CN105417573A - Method for preparing Cu2O nano-microsphere by utilizing lauramidopropyl betaine - Google Patents
Method for preparing Cu2O nano-microsphere by utilizing lauramidopropyl betaine Download PDFInfo
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- CN105417573A CN105417573A CN201510909222.XA CN201510909222A CN105417573A CN 105417573 A CN105417573 A CN 105417573A CN 201510909222 A CN201510909222 A CN 201510909222A CN 105417573 A CN105417573 A CN 105417573A
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- lauroylamidopropyl betaine
- nano microsphere
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01P2002/72—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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The invention relates to a method for preparing a Cu2O nano-microsphere by utilizing lauramidopropyl betaine, belongs to the field of preparation of inorganic nanometer materials, and particularly relates to a method for preparing the Cu2O nano-microsphere. The method aims to solve the technical problem that a product obtained by an existing method for preparing Cu2O microspheres is simple in structure. The method comprises a step 1 of preparing lauramidopropyl betaine solution, a step 2 of adding copper acetate solution dropwise to the lauramidopropyl betaine solution first and adjusting the pH or adjusting the pH of the lauramidopropyl betaine solution first and adding the copper acetate solution dropwise to obtain mixed liquor, and a step 3 of adding ascorbic acid solution dropwise first and performing stirring and reaction, separation and drying to obtain the Cu2O nano-microsphere. Building blocks of the nano-microsphere are needle-like or spherical nanoparticles, and the nano-microsphere has a mesoporous or hollow structure and can be utilized as solar cells, optical devices, biosensors and negative electrode materials and the like.
Description
Technical field
The invention belongs to the preparation field of inorganic nano material, be specifically related to Cu
2the preparation method of O Nano microsphere
Background technology
Red copper oxide (Cu
2o) be a kind of important metal oxide, belong to P-type semiconductor material, be with a wide range of applications in solar cell, optics, biosensor and electrode anode material etc.Based on Cu
2the using value that O is important and special property, the nanometer Cu of different-shape and structure
2the research of O, sign and correlated performance is subject to the extensive concern of investigator.Wherein there is the Cu of hollow structure
2the preparation method of O microballoon is more, and the 1489-1492 page as the 46th volume every 9 phases in 2007 of " German applied chemistry " (AngewandteChemicInternationalEdition) discloses one with tensio-active agent cetyl trimethylammonium bromide (CTAB) for templated synthesis nanometer Cu
2the method of the many shell hollow spheres of O, and the ball wall of hollow ball is monocrystalline.Publication number is that the Chinese patent of CN100486896 discloses one and utilizes aqueous phase cluster soft mold plates legal system for monodispersed Cu
2the method of O hollow sub-micro ball, the cluster that the method utilizes polyvinylpyrrolidone and sodium lauryl sulphate to be formed is as soft template, to contain the aqueous solution and the cluster soft mold plates aqueous solution of mantoquita, make reductive agent with hydrazine hydrate after adjust ph, cupric ion fast restore obtains Cu
2o hollow sub-micro spherocolloid solution.Reaction product is through centrifugation, and precipitate with deionized water and washes of absolute alcohol, obtain being formed by the cuprous nano particle self-assembly of particle diameter about 11 ~ 22nm and having the monodispersed Cu of the diameter 400 ~ 550nm of narrow Size Distribution
2o hollow sub-micro ball.But above-mentioned method can only obtain the Cu of single structure
2o Nano microsphere.
Summary of the invention
The present invention is the Cu that will solve existing hollow structure
2the technical problem that the product structure that the preparation method of O microballoon obtains is single, and provide one to utilize lauroylamidopropyl betaine to prepare Cu
2the method of O Nano microsphere.
The lauroylamidopropyl betaine that utilizes of the present invention prepares Cu
2the method of O Nano microsphere, carry out according to the following steps:
One, be 0.2% ~ 0.3% by the concentration of lauroylamidopropyl betaine, lauroylamidopropyl betaine joined in deionized water, stir 30 ~ 40min, obtain lauroylamidopropyl betaine solution;
Two, neutralized verdigris solution is added drop-wise in lauroylamidopropyl betaine solution, after dropwising, stirs 30 ~ 40min, then regulate pH to be 10.0 ~ 10.5 by NaOH solution, obtain mixed solution; Or with NaOH solution adjustment lauroylamidopropyl betaine solution is 10.0 ~ 10.5, then is added drop-wise in lauroylamidopropyl betaine solution by neutralized verdigris solution, after dropwising, stirs 30 ~ 40min, obtains mixed solution;
Three, ascorbic acid solution is added drop-wise to stirring reaction 40 ~ 60min in mixed solution, obtains suspension liquid; Wherein the mol ratio of neutralized verdigris and xitix is 1:(2 ~ 2.5); Suspension liquid is carried out centrifugation, and solid formation water wherein and ethanol wash respectively, then dry, obtain Cu
2o Nano microsphere.
The present invention, under the comprehensive action of lauroylamidopropyl betaine and other compositions, obtains the Cu with pore passage structure of high dispersive
2o microballoon, and utilize the feature of lauroylamidopropyl betaine in different liqs environment, adds order by feed change, just can obtain the different Cu of two kinds of construction units
2o Nano microsphere, adds Cu prepared by raw material by the order of lauroylamidopropyl betaine, neutralized verdigris, NaOH
2the construction unit of O microballoon is acicular nanometer particle, and adds Cu prepared by raw material by the order of lauroylamidopropyl betaine, NaOH, neutralized verdigris
2the construction unit of O microballoon is spherical nanoparticles, adopts identical raw material, can prepare two kinds of different structure unit and all have the Cu of pore passage structure
2o Nano microsphere.Preparation method is simple, and advantages of nontoxic raw materials, meets the requirement of energy-conserving and environment-protective aspect.
Accompanying drawing explanation
Fig. 1 is Cu prepared by embodiment 1 and 2
2the X-ray diffraction spectrogram of O Nano microsphere;
Fig. 2 is Cu prepared by embodiment 1
2the stereoscan photograph of O Nano microsphere;
Fig. 3 is Cu prepared by embodiment 1
2the transmission electron microscope photo of O Nano microsphere;
Fig. 4 is Cu prepared by embodiment 1 and 2
2the pore size distribution curve of O Nano microsphere;
Fig. 5 is Cu prepared by embodiment 2
2the stereoscan photograph of O Nano microsphere;
Fig. 6 is Cu prepared by embodiment 2
2the transmission electron microscope photo of O Nano microsphere.
Embodiment
Embodiment one: the lauroylamidopropyl betaine that utilizes of present embodiment prepares Cu
2the method of O Nano microsphere, carry out according to the following steps:
One, be 0.2 ~ 0.3% by the concentration of lauroylamidopropyl betaine, lauroylamidopropyl betaine joined in deionized water, stir 30 ~ 40min, obtain lauroylamidopropyl betaine solution;
Two, neutralized verdigris solution is added drop-wise in lauroylamidopropyl betaine solution, after dropwising, stirs 30 ~ 40min, then regulate pH to be 10.0 ~ 10.5 by NaOH solution, obtain mixed solution; Or with NaOH solution adjustment lauroylamidopropyl betaine solution is 10.0 ~ 10.5, then is added drop-wise in lauroylamidopropyl betaine solution by neutralized verdigris solution, after dropwising, stirs 30 ~ 40min, obtains mixed solution;
Three, ascorbic acid solution is added drop-wise to stirring reaction 40 ~ 60min in mixed solution, obtains suspension liquid; Wherein the mol ratio of neutralized verdigris and xitix is 1:(2 ~ 2.5); Suspension liquid is carried out centrifugation, and solid formation water wherein and ethanol wash respectively, then dry, obtain Cu
2o Nano microsphere.
Embodiment two: present embodiment and embodiment one are 0.25% unlike the concentration of lauroylamidopropyl betaine in step one.Other is identical with embodiment one.
Embodiment three: neutralized verdigris solution is added drop-wise in lauroylamidopropyl betaine solution unlike in step 2 by present embodiment and embodiment one or two, after dropwising, stirs 35min, then regulates pH to be 10.2 by NaOH solution.Other is identical with embodiment one or two.
Embodiment four: neutralized verdigris solution is added drop-wise in lauroylamidopropyl betaine solution unlike in step 2 by one of present embodiment and embodiment one to three, after dropwising, stirs 35min, then regulates pH to be 10.5 by NaOH solution.Other is identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to three regulate the pH value of lauroylamidopropyl betaine solution to be 10.5 unlike in step 2 by NaOH solution, drip neutralized verdigris solution again, after dropwising, stir 35min, obtain mixed solution.Other is identical with one of embodiment one to three.
Embodiment six: one of present embodiment and embodiment one to five are added drop-wise to stirring reaction 50min in mixed solution unlike ascorbic acid solution in step 3.Other is identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six are 1:2.2 unlike the mol ratio of step 3 neutralized verdigris and xitix.Other is identical with one of embodiment one to six.
Embodiment eight: present embodiment and one of embodiment one to seven are 1mmol:(300 ~ 350 unlike the amount of substance of neutralized verdigris in neutralized verdigris solution in step 2 and the ratio of the volume of lauroylamidopropyl betaine solution) mL.Other are identical with one of embodiment one to seven.
With following verification experimental verification beneficial effect of the present invention:
Embodiment 1: the lauroylamidopropyl betaine that utilizes of the present embodiment prepares Cu
2the method of O Nano microsphere, carry out according to the following steps:
One, by 0.22mL mass percent concentration be 35% lauroylamidopropyl betaine add and fill in 100mL deionized water, stir 30min, obtain lauroylamidopropyl betaine solution;
Two, be 0.1molL by 3mL concentration
-1neutralized verdigris solution be added drop-wise in lauroylamidopropyl betaine solution, after dropwising, stirring 30min, is then 0.5molL by concentration
-1naOH solution regulate pH be 10.0, obtain mixed solution;
Three, be 0.2molL by 3mL concentration
-1ascorbic acid solution to be added drop-wise in mixed solution induction stirring reaction 40min, obtain suspension liquid; Suspension liquid is carried out centrifugation, and solid formation water wherein and ethanol wash respectively, then dry, obtain Cu
2o Nano microsphere.
Cu prepared by the present embodiment
2the XRD spectra of O Nano microsphere as shown in fig. ia, as can be seen from Figure 1, the Cu of preparation
2o is cubic phase crystal structure, and degree of crystallinity is high.
Cu prepared by the present embodiment
2the stereoscan photograph of O Nano microsphere as shown in Figure 2, transmission electron microscope photo as shown in Figure 3, as can be seen from Figure 2, Cu
2the diameter of O Nano microsphere is 170 ~ 220nm, as can be seen from Figure 3, and Cu
2the ball wall of O Nano microsphere is by the Cu of class needle-like
2o nano particle builds, and more clearly can find out the nano particle of its class needle-like from the partial enlarged drawing in this figure lower left corner, and Cu
2there is duct in O Nano microsphere.
Cu prepared by the present embodiment
2the pore size distribution curve of O Nano microsphere as shown in a of Fig. 4, as can be seen from Figure 4, Cu
2it is mesoporous level that O Nano microsphere exists duct.
Embodiment 2: the lauroylamidopropyl betaine that utilizes of the present embodiment prepares Cu
2the method of O Nano microsphere, carry out according to the following steps:
One, by 0.22mL mass percent concentration be 35% lauroylamidopropyl betaine add and fill in 100mL deionized water, stir 30min, obtain lauroylamidopropyl betaine solution;
Two, be 0.5molL by concentration
-1naOH solution be 10.0 by the pH regulator of lauroylamidopropyl betaine solution, be then 0.1molL by 3mL concentration
-1neutralized verdigris solution be added drop-wise in lauroylamidopropyl betaine solution, after dropwising, stir 30min, obtain mixed solution;
Three, be 0.2molL by 3mL concentration
-1ascorbic acid solution to be added drop-wise in mixed solution induction stirring reaction 40min, obtain suspension liquid; Suspension liquid is carried out centrifugation, and solid formation water wherein and ethanol wash respectively, then dry, obtain Cu
2o Nano microsphere.
Cu prepared by the present embodiment
2the XRD spectra of O Nano microsphere as shown in fig. ib, as can be seen from the b of Fig. 1, the Cu of preparation
2o is cubic phase crystal structure, and degree of crystallinity is high.
Cu prepared by the present embodiment
2the stereoscan photograph of O Nano microsphere as shown in Figure 5, transmission electron microscope photo as shown in Figure 6, as can be seen from Figure 5, Cu
2the diameter of O Nano microsphere is 170 ~ 220nm, as can be seen from Figure 6, and Cu
2the ball wall of O Nano microsphere is by spherical Cu
2o nano particle builds, and Cu
2o Nano microsphere is the spheroid of hollow.
Cu prepared by the present embodiment
2the pore size distribution curve of O Nano microsphere as shown in the b of Fig. 4, as can be seen from the b of Fig. 4, Cu
2it is mesoporous level that O Nano microsphere exists duct.
Claims (8)
1. one kind utilizes lauroylamidopropyl betaine to prepare Cu
2the method of O Nano microsphere, is characterized in that the method is carried out according to the following steps:
One, be 0.2% ~ 0.3% by the concentration of lauroylamidopropyl betaine, lauroylamidopropyl betaine joined in deionized water, stir 30 ~ 40min, obtain lauroylamidopropyl betaine solution;
Two, neutralized verdigris solution is added drop-wise in lauroylamidopropyl betaine solution, after dropwising, stirs 30 ~ 40min, then regulate pH to be 10.0 ~ 10.5 by NaOH solution, obtain mixed solution; Or with NaOH solution adjustment lauroylamidopropyl betaine solution is 10.0 ~ 10.5, then is added drop-wise in lauroylamidopropyl betaine solution by neutralized verdigris solution, after dropwising, stirs 30 ~ 40min, obtains mixed solution;
Three, ascorbic acid solution is added drop-wise to stirring reaction 40 ~ 60min in mixed solution, obtains suspension liquid; Wherein the mol ratio of neutralized verdigris and xitix is 1:(2 ~ 2.5); Suspension liquid is carried out centrifugation, and solid formation water wherein and ethanol wash respectively, then dry, obtain Cu
2o Nano microsphere.
2. one according to claim 1 utilizes lauroylamidopropyl betaine to prepare Cu
2the method of O Nano microsphere, is characterized in that the concentration of lauroylamidopropyl betaine in step one is 0.25%.
3. one according to claim 1 and 2 utilizes lauroylamidopropyl betaine to prepare Cu
2the method of O Nano microsphere, is characterized in that being added drop-wise in lauroylamidopropyl betaine solution by neutralized verdigris solution in step 2, after dropwising, stirs 35min, then regulates pH to be 10.2 by NaOH solution.
4. one according to claim 1 and 2 utilizes lauroylamidopropyl betaine to prepare Cu
2the method of O Nano microsphere, is characterized in that being added drop-wise in lauroylamidopropyl betaine solution by neutralized verdigris solution in step 2, after dropwising, stirs 35min, then regulates pH to be 10.5 by NaOH solution.
5. one according to claim 1 and 2 utilizes lauroylamidopropyl betaine to prepare Cu
2the method of O Nano microsphere, is characterized in that regulating the pH value of lauroylamidopropyl betaine solution to be 10.5 by NaOH solution in step 2, then drips neutralized verdigris solution, after dropwising, stir 35min, obtain mixed solution.
6. one according to claim 1 and 2 utilizes lauroylamidopropyl betaine to prepare Cu
2the method of O Nano microsphere, is characterized in that in step 3, ascorbic acid solution is added drop-wise to stirring reaction 50min in mixed solution.
7. one according to claim 1 and 2 utilizes lauroylamidopropyl betaine to prepare Cu
2the method of O Nano microsphere, is characterized in that the mol ratio of step 3 neutralized verdigris and xitix is 1:2.2.
8. one according to claim 1 and 2 utilizes lauroylamidopropyl betaine to prepare Cu
2the method of O Nano microsphere, is characterized in that the amount of substance of neutralized verdigris in neutralized verdigris solution in step 2 is 1mmol:(300 ~ 350 with the ratio of the volume of lauroylamidopropyl betaine solution) mL.
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| CN201510909222.XA CN105417573B (en) | 2015-12-10 | 2015-12-10 | One kind prepares Cu using lauroylamidopropyl betaine2The method of O nanoparticles |
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| CN201510909222.XA CN105417573B (en) | 2015-12-10 | 2015-12-10 | One kind prepares Cu using lauroylamidopropyl betaine2The method of O nanoparticles |
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| CN105417573B CN105417573B (en) | 2018-04-17 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107185600A (en) * | 2017-05-09 | 2017-09-22 | 安徽皖东化工有限公司 | A kind of preparation technology of groundwater treatment macroporous anion exchange resin |
| CN107321394A (en) * | 2017-05-09 | 2017-11-07 | 安徽皖东化工有限公司 | A kind of sewage disposal anion exchange resin preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041456A (en) * | 2007-03-02 | 2007-09-26 | 江南大学 | Method for preparing monodispersed copper-protoxide hollow microsphere by aqueous phase cluster soft mold plates process |
| CN101397137A (en) * | 2007-09-27 | 2009-04-01 | 刘文红 | Globular inorganic oxide material, synthetic method, modification method and use thereof |
| CN103204525A (en) * | 2012-01-17 | 2013-07-17 | 上海杰事杰新材料(集团)股份有限公司 | Application of lactam as solvent in nano-grade material preparation |
-
2015
- 2015-12-10 CN CN201510909222.XA patent/CN105417573B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041456A (en) * | 2007-03-02 | 2007-09-26 | 江南大学 | Method for preparing monodispersed copper-protoxide hollow microsphere by aqueous phase cluster soft mold plates process |
| CN101397137A (en) * | 2007-09-27 | 2009-04-01 | 刘文红 | Globular inorganic oxide material, synthetic method, modification method and use thereof |
| CN103204525A (en) * | 2012-01-17 | 2013-07-17 | 上海杰事杰新材料(集团)股份有限公司 | Application of lactam as solvent in nano-grade material preparation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107185600A (en) * | 2017-05-09 | 2017-09-22 | 安徽皖东化工有限公司 | A kind of preparation technology of groundwater treatment macroporous anion exchange resin |
| CN107321394A (en) * | 2017-05-09 | 2017-11-07 | 安徽皖东化工有限公司 | A kind of sewage disposal anion exchange resin preparation method |
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