CN104192889A - Method for preparing monodisperse cuprous oxide hollow sphere - Google Patents
Method for preparing monodisperse cuprous oxide hollow sphere Download PDFInfo
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- CN104192889A CN104192889A CN201410379338.2A CN201410379338A CN104192889A CN 104192889 A CN104192889 A CN 104192889A CN 201410379338 A CN201410379338 A CN 201410379338A CN 104192889 A CN104192889 A CN 104192889A
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- cuprous oxide
- hollow sphere
- copper salt
- sphere made
- disperseing
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Abstract
The invention discloses a method for preparing a monodisperse cuprous oxide hollow sphere. The method does not need surfactants and comprises the following steps: a, completely dissolving soluble copper salt in water to form a copper salt solution; b, adding a reducing agent in the copper salt solution under magnetic stirring to form a mixed solution; and c, putting the mixed solution in a thermostatic water bath for reaction to obtain the orange red monodisperse cuprous oxide hollow sphere. The method is free of surfactants, single in raw materials, low in cost, simple in steps, easy to operate, mild in conditions and beneficial for large-scale industrial production. The cuprous oxide hollow sphere prepared by the method is uniform in wall thickness, good in dispersibility and large in porosity and has a wide application prospect in the fields of solar batteries, lithium-ion batteries, gas sensors and photocatalysis.
Description
Technical field
The present invention relates to a kind of preparation method of nano material, relate in particular to a kind of single method of disperseing hollow sphere made from cuprous oxide of preparing.
Background technology
Red copper oxide is a kind of important p-type semiconductor material (the about 2.07eV of energy gap), there is the advantages such as higher photoelectricity theoretical conversion efficiency and preparation cost are cheap, nontoxic, in fields such as solar cell, lithium ion battery, gas sensor, photochemical catalysis, all have important application.Research shows, pattern, the size of the optical absorption characteristics of Red copper oxide and visible light photocatalysis performance and its material have important relationship.Can prepare now the micrometer/nanometer level Red copper oxide product of different morphologies and yardstick, comprise the crystal, one-dimentional structure, film etc. with particular geometric configuration.Preparation principle is to be mainly copper source with the solution of soluble copper salt or metallic copper, obtains the Red copper oxide of a valence state by the method for reducing or be oxidized.Preparation method comprises solution reduction, hydrothermal method, irradiation method, physical/chemical vapour deposition process, thermal oxidation method, electrochemical deposition method, template etc.
At present, prepare Red copper oxide material and use tensio-active agent as structure directing agent more, especially in the process of Red copper oxide ball material of preparing hollow structure.Tensio-active agent is easily adsorbed on sample surfaces, is difficult to clean, and the character of sample is impacted, and add tensio-active agent can increase the cost of preparation.
Through retrieval, the Chinese invention patent that publication number is CN1759965A, discloses " a kind of method of synthesizing Nano balls of cuprous oxide and the application of Nano balls of cuprous oxide ".Comprise the following steps: in the organic solvent that can dissolve each other with water, dissolve mantoquita, be made into copper ion solution; Add therein nonionic surfactant, stirring and dissolving, adds strong reductant, and constant temperature, between 70～90 ℃, refluxes in the system of opening wide, and obtains accurate monodispersed Nano balls of cuprous oxide.Tensio-active agent is used in this invention, and under comparatively high temps, reflux is reacted, and cost is higher.
Publication number is the Chinese invention patent of CN101805010A, " a kind of method of preparing hollow sphere made from cuprous oxide " disclosed, comprise the following steps: first metallic copper soluble salt and polyvinylpyrrolidone are dissolved in the water, form settled solution, again under the condition stirring, reductive agent is joined in the settled solution of preparation, react and within 5～150 minutes, be prepared into hollow sphere made from cuprous oxide product.The method has utilized polyvinylpyrrolidone as tensio-active agent, and wash-out difficulty, has increased preparation cost completely.
Therefore, those skilled in the art is devoted to develop a kind of synthesis of surfactant technology of not using, and directly obtains the method for monodispersed hollow sphere made from cuprous oxide, avoids using the defect of tensio-active agent.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of tensio-active agent that do not use and prepares single method of disperseing hollow sphere made from cuprous oxide.
For achieving the above object, the invention provides a kind of single method of disperseing hollow sphere made from cuprous oxide of preparing, in preparation process, do not use tensio-active agent, comprise the steps:
A. soluble copper salt is dissolved in the water completely, forms copper salt solution;
B. under magnetic agitation, in copper salt solution, add reductive agent, obtain mixing solutions;
C. mixing solutions reacts in water bath with thermostatic control, obtains orange red single hollow sphere made from cuprous oxide that disperses.
Preferably, soluble copper salt is a kind of among copper sulfate, cupric nitrate, venus crystals, cupric chloride or cupric nitrite.
Preferably, in step a, copper salt solution concentration range is 0.02～0.2mol/l.
Preferably, in step b, reductive agent is a kind of among hydrazine hydrate, phenylhydrazine, azanol, sodium borohydride, lithium aluminum hydride or sodium tert-butoxide.
Preferably, in step b, reductive agent is the aqueous solution of mass percent 15%～45%.
Preferably, in step b, in reductive agent and step a, the volume ratio of copper salt solution is 1:100～1:25.
Preferably, in step c, the temperature of water bath with thermostatic control is 0～50 ℃; The water bath with thermostatic control reaction times is 1～3h.
The present invention also provides single hollow sphere made from cuprous oxide that disperses of preparing according to aforesaid method.
Present method does not need to add tensio-active agent while disperseing hollow sphere made from cuprous oxide preparation is single, the single and low price of raw material, and step is simple, easy handling, mild condition, is conducive to large-scale industrial production.Product wall thickness prepared by present method evenly, good dispersity, porosity be large, in solar cell, lithium ion battery, gas sensor, photocatalysis field, has potential application.
Below with reference to accompanying drawing, the technique effect of design of the present invention, concrete structure and generation is described further, to understand fully object of the present invention, feature and effect.
Accompanying drawing explanation
Fig. 1 is single X-ray powder diffraction figure that disperses hollow sphere made from cuprous oxide of the embodiment of the present invention 1 preparation;
Fig. 2 is single uv-visible absorption spectra figure that disperses hollow sphere made from cuprous oxide of the embodiment of the present invention 1 preparation;
Fig. 3 is single scanning electron microscope (SEM) photograph that disperses hollow sphere made from cuprous oxide of the embodiment of the present invention 1 preparation.
Embodiment
Embodiment 1
Do not use tensio-active agent to prepare a single method of disperseing hollow sphere made from cuprous oxide, comprise the steps:
A. 0.25g copper sulfate is dissolved in 50ml deionized water completely, forms copper salt solution;
B. under magnetic agitation, in copper salt solution, adding 1ml massfraction is 20% hydrazine hydrate;
C. add the copper salt solution of reductive agent to react 1h under 25 ℃ of waters bath with thermostatic control, obtain orange red single hollow sphere made from cuprous oxide that disperses.
Fig. 1 is single X-ray powder diffraction figure that disperses hollow sphere made from cuprous oxide prepared by the present embodiment; Fig. 2 is single uv-visible absorption spectra figure that disperses hollow sphere made from cuprous oxide prepared by the present embodiment; Fig. 3 is single scanning electron microscope (SEM) photograph that disperses hollow sphere made from cuprous oxide prepared by the present embodiment; The left-half of Fig. 3 is the scanning electron microscope (SEM) photograph under low range, and upper right portion is the scanning electron microscope (SEM) photograph under high magnification, and as can be known from Fig. 3, hollow sphere made from cuprous oxide prepared by the present embodiment is monodisperse status, and hollow sphere made from cuprous oxide size is even, diameter 150nm.
Embodiment 2
Do not use tensio-active agent to prepare a single method of disperseing hollow sphere made from cuprous oxide, comprise the steps:
A. 0.5g copper sulfate is dissolved in 50ml deionized water completely, forms copper salt solution;
B. under magnetic agitation, in copper salt solution, adding 2ml massfraction is 20% hydrazine hydrate;
C. add the copper salt solution of reductive agent to react 2h under 25 ℃ of waters bath with thermostatic control, obtain orange red single hollow sphere made from cuprous oxide that disperses.
Embodiment 3
Do not use tensio-active agent to prepare a single method of disperseing hollow sphere made from cuprous oxide, comprise the steps:
A. 0.2g copper sulfate is dissolved in 50ml deionized water completely, forms copper salt solution;
B. under magnetic agitation, in copper salt solution, adding 1ml massfraction is 20% hydrazine hydrate;
C. add the copper salt solution of reductive agent to react 1h under 40 ℃ of waters bath with thermostatic control, obtain orange red single hollow sphere made from cuprous oxide that disperses.
Embodiment 4
Do not use tensio-active agent to prepare a single method of disperseing hollow sphere made from cuprous oxide, it comprises the steps:
A. 0.25g copper sulfate is dissolved in 50ml deionized water completely, forms copper salt solution;
B. under magnetic agitation, in copper salt solution, adding 1ml massfraction is 40% hydrazine hydrate;
C. add the copper salt solution of reductive agent to react 1h under 25 ℃ of waters bath with thermostatic control, obtain orange red single hollow sphere made from cuprous oxide that disperses.
Embodiment 5
Do not use tensio-active agent to prepare a single method of disperseing hollow sphere made from cuprous oxide, comprise the steps:
A. 1g cupric nitrate is dissolved in 50ml deionized water completely, forms copper salt solution;
B. under magnetic agitation, in copper salt solution, adding 2ml massfraction is 45% phenylhydrazine;
C. add the copper salt solution of reductive agent to react 2h under 50 ℃ of waters bath with thermostatic control, obtain orange red single hollow sphere made from cuprous oxide that disperses.
Embodiment 6
Do not use tensio-active agent to prepare a single method of disperseing hollow sphere made from cuprous oxide, it comprises the steps:
A. 0.5g venus crystals is dissolved in 100ml deionized water completely, forms copper salt solution;
B. under magnetic agitation, in copper salt solution, adding 1ml massfraction is 30% azanol;
C. add the copper salt solution of reductive agent to react 3h under 25 ℃ of waters bath with thermostatic control, obtain orange red single hollow sphere made from cuprous oxide that disperses.
Embodiment 7
Do not use tensio-active agent to prepare a single method of disperseing hollow sphere made from cuprous oxide, it comprises the steps:
A. 0.2g cupric chloride is dissolved in 50ml deionized water completely, forms copper salt solution;
B. under magnetic agitation, in copper salt solution, adding 0.5ml massfraction is 45% sodium borohydride;
C. add the copper salt solution of reductive agent to react 3h under 20 ℃ of waters bath with thermostatic control, obtain orange red single hollow sphere made from cuprous oxide that disperses.
Embodiment 8
Do not use tensio-active agent to prepare a single method of disperseing hollow sphere made from cuprous oxide, it comprises the steps:
A. 0.69g cupric nitrite is dissolved in 50ml deionized water completely, forms copper salt solution;
B. under magnetic agitation, in copper salt solution, adding 2ml massfraction is 15% lithium aluminum hydride;
C. add the copper salt solution of reductive agent to react 2h under 40 ℃ of waters bath with thermostatic control, obtain orange red single hollow sphere made from cuprous oxide that disperses.
Embodiment 9
Do not use tensio-active agent to prepare a single method of disperseing hollow sphere made from cuprous oxide, it comprises the steps:
A. 0.8g cupric nitrite is dissolved in 100ml deionized water completely, forms copper salt solution;
B. under magnetic agitation, in copper salt solution, adding 2ml massfraction is 15% sodium tert-butoxide;
C. add the copper salt solution of reductive agent to react 2h under 40 ℃ of waters bath with thermostatic control, obtain orange red single hollow sphere made from cuprous oxide that disperses.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that those of ordinary skill in the art just can design according to the present invention make many modifications and variations without creative work.Therefore, all technician in the art, all should be in the determined protection domain by claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (9)
1. prepare a single method of disperseing hollow sphere made from cuprous oxide, it is characterized in that, in preparation process, do not use tensio-active agent, comprise the steps:
A. soluble copper salt is dissolved in the water completely, forms copper salt solution;
B. under magnetic agitation, in described copper salt solution, add reductive agent, obtain mixing solutions;
C. described mixing solutions reacts in water bath with thermostatic control, obtains orange red single hollow sphere made from cuprous oxide that disperses.
2. a kind of single method of disperseing hollow sphere made from cuprous oxide of preparing according to claim 1, is characterized in that, described soluble copper salt is a kind of among copper sulfate, cupric nitrate, venus crystals, cupric chloride or cupric nitrite.
3. a kind of single method of disperseing hollow sphere made from cuprous oxide of preparing according to claim 1, is characterized in that, the concentration range of copper salt solution described in step a is 0.02～0.2mol/l.
4. a kind of single method of disperseing hollow sphere made from cuprous oxide of preparing according to claim 1, is characterized in that, reductive agent described in step b is a kind of among hydrazine hydrate, phenylhydrazine, azanol, sodium borohydride, lithium aluminum hydride or sodium tert-butoxide.
5. a kind of single method of disperseing hollow sphere made from cuprous oxide of preparing according to claim 1, is characterized in that, reductive agent described in step b is the aqueous solution of mass percent 15%～45%.
6. a kind of single method of disperseing hollow sphere made from cuprous oxide of preparing according to claim 1, is characterized in that, described in reductive agent described in step b and step a, the volume ratio of copper salt solution is 1:100～1:25.
7. a kind of single method of disperseing hollow sphere made from cuprous oxide of preparing according to claim 1, is characterized in that, the temperature of water bath with thermostatic control described in step c is 0～50 ℃.
8. a kind of single method of disperseing hollow sphere made from cuprous oxide of preparing according to claim 1, is characterized in that, the reaction times of water bath with thermostatic control described in step c is 1～3h.
9. a list of preparing according to method described in arbitrary claim in claim 1～8 disperses hollow sphere made from cuprous oxide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105836787A (en) * | 2016-05-23 | 2016-08-10 | 常州大学 | Environment-friendly preparation method of cuprous oxide |
| WO2019174171A1 (en) * | 2018-03-14 | 2019-09-19 | 全球能源互联网研究院有限公司 | Gas-sensitive material and preparation method therefor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805010A (en) * | 2010-04-02 | 2010-08-18 | 青岛科技大学 | Method for preparing hollow sphere made from cuprous oxide |
| US20100258759A1 (en) * | 2006-06-06 | 2010-10-14 | Cornell Research Foundation, Inc. | Nanostructured Metal Oxides Comprising Internal Voids and Methods of Use Thereof |
| CN102515244A (en) * | 2011-11-28 | 2012-06-27 | 上海交通大学 | Hollow cuprous oxide nanometre material and preparation method for same |
| CN103466681A (en) * | 2013-08-29 | 2013-12-25 | 河南师范大学 | Preparation method of graded spherical cuprous oxide hollow nano particle |
-
2014
- 2014-08-04 CN CN201410379338.2A patent/CN104192889A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100258759A1 (en) * | 2006-06-06 | 2010-10-14 | Cornell Research Foundation, Inc. | Nanostructured Metal Oxides Comprising Internal Voids and Methods of Use Thereof |
| CN101805010A (en) * | 2010-04-02 | 2010-08-18 | 青岛科技大学 | Method for preparing hollow sphere made from cuprous oxide |
| CN102515244A (en) * | 2011-11-28 | 2012-06-27 | 上海交通大学 | Hollow cuprous oxide nanometre material and preparation method for same |
| CN103466681A (en) * | 2013-08-29 | 2013-12-25 | 河南师范大学 | Preparation method of graded spherical cuprous oxide hollow nano particle |
Non-Patent Citations (2)
| Title |
|---|
| WANG NING ET AL.: "Room temperature preparation of cuprous oxide hollow microspheres by a facile wet-chemical approach", 《APPLIED SURFACE SCIENCE》 * |
| WANG WENZHONG ET AL.: "Template-free room temperature solution phase synthesis of Cu2O hollow spheres", 《CRYSTENGCOMM》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105836787A (en) * | 2016-05-23 | 2016-08-10 | 常州大学 | Environment-friendly preparation method of cuprous oxide |
| CN105836787B (en) * | 2016-05-23 | 2017-11-17 | 常州大学 | A kind of environment-friendly preparation method thereof of cuprous oxide |
| WO2019174171A1 (en) * | 2018-03-14 | 2019-09-19 | 全球能源互联网研究院有限公司 | Gas-sensitive material and preparation method therefor |
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Application publication date: 20141210 |