherein the step of forming Kocide SD-tannic acid composite precursor
In the time being stirred to react be 5~240 minutes.
14. preparation method according to claim 1, which is characterized in that the reducing agent is added in the form of a solution.
15. preparation method according to claim 14, wherein the molar concentration of reducing agent solution is 0.01~5M.
16. preparation method according to claim 15, wherein the molar concentration of reducing agent solution is 0.1~1M.
17. preparation method according to claim 14, wherein the solvent in reducing agent solution is water.
18. preparation method according to claim 1, which is characterized in that the reducing agent is ascorbic acid, glucose or
Sodium sulfite.
19. preparation method according to claim 1, which is characterized in that the addition reducing agent obtains the step of polycrystalline microballoon
Suddenly specifically: the Kocide SD-tannic acid composite precursor is dispersed, Kocide SD-tannic acid dispersion liquid, Xiang Suoshu are formed
Reducing agent solution is added dropwise in Kocide SD-tannic acid dispersion liquid, is stirred to react, is centrifugated, washs, freeze-drying obtains most
Final product cuprous oxide polycrystalline microballoon.
20. preparation method according to claim 19, which is characterized in that the addition reducing agent obtains polycrystalline microballoon step
In, the temperature being stirred to react is 10~70 DEG C；The time being stirred to react is 0.5~24 hour.
21. preparation method according to claim 19, wherein the reducing agent solution drips in 10~30 minutes.
22. a kind of cuprous oxide polycrystalline microballoon, which is characterized in that the microballoon is the preparation any using claim 1-21
Method is prepared, and the cuprous oxide polycrystalline microballoon is assembled by cuprous nano crystalline substance.
23. cuprous oxide polycrystalline microballoon according to claim 22, wherein the partial size of the cuprous oxide polycrystalline microballoon is
100~800nm.
24. the cuprous oxide polycrystalline microballoon according to claim 22 or 23, which is characterized in that the cuprous nano is brilliant
Size be 10nm~20nm.
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| CN102167388A (en) * | 2010-02-26 | 2011-08-31 | 上海亿金纳米科技有限公司 | Novel and large-scale preparation method of nano-cuprous oxide |
| CN103842295A (en) * | 2011-09-30 | 2014-06-04 | 同和电子科技有限公司 | Cuprous oxide powder and method of producing same |
| CN105621473A (en) * | 2014-11-06 | 2016-06-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method for nanometer cuprous oxide particle, and morphology and particle size controlling method |
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| CN102167388A (en) * | 2010-02-26 | 2011-08-31 | 上海亿金纳米科技有限公司 | Novel and large-scale preparation method of nano-cuprous oxide |
| CN103842295A (en) * | 2011-09-30 | 2014-06-04 | 同和电子科技有限公司 | Cuprous oxide powder and method of producing same |
| CN105621473A (en) * | 2014-11-06 | 2016-06-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method for nanometer cuprous oxide particle, and morphology and particle size controlling method |
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