CN104445358A - Cuprous oxide nano microspheres in double-layered structure and preparation method thereof - Google Patents
Cuprous oxide nano microspheres in double-layered structure and preparation method thereof Download PDFInfo
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2006/12—Surface area
Abstract
The invention discloses cuprous oxide nano microspheres in a double-layered structure and a preparation method thereof, belonging to the field of inorganic nano synthetic materials. The preparation method comprises the following steps: (1) dissolving copper salt in water to obtain a copper salt aqueous solution; dissolving sodium oleate in ethanol to obtain an ethanol solution of sodium oleate; (2) adding the copper salt aqueous solution and the ethanol solution of sodium oleate obtained in the step (1) into the reaction container, and after stirring for 5-10 minutes, dropwise adding a hydrazine hydrate aqueous solution into a reaction system; (3) after dropwise adding the hydrazine hydrate aqueous solution, stirring to react for 5-10 minutes at 20-30 DEG C; and (4) after reaction, carrying out centrifugal separation on the obtained reaction liquid, removing supernate, adding ethanol for ultrasonic treatment, and repeating for 2-4 times; and drying the obtained precipitate at 30-35 DEG C in vacuum to obtain the cuprous oxide nano microspheres in the double-layered structure. The cuprous oxide nano microspheres prepared by the method disclosed by the invention are small in diameter and uniform in size. As the cuprous oxide nano microspheres have the double-layered structure, the cuprous oxide nano microspheres are large in specific surface area.
Description
Technical field
The present invention relates to a kind of bilayer structure cuprous nano microballoon and preparation method thereof, belong to inorganic nano synthetic materials field.
Background technology
Red copper oxide has special optics, catalysis and photoelectric properties, has 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 converting, microelectronics, magnetic storage, catalysis, air-sensitive, the cuprous or traditional lithium cell cathode material of simultaneous oxidation.
The preparation method of current cuprous oxide nano particle mostly is hydrothermal method.Such as, application number be 201210006997.2 patent utilization hydrothermal method prepare the nanoparticle of octahedron, the shape such as spherical; Application number be 201310297480.8 patent with formic acid, acetaldehyde and propionic aldehyde for reductive agent, ethylenediamine tetraacetic acid (EDTA) is additive, utilizes hydrothermal method to prepare solid spherical nanoparticle.The particle diameter prepared of these methods is generally at 10-100 micron above, and therefore material resistance is comparatively large, and specific surface area is less, and application in the semiconductor device receives a definite limitation.Investigator attempts the nanoparticle having synthesized cubic, the different morphologies such as spherical, flower-shaped, banded with microemulsion method, microwave heating method, soft template method subsequently.Such as, application number be 20081022204.4 patent take polyvinylpyrrolidone as tensio-active agent, reduce mantoquita in aqueous with xitix and prepare cuprous oxide nano particle, surface topography becomes cubes or octahedron, and particle diameter is 800 ran; Application number be 201210006997.2 patent take lactic acid as reductive agent, prepared the cuprous oxide nano particle of octahedron, quincunx, the fluffy pattern such as spherical by hydrothermal method.Above two kinds of nano particle diameters are less than 10 microns, but surface is more smooth, and its semiconducter device signal is more weak, and specific surface area still needs further raising.
Realizing in process of the present invention, the present inventor finds at least there is following problem in prior art: the cuprous nano material diameter that the preparation method of prior art prepares is comparatively large, and particle surface is more smooth, and specific surface area is less.
Summary of the invention
Technical problem to be solved by this invention is, provides cuprous nano microballoon that a kind of diameter is little, specific surface area is large and preparation method thereof.
Specifically, following technical scheme is comprised:
One aspect of the present invention provides a kind of bilayer structure cuprous nano microballoon, and the diameter of this cuprous nano microballoon is 400-600nm; The Red copper oxide particle aggregation that this cuprous nano microballoon is 40-50nm by diameter forms.
Further, the diameter of described cuprous nano microballoon is 400-500nm.
Particularly, the specific surface area of described cuprous nano microballoon is 60-70m
2/ g.
The present invention provides a kind of preparation method of bilayer structure cuprous nano microballoon of first aspect present invention on the other hand, comprises the following steps:
Step (1), mantoquita is soluble in water, obtain copper salt solution; Sodium oleate is dissolved in ethanol, obtains the ethanolic soln of sodium oleate;
Step (2), adds in reaction vessel by the ethanolic soln of step (1) gained copper salt solution and sodium oleate, stirs and drips hydrazine hydrate aqueous solution in backward reaction system in 5-10 minute;
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 the centrifugation of gained reaction solution, adds ethanol after removing supernatant liquor and carries out ultrasonic, repeat 2-4 time; At gained being deposited in 30-35 DEG C, namely vacuum-drying obtain described bilayer structure cuprous nano microballoon.
Particularly, described in step (1), mantoquita is selected from cupric nitrate, copper sulfate, cupric chloride or neutralized verdigris.
Particularly, described in step (1), copper salt solution concentration is 10g/L-70g/L.
Particularly, described in step (1), copper salt solution concentration is 25g/L.
Particularly, described in step (1), the ethanol solution concentration of sodium oleate is 1g/L-10g/L.
Particularly, described in step (2), hydrazine hydrate aqueous solution concentration is 5%-8%.
Particularly, mantoquita described in step (1) and sodium oleate mass ratio be 5-50:1.
Particularly, mantoquita described in step (2) and hydrazine hydrate mass ratio be 1-5:1.
Particularly, described in step (1), the volume ratio of water and ethanol is 0.5-2:1.
Particularly, described in step (1), the volume ratio of water and ethanol is 1:1.
Particularly, described in step (3), the stirring velocity of stirring reaction is 500-700rpm.
Particularly, described in step (4), centrifuge speed is 9000-11000 rev/min.
The invention has the beneficial effects as follows:
(1) the cuprous nano microballoon obtained by preparation method of the present invention has bilayer structure, and gained cuprous nano microsphere surface morphology rule, diameter is less and homogeneous, and specific surface area is large.
(2) preparation method's 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 in the technical scheme in the embodiment of the present invention, in describing embodiment below, the required accompanying drawing used is briefly described.
Fig. 1 is the embodiment of the present invention 1 gained cuprous nano microballoon primary structure electron scanning micrograph;
Fig. 2 is the embodiment of the present invention 1 gained cuprous nano microballoon secondary structure electron scanning micrograph;
Fig. 3 is the diameter distribution profile of the embodiment of the present invention 1 gained cuprous nano microballoon;
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 microballoon;
Fig. 6 is the electron binding energy collection of illustrative plates of the embodiment of the present invention 1 gained cuprous nano microballoon;
Fig. 7 is in the embodiment of the present invention 1 gained cuprous nano microballoon
electron binding energy collection of illustrative plates;
Fig. 8 is O in the embodiment of the present invention 1 gained cuprous nano microballoon
1selectron binding energy collection of illustrative plates;
Fig. 9 is the electron scanning micrograph of the embodiment of the present invention 2 gained cuprous nano microballoon;
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 microballoon;
Figure 12 is the electron scanning micrograph of the embodiment of the present invention 5 gained cuprous nano microballoon.
Embodiment
For making technical scheme of the present invention 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 bilayer structure cuprous nano microballoon, and the diameter of this cuprous nano microballoon is 400-600nm; The Red copper oxide particle aggregation that this cuprous nano microballoon is 40-50nm by diameter forms.
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, cuprous nano microballoon specific surface area of the present invention is large, has more using value in fields such as solar cell, catalyzer, microelectronics.
Specifically, the diameter more preferably 400-500nm of above-mentioned cuprous nano microballoon; The specific surface area of gained cuprous nano microballoon can reach 60-70m
2/ g.
The present invention provides a kind of preparation method of bilayer structure nano cuprous oxide of first aspect present invention on the other hand, comprises the following steps:
Step (1), mantoquita is soluble in water, obtain copper salt solution; Sodium oleate is dissolved in ethanol, obtains the ethanolic soln of sodium oleate;
Step (2), adds in reaction vessel by the ethanolic soln of step (1) gained copper salt solution and sodium oleate, stirs and drips hydrazine hydrate aqueous solution in backward reaction system in 5-10 minute;
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 the centrifugation of gained reaction solution, adds ethanol after removing supernatant liquor and carries out ultrasonic, repeat 2-4 time; At gained being deposited in 30-35 DEG C, namely vacuum-drying obtain described bilayer structure nano cuprous oxide.
This preparation method is by the ratio of choose reasonable mantoquita concentration, concentrations of sodium oleate and water and ethanol, control the pattern of final cuprous oxide nano particle, obtain and have double-deck cuprous nano microballoon, namely diameter is the cuprous nano microballoon of 400-600nm is that the Red copper oxide particle aggregation being 40-50nm by diameter forms.Compared with prior art, surface topography is regular, and diameter is less and homogeneous for gained cuprous nano microballoon; Owing to having bilayer structure, make the specific surface area of gained cuprous oxide nano particle of the present invention large.And this preparation method's process is simple, reproducible, solvent for use is water and ethanol, safety non-pollution.
In above-mentioned preparation method, described in step (1), mantoquita is selected from cupric nitrate, copper sulfate, cupric chloride or neutralized verdigris.Described copper salt solution concentration is 10g/L-70g/L.The pattern of mantoquita concentration to final cuprous oxide nano particle has considerable influence, when mantoquita content is less, there is a large amount of fine granularity products in product, cannot generate the cuprous structure of secondary oxidation; When mantoquita content reaches 10g/L, in product, there is a large amount of microballoon and a small amount of incomplete microballoon.Visible, the content of mantoquita needs could form Nano microsphere product more than a threshold value.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 sodium oleate is 1g/L-10g/L.Sodium oleate is as tensio-active agent in this preparation method, and its concentration also affects the pattern of final product.When not containing sodium oleate in system, not only generating without any spherical product in solution, and generating the irregular product of a large amount of diameter more than 10 μm.This illustrates adding to have and reducing the particle diameter of product grain, the effect of the cuprous growth of inhibited oxidation of sodium oleate; When adding a small amount of sodium oleate (0.1g/L-0.5g/L) in system, in solution, produce small granular disintegration, but these small-particles cannot be self-assembled into microballoon.Along with the content of sodium oleate increases further, when containing 1g/L sodium oleate in system, microspheroidal product generates gradually, but still has irregular product to generate.During containing 1g/L-10g/L sodium oleate, product has been all almost Nano microsphere.
In above-mentioned preparation method, described in step (2), hydrazine hydrate aqueous solution mass percent is 5%-8%, because hydrazine hydrate reduction is very strong, reactive behavior is very high, therefore be added dropwise to again in reaction system after hydrazine hydrate will being diluted, avoiding reaction too violent, is copper by mantoquita direct-reduction.
In above-mentioned preparation method, described in step (1), the mass ratio of mantoquita and sodium oleate 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 reductive agent, and the cupric in mantoquita is reduced to monovalence copper, and therefore, the ratio of mantoquita and hydrazine hydrate should enable cupric be converted into monovalence copper completely, 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 impact of selection on the final nanoparticle formed of solvent is very large, this is because the mixed solution of water and ethanol can regulate sodium oleate existing forms in the solution, sodium oleate ordered state in a solvent can be had influence on, and then the pattern of the final nanoparticle formed of impact.Wherein, the volume ratio of water and ethanol more preferably 1:1.
In above-mentioned preparation method, described in step (3), the stirring velocity of stirring reaction is 500-700rpm.Such stirring velocity is conducive to the pattern forming expection.
In above-mentioned preparation method, described in step (4), centrifuge speed is 9000-11000 rev/min.In this speed range, precipitation both can be made fully to be separated with supernatant liquor, the pattern of gained cuprous nano microballoon can not have been destroyed again.
In above-mentioned preparation method, adding EtOH Sonicate after centrifugation in step (4) is to remove unreacted hydrazine hydrate and unnecessary sodium oleate, the amount of added ethanol, ultrasonic time and ultrasonic number of times do not have considered critical, as long as ensure that unreacted hydrazine hydrate and unnecessary sodium oleate are removed.
In above-mentioned preparation method, temperature of reaction does not have considered critical, at room temperature reacts.Vacuum-drying temperature in step (4), time of drying do not have considered critical yet, as long as the moisture in gained cuprous nano microballoon and ethanol can be removed.
In the embodiment of the present invention use chemical reagent as follows:
Neutralized verdigris, chemical pure, purchased from Beijing chemical reagents corporation;
Cupric nitrate, chemical pure, purchased from Beijing chemical reagents corporation;
Copper sulfate, chemical pure, purchased from Beijing chemical reagents corporation;
Cupric chloride, chemical pure, purchased from Beijing chemical reagents corporation;
Sodium oleate, chemical pure, purchased from Xi Long chemical plant, Shantou, Guangdong city;
Hydrazine hydrate, purity 80% (massfraction), 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:
Sirion 200 scanning electronic microscope (SEM, Dutch FEI Co.);
X ' Pert Pro MRD type X-ray diffractometer (XRD, Shimadzu Corporation);
AXIS Ultra type x-ray photoelectron power spectrum (XPS, Shimadzu Corporation);
TGL-16C type whizzer (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 present embodiment provides a kind of preparation method of bilayer structure cuprous nano microballoon.
Step (1), is dissolved in 2.5g neutralized verdigris in 50ml water, obtains the neutralized verdigris aqueous solution; 0.25g sodium oleate is dissolved in 50ml ethanol, obtains the ethanolic soln of sodium oleate;
Step (2), adds in three-necked flask by the ethanolic soln of step (1) the gained neutralized verdigris aqueous solution and sodium oleate, stirs 5 minutes; By the dilution of the hydrazine hydrate solution of 1ml massfraction 80% for being added drop-wise in reaction system after 10ml;
Step (3), after hydrazine hydrate aqueous solution drips, stirring reaction 10 minutes at 20 DEG C, stirring velocity 600rpm;
Step (4), after reaction terminates, by the centrifugation of gained reaction solution, adds 10ml EtOH Sonicate 10 minutes after removing supernatant liquor, repeats 3 times; At gained being deposited in 30 DEG C, namely vacuum-drying obtain described bilayer structure nano cuprous oxide.
By scanning electronic microscope, X-ray diffractometer, x-ray photoelectron spectroscopy instrument etc., gained cuprous nano microballoon is tested.
Can be found out by gained cuprous nano microballoon primary structure electron scanning micrograph (Fig. 1), secondary structure electron scanning micrograph (Fig. 2), gained cuprous nano microballoon has bilayer structure, and namely diameter shown in figure is the Nano microsphere of 400-600nm is that the Red copper oxide particle aggregation being 40-50nm by diameter forms.As can be seen from the diameter distribution profile (Fig. 3) of gained cuprous nano microballoon, gained cuprous nano microsphere diameter is more even, carry out statistics discovery to the diameter of more than 50 complete microballoons, the diameter of the microballoon of more than 90% is between 400-600nm.Owing to having bilayer structure, therefore the specific surface area of gained cuprous nano microballoon reaches 65.1m
2/ g.
Fig. 4 is the XRD figure spectrum of the present embodiment gained Red copper oxide, and the diffraction peak in figure is the diffraction peak of the crystal face such as Red copper oxide (110), (111), (200), (221), (220), (310), (311), (222) respectively; Do not have the diffraction peak of copper, cupric oxide, copper hydroxide and neutralized verdigris 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 microballoon, in figure, Cu peak-to-peak value is 0.94keV, 8.08keV, 8.96keV, O peak-to-peak value is 0.54keV, and the atomic quantity that wherein atomic quantity of Cu accounts for 58.46%, O of total statistical magnitude accounts for 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.
Fig. 6, Fig. 7 and Fig. 8 be respectively the cuprous nano microballoon that the present embodiment obtains electron binding energy collection of illustrative plates,
electron binding energy collection of illustrative plates and O
1selectron binding energy collection of illustrative plates, can obtain from figure,
electron binding energy be 932.18eV, O
1selectron binding energy be respectively 530.3eV, 531.5eV and 532.4eV, same illustrate that gained Nano microsphere is Red copper oxide.
Embodiment 2
The present embodiment provides a kind of preparation method of bilayer structure cuprous nano microballoon.
Step (1), is dissolved in 1.0g neutralized verdigris in 50ml water, obtains the neutralized verdigris aqueous solution; 0.25g sodium oleate is dissolved in 50ml ethanol, obtains the ethanolic soln of sodium oleate;
Step (2), adds in three-necked flask by the ethanolic soln of step (1) the gained neutralized verdigris aqueous solution and sodium oleate, stirs 5 minutes; By the dilution of the hydrazine hydrate solution of 1ml massfraction 80% for being added drop-wise in reaction system after 10ml;
Step (3), after hydrazine hydrate aqueous solution drips, stirring reaction 10 minutes at 20 DEG C, stirring velocity 600rpm;
Step (4), after reaction terminates, by the centrifugation of gained reaction solution, adds 10ml EtOH Sonicate 10 minutes after removing supernatant liquor, repeats 3 times; At gained being deposited in 30 DEG C, namely vacuum-drying obtain described bilayer structure nano cuprous oxide.
As shown in Figure 9, the present embodiment, compared with embodiment 1, reduces the concentration of copper salt solution to the stereoscan photograph of the present embodiment gained nano cuprous oxide.Comparison diagram 9 and Fig. 1 can find out, the pattern of the nano cuprous oxide that the present embodiment obtains is irregular, there is incomplete Nano microsphere.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 neutralized verdigris in 50ml water, obtains the neutralized verdigris aqueous solution;
Step (2), adds in three-necked flask by step (1) the gained neutralized verdigris aqueous solution and 50ml ethanolic soln, stirs 5 minutes; By the dilution of the hydrazine hydrate solution of 1ml massfraction 80% for being added drop-wise in reaction system after 10ml;
Step (3), after hydrazine hydrate aqueous solution drips, stirring reaction 10 minutes at 20 DEG C, stirring velocity 600rpm;
Step (4), after reaction terminates, by the centrifugation of gained reaction solution, adds 10ml EtOH Sonicate 10 minutes after removing supernatant liquor, repeats 3 times; At gained being deposited in 30 DEG C, namely vacuum-drying obtain described bilayer structure nano cuprous oxide.
The stereoscan photograph of the present embodiment gained Red copper oxide as shown in Figure 10, tensio-active agent is not added in the present embodiment---sodium oleate, as can be seen from stereoscan photograph, the Red copper oxide that the present embodiment obtains is the irregular particle of particle diameter more than 10 μm, does not have spherical product to generate.
Embodiment 4
Step (1), is dissolved in 2.5g neutralized verdigris in 50ml water, obtains the neutralized verdigris aqueous solution; 0.10g sodium oleate is dissolved in 50ml ethanol, obtains the ethanolic soln of sodium oleate;
Step (2), adds in three-necked flask by the ethanolic soln of step (1) the gained neutralized verdigris aqueous solution and sodium oleate, stirs 5 minutes; By the dilution of the hydrazine hydrate solution of 1ml massfraction 80% for being added drop-wise in reaction system after 10ml;
Step (3), after hydrazine hydrate aqueous solution drips, stirring reaction 10 minutes at 20 DEG C, stirring velocity 600rpm;
Step (4), after reaction terminates, by the centrifugation of gained reaction solution, adds 10ml EtOH Sonicate 10 minutes after removing supernatant liquor, repeats 3 times; At gained being deposited in 30 DEG C, namely vacuum-drying obtain described bilayer structure nano cuprous oxide.
As shown in figure 11, the present embodiment, compared with embodiment 1, reduces the concentration of sodium oleate ethanolic soln to the stereoscan photograph of the present embodiment gained Red copper oxide, namely reduces surfactant concentration in reaction system.Contrast Figure 11 and Fig. 1 can find out, generate Nano microsphere, but particle diameter is uneven, and still there is irregular small-particle in product.
Embodiment 5
Step (1), is dissolved in 2.5g neutralized verdigris in 50ml water, obtains the neutralized verdigris aqueous solution; 0.50g sodium oleate is dissolved in 50ml ethanol, obtains the ethanolic soln of sodium oleate;
Step (2), adds in three-necked flask by the ethanolic soln of step (1) the gained neutralized verdigris aqueous solution and sodium oleate, stirs 5 minutes; By the dilution of the hydrazine hydrate solution of 1ml massfraction 80% for being added drop-wise in reaction system after 10ml;
Step (3), after hydrazine hydrate aqueous solution drips, stirring reaction 10 minutes at 20 DEG C, stirring velocity 600rpm;
Step (4), after reaction terminates, by the centrifugation of gained reaction solution, adds 10ml EtOH Sonicate 10 minutes after removing supernatant liquor, repeats 3 times; At gained being deposited in 30 DEG C, namely vacuum-drying obtain described bilayer structure nano cuprous oxide.
As shown in figure 12, the present embodiment, compared with embodiment 1, adds the concentration of sodium oleate ethanolic soln 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 microballoon has bilayer structure as can be seen from Figure 12, and wherein, the particle diameter major part of its secondary structure is between 400-500nm.Contrast Figure 12 and Fig. 1 can find out, the present embodiment gained cuprous nano Microsphere Size is more homogeneous, and shape is more regular, and dispersed better.
In sum, by the ratio of choose reasonable 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, less, the specific surface area of particle diameter large there is double-deck cuprous nano microballoon.
The above is only understand technical scheme of the present invention for the ease of those skilled in the art, not in order to limit the present invention.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (15)
1. a bilayer structure cuprous nano microballoon, is characterized in that, the diameter of described cuprous nano microballoon is 400-600nm; The Red copper oxide particle aggregation that described cuprous nano microballoon is 40-50nm by diameter forms.
2. cuprous nano microballoon according to claim 1, is characterized in that, the diameter of described cuprous nano microballoon is 400-500nm.
3. cuprous nano microballoon according to claim 1, is characterized in that, the specific surface area of described cuprous nano microballoon is 60-70m
2/ g.
4. a preparation method for bilayer structure cuprous nano microballoon, is characterized in that, described preparation method comprises the following steps:
Step (1), mantoquita is soluble in water, obtain copper salt solution; Sodium oleate is dissolved in ethanol, obtains the ethanolic soln of sodium oleate;
Step (2), adds in reaction vessel by the ethanolic soln of step (1) gained copper salt solution and sodium oleate, stirs and drips hydrazine hydrate aqueous solution in backward reaction system in 5-10 minute;
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 the centrifugation of gained reaction solution, adds ethanol after removing supernatant liquor and carries out ultrasonic, repeat 2-4 time; At gained being deposited in 30-35 DEG C, namely vacuum-drying obtain described bilayer structure cuprous nano microballoon.
5. preparation method according to claim 4, is characterized in that, described in step (1), mantoquita is selected from cupric nitrate, copper sulfate, cupric chloride or neutralized verdigris.
6. want the preparation method described in 4 according to right, it is characterized in that, described in step (1), copper salt solution concentration is 10g/L-70g/L.
7. preparation method according to claim 6, is characterized in that, described in step (1), copper salt solution concentration is 25g/L.
8. preparation method according to claim 4, is characterized in that, described in step (1), the ethanol solution concentration of sodium oleate is 1g/L-10g/L.
9. preparation method according to claim 4, is characterized in that, described in step (2), hydrazine hydrate aqueous solution mass percent is 5%-8%.
10. preparation method according to claim 4, is characterized in that, described in step (1), the mass ratio of mantoquita and sodium oleate is 5-50:1.
11. preparation methods according to claim 4, is characterized in that, described in step (2), the mass ratio of mantoquita and hydrazine hydrate is 1-5:1.
12. preparation methods according to claim 4, is characterized in that, described in step (1), the volume ratio of water and ethanol is 0.5-2:1.
13. preparation methods according to claim 13, is characterized in that, described in step (1), the volume ratio of water and ethanol is 1:1.
14. preparation methods according to claim 4, is characterized in that, described in step (3), the stirring velocity of stirring reaction is 500-700rpm.
15. preparation methods according to claim 4, is characterized in that, described in step (4), centrifuge speed is 9000-11000 rev/min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105905936A (en) * | 2016-04-14 | 2016-08-31 | 青岛大学 | Cuprous oxide nanocrystalline assembly |
| CN107814407A (en) * | 2017-11-06 | 2018-03-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Method that supercritical carbon dioxide prepares ultra-thin two-dimension cuprous oxide and products thereof and application |
| CN108083742A (en) * | 2017-12-25 | 2018-05-29 | 芜湖林电子科技有限公司 | A kind of 3D printing method for preparing mortar of high compressive strength |
| CN112978783A (en) * | 2021-02-19 | 2021-06-18 | 中国科学技术大学 | Cuprous oxide nano material, preparation method and application thereof |
| CN115028187A (en) * | 2022-08-02 | 2022-09-09 | 沈阳工业大学 | Chemical preparation method of copper oxide nanoparticles |
| CN115028187B (en) * | 2022-08-02 | 2024-04-19 | 沈阳工业大学 | Chemical preparation method of copper oxide nano particles |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105905936A (en) * | 2016-04-14 | 2016-08-31 | 青岛大学 | Cuprous oxide nanocrystalline assembly |
| CN105905936B (en) * | 2016-04-14 | 2017-11-14 | 青岛大学 | A kind of cuprous nano crystalline substance assembly |
| CN107814407A (en) * | 2017-11-06 | 2018-03-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Method that supercritical carbon dioxide prepares ultra-thin two-dimension cuprous oxide and products thereof and application |
| CN108083742A (en) * | 2017-12-25 | 2018-05-29 | 芜湖林电子科技有限公司 | A kind of 3D printing method for preparing mortar of high compressive strength |
| CN112978783A (en) * | 2021-02-19 | 2021-06-18 | 中国科学技术大学 | Cuprous oxide nano material, preparation method and application thereof |
| CN115028187A (en) * | 2022-08-02 | 2022-09-09 | 沈阳工业大学 | Chemical preparation method of copper oxide nanoparticles |
| CN115028187B (en) * | 2022-08-02 | 2024-04-19 | 沈阳工业大学 | Chemical preparation method of copper oxide nano particles |
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| CN104445358B (en) | 2016-06-22 |
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