CN104445358B - A kind of double-decker cuprous nano microsphere and preparation method thereof - Google Patents

A kind of double-decker cuprous nano microsphere and preparation method thereof Download PDF

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CN104445358B
CN104445358B CN201410637164.5A CN201410637164A CN104445358B CN 104445358 B CN104445358 B CN 104445358B CN 201410637164 A CN201410637164 A CN 201410637164A CN 104445358 B CN104445358 B CN 104445358B
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nano microsphere
enuatrol
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cuprous
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CN104445358A (en
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王可为
葛小玲
徐秀萍
崔映红
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State Nuclear Electric Power Planning Design and Research Institute Co Ltd
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    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00Compounds of copper
    • C01G3/02Oxides; Hydroxides
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    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/70Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72Crystal-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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00Crystal-structural characteristics
    • C01P2002/80Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • C01P2004/32Spheres
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/62Submicrometer sized, i.e. from 0.1-1 micrometer
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/12Surface area

Abstract

The invention discloses a kind of double-decker cuprous nano microsphere and preparation method thereof, belong to inorganic nano synthetic material field。This preparation method comprises the following steps: (1), and mantoquita is soluble in water, obtains copper salt solution;Enuatrol is dissolved in ethanol, obtains the alcoholic solution of enuatrol;(2), the alcoholic solution of step (1) gained copper salt solution and enuatrol is added in reaction vessel, stir dropping hydrazine hydrate aqueous solution in 5-10 minute backward reaction system;(3), after described hydrazine hydrate aqueous solution drips, stirring reaction 5-10 minute at 20-30 DEG C;(4), after reaction terminates, by gained reactant liquor centrifugation, add ethanol after removing supernatant and carry out ultrasonic, repeat 2-4 time;At gained is deposited in 30-35 DEG C, namely vacuum drying obtains described double-decker nano cuprous oxide。The cuprous nano microsphere diameter prepared by the method is little, size uniformity, and owing to having double-decker, therefore specific surface area is big。

Description

A kind of double-decker cuprous nano microsphere and preparation method thereof
Technical field
The present invention relates to a kind of double-decker cuprous nano microsphere and preparation method thereof, belong to inorganic nano synthetic material field。
Background technology
Red copper oxide has special optics, catalysis and photoelectric properties, it has also become one of focus of present material scientific research。Red copper oxide is P-type semiconductor, can be applicable to the fields such as solar energy conversion, microelectronics, magnetic storage, catalysis, air-sensitive, and simultaneous oxidation is cuprous or traditional lithium cell cathode material。
The preparation method of current cuprous oxide nano particle mostly is hydro-thermal method。Such as, application number be 201210006997.2 patent utilization hydro-thermal method prepare the nanoparticle of octahedron, the shape such as spherical;Application number be the patent of 201310297480.8 with formic acid, acetaldehyde and propionic aldehyde for reducing agent, ethylenediaminetetraacetic acid is additive, utilizes hydro-thermal method to prepare solid spherical nanoparticle。Particle diameter prepared by the above method is typically in 10-100 micron, and therefore material resistance is relatively big, and specific surface area is less, and application in the semiconductor device receives a definite limitation。The microemulsion method of researcher trial subsequently, microwave heating method, soft template method have synthesized the nanoparticle of the different morphologies such as cubic, spherical, flower-shaped, banding。Such as, application number be the patent of 20081022204.4 with polyvinylpyrrolidone for surfactant, the mantoquita that reduces in aqueous with ascorbic acid prepares cuprous oxide nano particle, and surface topography becomes cube or octahedron, and particle diameter is 800 ran;Application number be the patent of 201210006997.2 with lactic acid for reducing agent, prepared the cuprous oxide nano particle of octahedron, the pattern such as spherical quincunx, fluffy by hydro-thermal method。Both the above nano particle diameter is less than 10 microns, but surface is more smooth, and its semiconductor device signal is more weak, and specific surface area remains a need for further raising。
In the process realizing the present invention, the inventors discovered that and at least there is problems in that in prior art that the cuprous nano material diameter that the preparation method of prior art prepares is relatively big, and particle surface is more smooth, specific surface area is less。
Summary of the invention
The technical problem to be solved is in that, it is provided that cuprous nano microsphere that a kind of diameter is little, specific surface area is big and preparation method thereof。
Specifically, including following technical scheme:
One aspect of the present invention provides a kind of double-decker cuprous nano microsphere, and the diameter of this cuprous nano microsphere is 400-600nm;This cuprous nano microsphere is formed by the Red copper oxide particle aggregation that diameter is 40-50nm。
Further, the diameter of described cuprous nano microsphere is 400-500nm。
Specifically, the specific surface area of described cuprous nano microsphere is 60-70m2/g。
The preparation method that another aspect of the present invention provides the double-decker cuprous nano microsphere of a kind of first aspect present invention, comprises the following steps:
Step (1), mantoquita is soluble in water, obtain copper salt solution;Enuatrol is dissolved in ethanol, obtains the alcoholic solution of enuatrol;
Step (2), adds the alcoholic solution of step (1) gained copper salt solution and enuatrol in reaction vessel, stirs dropping hydrazine hydrate aqueous solution in 5-10 minute backward reaction system;
Step (3), after described hydrazine hydrate aqueous solution drips, stirring reaction 5-10 minute at 20-30 DEG C;
Step (4), after reaction terminates, by gained reactant liquor centrifugation, adds ethanol and carries out ultrasonic, repeat 2-4 time after removing supernatant;At gained is deposited in 30-35 DEG C, namely vacuum drying obtains described double-decker cuprous nano microsphere。
Specifically, mantoquita described in step (1) is selected from copper nitrate, copper sulfate, copper chloride or Schweinfurt green。
Specifically, copper salt solution concentration described in step (1) is 10g/L-70g/L。
Specifically, copper salt solution concentration described in step (1) is 25g/L。
Specifically, described in step (1), the ethanol solution concentration of enuatrol is 1g/L-10g/L。
Specifically, hydrazine hydrate aqueous solution concentration described in step (2) is 5%-8%。
Specifically, mantoquita described in step (1) and enuatrol mass ratio be 5-50:1。
Specifically, mantoquita described in step (2) and hydrazine hydrate mass ratio be 1-5:1。
Specifically, described in step (1), the volume ratio of water and ethanol is 0.5-2:1。
Specifically, described in step (1), the volume ratio of water and ethanol is 1:1。
Specifically, described in step (3), the mixing speed of stirring reaction is 500-700rpm。
Specifically, centrifuge speed described in step (4) is 9000-11000 rev/min。
The invention has the beneficial effects as follows:
(1) the cuprous nano microsphere obtained by the preparation method of the present invention has double-decker, and gained cuprous nano microsphere surface morphology rule, diameter is less and homogeneous, and specific surface area is big。
(2) the preparation method process of the present invention is simple, reproducible, and solvent for use is water and ethanol, safety non-pollution。
Accompanying drawing explanation
In order to be illustrated more clearly that the technical scheme in the embodiment of the present invention, in below embodiment being described, the required accompanying drawing used is briefly described。
Fig. 1 is the embodiment of the present invention 1 gained cuprous nano microsphere primary structure electron scanning micrograph;
Fig. 2 is the embodiment of the present invention 1 gained cuprous nano microsphere secondary structure electron scanning micrograph;
Fig. 3 is the diameter distribution profile of the embodiment of the present invention 1 gained cuprous nano microsphere;
Fig. 4 is the XRD figure spectrum of the embodiment of the present invention 1 gained Red copper oxide;
Fig. 5 is the EDS collection of illustrative plates of the embodiment of the present invention 1 gained cuprous nano microsphere;
Fig. 6 is the electron binding energy collection of illustrative plates of the embodiment of the present invention 1 gained cuprous nano microsphere;
Fig. 7 is in the embodiment of the present invention 1 gained cuprous nano microsphereElectron binding energy collection of illustrative plates;
Fig. 8 is O in the embodiment of the present invention 1 gained cuprous nano microsphere1sElectron binding energy collection of illustrative plates;
Fig. 9 is the electron scanning micrograph of the embodiment of the present invention 2 gained cuprous nano microsphere;
Figure 10 is the electron scanning micrograph of the embodiment of the present invention 3 gained cuprous oxide nano particle;
Figure 11 is the electron scanning micrograph of the embodiment of the present invention 4 gained cuprous nano microsphere;
Figure 12 is the electron scanning micrograph of the embodiment of the present invention 5 gained cuprous nano microsphere。
Detailed description of the invention
For making technical scheme and advantage clearly, below in conjunction with accompanying drawing, embodiment of the present invention is described further in detail。
One aspect of the present invention provides a kind of double-decker cuprous nano microsphere, and the diameter of this cuprous nano microsphere is 400-600nm;This cuprous nano microsphere is formed by the Red copper oxide particle aggregation that diameter is 40-50nm。
Above-mentioned cuprous nano microsphere diameter is only 400-600nm, and owing to being formed by the Red copper oxide particle aggregation of 40-50nm, therefore compared with prior art, the cuprous nano microsphere specific surface area of the present invention is big, has more using value in fields such as solaode, catalyst, microelectronics。
Specifically, the diameter more preferably 400-500nm of above-mentioned cuprous nano microsphere;The specific surface area of gained cuprous nano microsphere can reach 60-70m2/g。
The preparation method that another aspect of the present invention provides the double-decker nano cuprous oxide of a kind of first aspect present invention, comprises the following steps:
Step (1), mantoquita is soluble in water, obtain copper salt solution;Enuatrol is dissolved in ethanol, obtains the alcoholic solution of enuatrol;
Step (2), adds the alcoholic solution of step (1) gained copper salt solution and enuatrol in reaction vessel, stirs dropping hydrazine hydrate aqueous solution in 5-10 minute backward reaction system;
Step (3), after described hydrazine hydrate aqueous solution drips, stirring reaction 5-10 minute at 20-30 DEG C;
Step (4), after reaction terminates, by gained reactant liquor centrifugation, adds ethanol and carries out ultrasonic, repeat 2-4 time after removing supernatant;At gained is deposited in 30-35 DEG C, namely vacuum drying obtains described double-decker nano cuprous oxide。
This preparation method is by rationally selecting the ratio of mantoquita concentration, concentrations of sodium oleate and water and ethanol, control the pattern of final cuprous oxide nano particle, obtaining and have double-deck cuprous nano microsphere, namely diameter is the cuprous nano microsphere of 400-600nm is formed by the Red copper oxide particle aggregation that diameter is 40-50nm。Compared with prior art, surface topography rule, diameter is less and homogeneous for gained cuprous nano microsphere;Owing to having double-decker so that the specific surface area of gained cuprous oxide nano particle of the present invention is big。And this preparation method process is simple, reproducible, solvent for use is water and ethanol, safety non-pollution。
In above-mentioned preparation method, mantoquita described in step (1) is selected from copper nitrate, copper sulfate, copper chloride or Schweinfurt green。Described copper salt solution concentration is 10g/L-70g/L。The pattern of final cuprous oxide nano particle is had considerable influence by mantoquita concentration, when mantoquita content is less, there is substantial amounts of fine granularity product in product, it is impossible to generate the cuprous structure of secondary oxidation;When mantoquita content reaches 10g/L, product occurs a large amount of microsphere and a small amount of incomplete microsphere。Visible, the content of mantoquita requires more than a marginal value could form Nano microsphere product。Wherein, when the content of mantoquita reaches 25g/L, product is entirely Nano microsphere。
In above-mentioned preparation method, described in step (1), the ethanol solution concentration of enuatrol is 1g/L-10g/L。Enuatrol is as surfactant in this preparation method, and its concentration also contributes to the pattern of end product。When in system without enuatrol, solution not only generates without any spherical product, and generates the irregular product of a large amount of diameters more than 10 μm。This illustrates the particle diameter being added with reduction product grain of enuatrol, it is suppressed that the effect of Red copper oxide growth;When system adds a small amount of enuatrol (0.1g/L-0.5g/L), solution produces small granular disintegration, but these little granules cannot be self-assembled into microsphere。Along with the content of enuatrol increases further, when in system containing 1g/L enuatrol, microspheroidal product increasingly generates, but still has irregular product to generate。During containing 1g/L-10g/L enuatrol, product has almost been entirely Nano microsphere。
In above-mentioned preparation method, hydrazine hydrate aqueous solution mass percent described in step (2) is 5%-8%, owing to hydrazine hydrate reduction is very strong, reactivity is significantly high, therefore to be added dropwise to again in reaction system after hydrazine hydrate is diluted, avoid reaction excessively violent, be copper by mantoquita direct-reduction。
In above-mentioned preparation method, described in step (1), the mass ratio of mantoquita and enuatrol is 5-50:1。
In above-mentioned preparation method, mantoquita described in step (2) and hydrazine hydrate mass ratio be 1-5:1。In this preparation method, hydrazine hydrate is reducing agent, and the cupric in mantoquita is reduced to monovalence copper, and therefore, the ratio of mantoquita and hydrazine hydrate should enable cupric be fully converted to monovalence copper, makes final gained Red copper oxide purity higher。
In above-mentioned preparation method, described in step (1), the volume ratio of water and ethanol is 0.5-2:1。The pattern of the nanoparticle ultimately formed is affected very big by the selection of solvent, this is because the mixed liquor of water and ethanol can regulate enuatrol existing forms in the solution, enuatrol ordered state in a solvent can be had influence on, and then affect the pattern of the nanoparticle ultimately formed。Wherein, the volume ratio of water and ethanol more preferably 1:1。
In above-mentioned preparation method, described in step (3), the mixing speed of stirring reaction is 500-700rpm。Such mixing speed advantageously forms intended pattern。
In above-mentioned preparation method, centrifuge speed described in step (4) is 9000-11000 rev/min。In this range of speeds, precipitation and supernatant both can be made to be sufficiently separated, the pattern of gained cuprous nano microsphere can not have been destroyed again。
In above-mentioned preparation method, adding EtOH Sonicate in step (4) after centrifugation is to remove unreacted hydrazine hydrate and unnecessary enuatrol, the added amount of ethanol, ultrasonic time and ultrasonic number of times do not have considered critical, as long as ensureing that unreacted hydrazine hydrate and unnecessary enuatrol are removed。
In above-mentioned preparation method, reaction temperature does not have considered critical, at room temperature reacts。Vacuum drying temperature in step (4), drying time also without considered critical, as long as the moisture in gained cuprous nano microsphere and ethanol can be removed。
In the embodiment of the present invention, used chemical reagent is as follows:
Schweinfurt green, chemical pure, purchased from Beijing chemical reagents corporation;
Copper nitrate, chemical pure, purchased from Beijing chemical reagents corporation;
Copper sulfate, chemical pure, purchased from Beijing chemical reagents corporation;
Copper chloride, chemical pure, purchased from Beijing chemical reagents corporation;
Enuatrol, chemical pure, purchased from Xi Long chemical plant, Shantou, Guangdong city;
Hydrazine hydrate, purity 80% (mass fraction), purchased from Xi Long chemical plant, Shantou, Guangdong city;
Ethanol, chemical pure, purchased from Beijing chemical reagents corporation。
In the embodiment of the present invention, instrument is as follows:
Sirion200 scanning electron microscope (SEM, FEI Co. of Holland);
X ' PertProMRD type X-ray diffractometer (XRD, Shimadzu Corporation);
AXISUltra type x-ray photoelectron power spectrum (XPS, Shimadzu Corporation);
TGL-16C type centrifuge (ANKE instrument company);
KQ-300GVDV type ultrasonic machine (Kunshan Ultrasonic Instruments Co., Ltd.);
AL204/01 type analysis balance (Mettler Toledo Inc.);
3H-2000BET-M type specific surface area analysis instrument (Bei Shide company)。
Embodiment 1
The preparation method that the present embodiment provides a kind of double-decker cuprous nano microsphere。
Step (1), is dissolved in 2.5g Schweinfurt green in 50ml water, obtains Schweinfurt green aqueous solution;0.25g enuatrol is dissolved in 50ml ethanol, obtains the alcoholic solution of enuatrol;
Step (2), adds the alcoholic solution of step (1) gained Schweinfurt green aqueous solution and enuatrol in three-neck flask, stirs 5 minutes;The hydrazine hydrate solution of 1ml mass fraction 80% is diluted for being added drop-wise in reaction system after 10ml;
Step (3), after hydrazine hydrate aqueous solution drips, stirring reaction 10 minutes, mixing speed 600rpm at 20 DEG C;
Step (4), after reaction terminates, by gained reactant liquor centrifugation, adds 10ml EtOH Sonicate 10 minutes after removing supernatant, repeats 3 times;Namely gained is deposited at 30 DEG C vacuum drying obtains described double-decker nano cuprous oxide。
By scanning electron microscope, X-ray diffractometer, x-ray photoelectron spectroscopy instrument etc., gained cuprous nano microsphere is tested。
Be can be seen that by gained cuprous nano microsphere primary structure electron scanning micrograph (Fig. 1), secondary structure electron scanning micrograph (Fig. 2), gained cuprous nano microsphere has double-decker, and namely diameter shown in figure is the Nano microsphere of 400-600nm is formed by the Red copper oxide particle aggregation that diameter is 40-50nm。From the diameter distribution profile (Fig. 3) of gained cuprous nano microsphere it can be seen that gained cuprous nano microsphere diameter is more uniform, the diameter of more than 50 complete microspheres being carried out statistics discovery, the diameter of the microsphere of more than 90% is between 400-600nm。Owing to having double-decker, therefore the specific surface area of gained cuprous nano microsphere has reached 65.1m2/g。
Fig. 4 is the XRD figure spectrum of the present embodiment gained Red copper oxide, and the diffraction maximum in figure is the diffraction maximum of the crystal faces such as Red copper oxide (110), (111), (200), (221), (220), (310), (311), (222) respectively;Not having the diffraction maximum of copper, copper oxide, Copper hydrate and Schweinfurt green in figure, therefore, gained cuprous oxide crystal purity is higher。
Fig. 5 is the EDS collection of illustrative plates of the present embodiment gained cuprous nano microsphere, in figure, Cu peak-to-peak value is 0.94keV, 8.08keV, 8.96keV, O peak-to-peak value is 0.54keV, and wherein the atomic quantity of Cu accounts for the 58.46% of total statistical magnitude, and the atomic quantity of O accounts for the 31.73% of total quantity, the ratio of copper atom number and oxygen atomicity, close to 2:1, further illustrates gained Red copper oxide purity higher。
The electron binding energy collection of illustrative plates of the cuprous nano microsphere that Fig. 6, Fig. 7 and Fig. 8 respectively the present embodiment obtains,Electron binding energy collection of illustrative plates and O1sElectron binding energy collection of illustrative plates, can obtain from figure,Electron binding energy be 932.18eV, O1sElectron binding energy respectively 530.3eV, 531.5eV and 532.4eV, same illustrate that gained Nano microsphere is Red copper oxide。
Embodiment 2
The preparation method that the present embodiment provides a kind of double-decker cuprous nano microsphere。
Step (1), is dissolved in 1.0g Schweinfurt green in 50ml water, obtains Schweinfurt green aqueous solution;0.25g enuatrol is dissolved in 50ml ethanol, obtains the alcoholic solution of enuatrol;
Step (2), adds the alcoholic solution of step (1) gained Schweinfurt green aqueous solution and enuatrol in three-neck flask, stirs 5 minutes;The hydrazine hydrate solution of 1ml mass fraction 80% is diluted for being added drop-wise in reaction system after 10ml;
Step (3), after hydrazine hydrate aqueous solution drips, stirring reaction 10 minutes, mixing speed 600rpm at 20 DEG C;
Step (4), after reaction terminates, by gained reactant liquor centrifugation, adds 10ml EtOH Sonicate 10 minutes after removing supernatant, repeats 3 times;Namely gained is deposited at 30 DEG C vacuum drying obtains described double-decker nano cuprous oxide。
The stereoscan photograph of the present embodiment gained nano cuprous oxide, as it is shown in figure 9, the present embodiment is compared with embodiment 1, reduces the concentration of copper salt solution。It can be seen that the pattern of nano cuprous oxide that obtains of the present embodiment is irregular, there is incomplete Nano microsphere in comparison diagram 9 and Fig. 1。As can be seen here, the concentration of copper salt solution can affect the pattern of final Red copper oxide。
Embodiment 3
Step (1), is dissolved in 2.5g Schweinfurt green in 50ml water, obtains Schweinfurt green aqueous solution;
Step (2), adds step (1) gained Schweinfurt green aqueous solution and 50ml alcoholic solution in three-neck flask, stirs 5 minutes;The hydrazine hydrate solution of 1ml mass fraction 80% is diluted for being added drop-wise in reaction system after 10ml;
Step (3), after hydrazine hydrate aqueous solution drips, stirring reaction 10 minutes, mixing speed 600rpm at 20 DEG C;
Step (4), after reaction terminates, by gained reactant liquor centrifugation, adds 10ml EtOH Sonicate 10 minutes after removing supernatant, repeats 3 times;Namely gained is deposited at 30 DEG C vacuum drying obtains described double-decker nano cuprous oxide。
The stereoscan photograph of the present embodiment gained Red copper oxide is as shown in Figure 10, the present embodiment does not add surfactant enuatrol, from stereoscan photograph it can be seen that the irregular particle that the Red copper oxide that the present embodiment obtains is particle diameter more than 10 μm, it does not have spherical product generates。
Embodiment 4
Step (1), is dissolved in 2.5g Schweinfurt green in 50ml water, obtains Schweinfurt green aqueous solution;0.10g enuatrol is dissolved in 50ml ethanol, obtains the alcoholic solution of enuatrol;
Step (2), adds the alcoholic solution of step (1) gained Schweinfurt green aqueous solution and enuatrol in three-neck flask, stirs 5 minutes;The hydrazine hydrate solution of 1ml mass fraction 80% is diluted for being added drop-wise in reaction system after 10ml;
Step (3), after hydrazine hydrate aqueous solution drips, stirring reaction 10 minutes, mixing speed 600rpm at 20 DEG C;
Step (4), after reaction terminates, by gained reactant liquor centrifugation, adds 10ml EtOH Sonicate 10 minutes after removing supernatant, repeats 3 times;Namely gained is deposited at 30 DEG C vacuum drying obtains described double-decker nano cuprous oxide。
As shown in figure 11, the present embodiment, compared with embodiment 1, reduces the concentration of enuatrol alcoholic solution to the stereoscan photograph of the present embodiment gained Red copper oxide, namely reduces surfactant concentration in reaction system。Figure 11 and Fig. 1 is it can be seen that generate Nano microsphere in product in contrast, but particle diameter is uneven, and yet suffers from irregular little granule。
Embodiment 5
Step (1), is dissolved in 2.5g Schweinfurt green in 50ml water, obtains Schweinfurt green aqueous solution;0.50g enuatrol is dissolved in 50ml ethanol, obtains the alcoholic solution of enuatrol;
Step (2), adds the alcoholic solution of step (1) gained Schweinfurt green aqueous solution and enuatrol in three-neck flask, stirs 5 minutes;The hydrazine hydrate solution of 1ml mass fraction 80% is diluted for being added drop-wise in reaction system after 10ml;
Step (3), after hydrazine hydrate aqueous solution drips, stirring reaction 10 minutes, mixing speed 600rpm at 20 DEG C;
Step (4), after reaction terminates, by gained reactant liquor centrifugation, adds 10ml EtOH Sonicate 10 minutes after removing supernatant, repeats 3 times;Namely gained is deposited at 30 DEG C vacuum drying obtains described double-decker nano cuprous oxide。
As shown in figure 12, the present embodiment, compared with embodiment 1, adds the concentration of enuatrol alcoholic solution to the stereoscan photograph of the present embodiment gained Red copper oxide, namely adds surfactant concentration in reaction system。The present embodiment gained cuprous nano microsphere has double-decker as can be seen from Figure 12, and wherein, the particle diameter major part of its secondary structure is between 400-500nm。Figure 12 and Fig. 1 is it can be seen that the present embodiment gained cuprous nano Microsphere Size is more homogeneous in contrast, and shape is more regular, and dispersibility is better。
In sum, by rationally selecting the ratio of mantoquita concentration, concentrations of sodium oleate and water and ethanol, the pattern of final gained cuprous oxide nano particle can be controlled, obtain size uniformity, pattern rule, particle diameter is less, specific surface area is big has double-deck cuprous nano microsphere。
The above is for only for ease of those skilled in the art and understands technical scheme, not in order to limit the present invention。All within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention。

Claims (11)

1. a double-decker cuprous nano microsphere, it is characterised in that the diameter of described cuprous nano microsphere is 400-600nm;Described cuprous nano microsphere is formed by the Red copper oxide particle aggregation that diameter is 40-50nm;The specific surface area of described cuprous nano microsphere is 60-70m2/g。
2. cuprous nano microsphere according to claim 1, it is characterised in that the diameter of described cuprous nano microsphere is 400-500nm。
3. the preparation method of double-decker cuprous nano microsphere described in a claim 1, it is characterised in that described preparation method comprises the following steps:
Step (1), mantoquita is soluble in water, obtain copper salt solution;Enuatrol is dissolved in ethanol, obtains the alcoholic solution of enuatrol;
Step (2), adds the alcoholic solution of step (1) gained copper salt solution and enuatrol in reaction vessel, stirs dropping hydrazine hydrate aqueous solution in 5-10 minute backward reaction system;
Step (3), after described hydrazine hydrate aqueous solution drips, stirring reaction 5-10 minute at 20-30 DEG C;
Step (4), after reaction terminates, by gained reactant liquor centrifugation, adds ethanol and carries out ultrasonic, repeat 2-4 time after removing supernatant;At gained is deposited in 30-35 DEG C, namely vacuum drying obtains described double-decker cuprous nano microsphere;
Described in step (1), the ethanol solution concentration of enuatrol is 1g/L-10g/L;
Described in step (1), the mass ratio of mantoquita and enuatrol is 5-50:1;
Described in step (1), the volume ratio of water and ethanol is 0.5-2:1。
4. preparation method according to claim 3, it is characterised in that mantoquita described in step (1) is selected from copper nitrate, copper sulfate, copper chloride or Schweinfurt green。
5. preparation method according to claim 3, it is characterised in that copper salt solution concentration described in step (1) is 10g/L-70g/L。
6. preparation method according to claim 5, it is characterised in that copper salt solution concentration described in step (1) is 25g/L。
7. preparation method according to claim 3, it is characterised in that hydrazine hydrate aqueous solution mass percent described in step (2) is 5%-8%。
8. preparation method according to claim 3, it is characterised in that described in step (2), the mass ratio of mantoquita and hydrazine hydrate is 1-5:1。
9. preparation method according to claim 3, it is characterised in that described in step (1), the volume ratio of water and ethanol is 1:1。
10. preparation method according to claim 3, it is characterised in that described in step (3), the mixing speed of stirring reaction is 500-700rpm。
11. preparation method according to claim 3, it is characterised in that centrifugal rotational speed described in step (4) is 9000-11000 rev/min。
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CN105905936B (en) * 2016-04-14 2017-11-14 青岛大学 A kind of cuprous nano crystalline substance assembly
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CN103466681A (en) * 2013-08-29 2013-12-25 河南师范大学 Preparation method of graded spherical cuprous oxide hollow nano particle

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CN103466681A (en) * 2013-08-29 2013-12-25 河南师范大学 Preparation method of graded spherical cuprous oxide hollow nano particle

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