CN100486896C - Method for preparing monodispersed copper-protoxide hollow microsphere by aqueous phase cluster soft mold plates process - Google Patents
Method for preparing monodispersed copper-protoxide hollow microsphere by aqueous phase cluster soft mold plates process Download PDFInfo
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- CN100486896C CN100486896C CNB2007100202003A CN200710020200A CN100486896C CN 100486896 C CN100486896 C CN 100486896C CN B2007100202003 A CNB2007100202003 A CN B2007100202003A CN 200710020200 A CN200710020200 A CN 200710020200A CN 100486896 C CN100486896 C CN 100486896C
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Abstract
The invention discloses a preparing method of monodisperse cuprous oxide hollow submicroballoon with aqueous phase cluster soft mold plates method in preparing technical domain of inorganic functional material, which comprises the following steps: forming cluster with polyvinyl pyrrolidon and dodecyl sodium sulfate; setting the cluster as soft mold plate; mixing water solution of nantokite with water solution of cluster soft mold plate; adjusting pH value; using hydrazine hydrate as reducer; deacidizing copper ion quickly; getting copper-protoxide hollow submicroballoon colloidal solution; making the soft mold plate with the function of controlling outlook and size of particle during reacting course; whizzing; depositing; washing with deionized water and absolute ethyl alcohol; getting copper-protoxide nanometer particle with grain diameter at 11-22 nm; self-assembling; forming monodisperse cuprous oxide hollow submicroballoon with diameter of particle at 400-550 nm.
Description
Technical field
The present invention relates to a kind of method, belong to the preparing technical field of inorganic functional material by the single fully dispersion Red copper oxide of aqueous phase cluster soft mold plates legal system hollow sub-micro ball.
Background technology
Nano/micron level inorganic oxide hollow ball,, characteristics such as specific surface area big, thermodynamic stability height low because of its density have very wide application prospect.They not only can be used as light filler, high-selectivity catalyst or support of the catalyst, the controlled transportation and the delivery systme that can also be widely used in medicine, dyestuff, makeup, susceptibility reagent such as enzyme and protein etc. as microencapsulation material, and also have extremely important using value in fields such as artificial cell, medical diagnosis on disease, environmental protection.Red copper oxide is a kind of P-type semiconductor, has special optics, photoelectricity and catalytic performance, can be used as the sterilant in coatings industry and the agricultural, the tinting material in the glass industry; Current research shows, Red copper oxide also can be used as the negative material of catalyzer, photoelectron transition material, lithium ion battery of photolysis water and ballast material etc.
Up to the present, bright both at home and abroad rarely relevant for the report for preparing Red copper oxide hollow nanometer/sub-micron ball.People such as Liu Hongjiang had once reported and have utilized the multiple microemulsion of O/W/O to prepare Red copper oxide hollow microsphere (particle diameter 600～1200nm) for template, but the structural stability of the multiple microemulsion of O/W/O is poor, must be by microwave heating, be unfavorable for scale operation, and the particle diameter of preparation distributes wide.Do not see as yet both at home and abroad with the aqueous phase cluster soft mold plates legal system and be equipped with single report that disperses Red copper oxide hollow sub-micro ball.
Summary of the invention
The objective of the invention is to: provide a kind of aqueous phase cluster soft mold plates to prepare single method of disperseing Red copper oxide hollow sub-micro ball fast.This method can utilize the cluster of polyvinylpyrrolidone and sodium lauryl sulphate formation as the adjustability soft template, prepares monodispersed Red copper oxide hollow sub-micro ball by the quick water of simple reduction reaction.
Technical scheme of the present invention: utilize the soft template of the cluster of polyvinylpyrrolidone and sodium lauryl sulphate formation as preparation Red copper oxide hollow sub-micro ball, thus the particle diameter and the pattern of regulation and control Red copper oxide hollow sub-micro ball; The aqueous solution that will contain mantoquita joins in the above-mentioned cluster soft mold plates aqueous solution, regulates the pH value back of mixing solutions and uses hydrazine hydrate as reductive agent, fast cupric ion is reduced into single Red copper oxide hollow sub-micro ball that disperses.Concrete technology is:
1) a certain amount of polyvinylpyrrolidone and sodium lauryl sulphate are joined in the deionized water, being heated to 40～60 ℃ fully dissolves it and is self-assembled into cluster, treat to mix with copper salt solution after solution is cooled to room temperature, make that each component ultimate density is respectively in the solution: cupric ion 1～10mmol/L, polyvinylpyrrolidone 1～10g/L, sodium lauryl sulphate 5～45mmol/L;
2) with aqueous sodium hydroxide solution regulating step 1) the pH value of the mixing solutions that obtains is 8.5～11.5;
3) in the stirring, with mass concentration is that 50% hydrazine hydrate aqueous solution joins step 2) in the mixing solutions that obtains, the mol ratio of cupric ion and hydrazine hydrate is 1: 10～30, behind the uniform mixing in 40～60 ℃ water bath with thermostatic control standing and reacting 50～80 minutes, obtain containing single colloidal solution that disperses Red copper oxide hollow sub-micro ball;
4) colloidal solution that step 3) is obtained carries out centrifugation, and precipitate with deionized water and dehydrated alcohol clean and obtain single Red copper oxide hollow sub-micro ball that disperses.
Used mantoquita is copper sulfate or cupric chloride.
Beneficial effect of the present invention: use polyvinylpyrrolidone and sodium lauryl sulphate as protective material among the present invention, in the aqueous solution, can self-assembly form cluster; And the cluster that can form shape under the different condition and vary in size.The present invention utilizes hydrazine hydrate as reductive agent, the cluster that forms with polyvinylpyrrolidone and sodium lauryl sulphate is as the soft template of preparation Red copper oxide hollow sub-micro ball, fast cupric ion is reduced into monodispersed Red copper oxide hollow sub-micro ball, can regulate and control the size distribution of product, obtain the about 400～550nm of diameter easily, single Red copper oxide hollow sub-micro ball, the particle diameter that technology is simple and prepared and pattern homogeneous of disperseing with narrow size distribution feature.
The product of the present invention preparation is that the cuprous nano particle self-assembly by the about 11～22nm of particle diameter forms.
Preparation technology of the present invention is simple, reaction temperature and, condition control is convenient, easy handling and repetition, cost is low, is convenient to suitability for industrialized production.
Description of drawings
The X-ray diffractogram of the Red copper oxide hollow sub-micro ball of Fig. 1 embodiment 1 preparation.
The transmission electron microscope picture of the Red copper oxide hollow sub-micro ball of Fig. 2 embodiment 1 preparation.
The X-ray diffractogram of the Red copper oxide hollow sub-micro ball of Fig. 3 embodiment 2 preparations.
The transmission electron microscope picture of the Red copper oxide hollow sub-micro ball of Fig. 4 embodiment 2 preparations.
Embodiment
Embodiment 1
1) a certain amount of polyvinylpyrrolidone and sodium lauryl sulphate are joined in the deionized water, being heated to 40～60 ℃ fully dissolves it and is self-assembled into cluster, treat to mix with copper sulfate solution after solution is cooled to room temperature, make that each component ultimate density is respectively in the solution: copper sulfate 1mmol/L, polyvinylpyrrolidone 10g/L, sodium lauryl sulphate 9mmol/L;
2) with aqueous sodium hydroxide solution regulating step 1) the pH value of the mixing solutions that obtains is 8.5～11.5;
3) stirring, is that 50% hydrazine hydrate aqueous solution joins step 2 with concentration) in the mixing solutions that obtains, the mol ratio of copper sulfate and hydrazine hydrate is 1: 20.Be statically placed in 40～60 ℃ the water bath with thermostatic control reaction behind the uniform mixing 55 minutes, and obtained containing single colloidal solution that disperses Red copper oxide hollow sub-micro ball;
4) colloidal solution that step 3) is obtained carries out centrifugation, promptly obtains monodispersed Red copper oxide hollow sub-micro ball with deionized water and dehydrated alcohol washing and precipitating.
Fig. 1 and Fig. 2 are respectively the X-ray diffractogram and the transmission electron microscope pictures of the Red copper oxide hollow sub-micro ball of embodiment 1 preparation, and the median size of Red copper oxide hollow sub-micro ball is 500nm.
Embodiment 2
1) a certain amount of polyvinylpyrrolidone and sodium lauryl sulphate are joined in the deionized water, being heated to 40～60 ℃ fully dissolves it and is self-assembled into cluster, treat to mix with copper chloride solution after solution is cooled to room temperature, make that each component ultimate density is respectively in the solution: cupric chloride 1mmol/L, polyvinylpyrrolidone 10g/L, sodium lauryl sulphate 35mmol/L;
2) with aqueous sodium hydroxide solution regulating step 1) the pH value of the mixing solutions that obtains is 8.5～11.5;
3) stirring, is that 50% hydrazine hydrate aqueous solution joins step 2 with concentration) in the mixing solutions that obtains, the mol ratio of copper sulfate and hydrazine hydrate is 1: 20.Be statically placed in 40～60 ℃ the water bath with thermostatic control reaction behind the uniform mixing 55 minutes, and obtained containing single colloidal solution that disperses Red copper oxide hollow sub-micro ball;
4) colloidal solution that step 3) is obtained carries out centrifugation, and precipitate with deionized water and dehydrated alcohol clean and promptly obtain monodispersed Red copper oxide hollow sub-micro ball.
Fig. 3 and Fig. 4 are respectively the X-ray diffractogram and the transmission electron microscope pictures of the Red copper oxide hollow sub-micro ball of embodiment 2 preparations, and the median size of Red copper oxide hollow sub-micro ball is 420nm.
Embodiment 3
1) a certain amount of polyvinylpyrrolidone and sodium lauryl sulphate are joined in the deionized water, being heated to 40～60 ℃ fully dissolves it and is self-assembled into cluster, treat to mix with copper sulfate solution after solution is cooled to room temperature, make that each component ultimate density is respectively in the solution: copper sulfate 5mmol/L, polyvinylpyrrolidone 2g/L, sodium lauryl sulphate 9mmol/L;
2) with aqueous sodium hydroxide solution regulating step 1) the pH value of the mixing solutions that obtains is 8.5～11.5;
3) stirring, is that 50% hydrazine hydrate aqueous solution joins step 2 with concentration) in the mixing solutions that obtains, the mol ratio of copper sulfate and hydrazine hydrate is 1: 20.Be statically placed in 40～60 ℃ the water bath with thermostatic control reaction behind the uniform mixing 55 minutes, and obtained containing single colloidal solution that disperses Red copper oxide hollow sub-micro ball;
4) colloidal solution that step 3) is obtained carries out centrifugation, and precipitate with deionized water and dehydrated alcohol clean and promptly obtain monodispersed Red copper oxide hollow sub-micro ball.
The median size of Red copper oxide hollow sub-micro ball is 530nm.
Embodiment 4
1) a certain amount of polyvinylpyrrolidone and sodium lauryl sulphate are joined in the deionized water, being heated to 40～60 ℃ fully dissolves it and is self-assembled into cluster, treat to mix with copper sulfate solution after solution is cooled to room temperature, make that each component ultimate density is respectively in the solution: copper sulfate 1mmol/L, polyvinylpyrrolidone 2g/L, sodium lauryl sulphate 9mmol/L;
2) with aqueous sodium hydroxide solution regulating step 1) the pH value of the mixing solutions that obtains is 8.5～11.5;
3) stirring, is that 50% hydrazine hydrate aqueous solution joins step 2 with concentration) in the mixing solutions that obtains, the mol ratio of copper sulfate and hydrazine hydrate is 1: 10.Be statically placed in 40～60 ℃ the water bath with thermostatic control reaction behind the uniform mixing 80 minutes, and obtained containing single colloidal solution that disperses Red copper oxide hollow sub-micro ball;
4) colloidal solution that step 3) is obtained carries out centrifugation, and precipitate with deionized water and dehydrated alcohol clean and promptly obtain monodispersed Red copper oxide hollow sub-micro ball.
The median size of Red copper oxide hollow sub-micro ball is 505nm.
Embodiment 5
1) a certain amount of polyvinylpyrrolidone and sodium lauryl sulphate are joined in the deionized water, being heated to 40～60 ℃ fully dissolves it and is self-assembled into cluster, treat to mix with copper sulfate solution after solution is cooled to room temperature, make that each component ultimate density is respectively in the solution: copper sulfate 10mmol/L, polyvinylpyrrolidone 5g/L, sodium lauryl sulphate 20mmol/L;
2) with aqueous sodium hydroxide solution regulating step 1) the pH value of the mixing solutions that obtains is 8.5～11.5;
3) stirring, is that 50% hydrazine hydrate aqueous solution joins step 2 with concentration) in the mixing solutions that obtains, the mol ratio of copper sulfate and hydrazine hydrate is 1: 30.Be statically placed in 40～60 ℃ the water bath with thermostatic control reaction behind the uniform mixing 50 minutes, and obtained containing single colloidal solution that disperses Red copper oxide hollow sub-micro ball;
4) colloidal solution that step 3) is obtained carries out centrifugation, and precipitate with deionized water and dehydrated alcohol clean and promptly obtain monodispersed Red copper oxide hollow sub-micro ball.
The median size of Red copper oxide hollow sub-micro ball is 550nm.
Embodiment 6
1) a certain amount of polyvinylpyrrolidone and sodium lauryl sulphate are joined in the deionized water, being heated to 40～60 ℃ fully dissolves it and is self-assembled into cluster, treat to mix with copper chloride solution after solution is cooled to room temperature, make that each component ultimate density is respectively in the solution: cupric chloride 5mmol/L, polyvinylpyrrolidone 10g/L, sodium lauryl sulphate 45mmol/L;
2) with aqueous sodium hydroxide solution regulating step 1) the pH value of the mixing solutions that obtains is 8.5～11.5;
3) stirring, is that 50% hydrazine hydrate aqueous solution joins step 2 with concentration) in the mixing solutions that obtains, the mol ratio of copper sulfate and hydrazine hydrate is 1: 20.Be statically placed in 40～60 ℃ the water bath with thermostatic control reaction behind the uniform mixing 55 minutes, and obtained containing single colloidal solution that disperses Red copper oxide hollow sub-micro ball;
4) colloidal solution that step 3) is obtained carries out centrifugation, and precipitate with deionized water and dehydrated alcohol clean and promptly obtain monodispersed Red copper oxide hollow sub-micro ball.
The median size of Red copper oxide hollow sub-micro ball is 520nm.
Claims (2)
1. the aqueous phase cluster soft mold plates legal system is equipped with single method of disperseing Red copper oxide hollow sub-micro ball, it is characterized in that utilizing the soft template of the cluster of polyvinylpyrrolidone and sodium lauryl sulphate formation as preparation Red copper oxide hollow sub-micro ball, the aqueous solution that will contain mantoquita joins in the above-mentioned cluster shape soft template aqueous solution, regulating the pH value back of mixing solutions uses hydrazine hydrate as reductive agent, fast cupric ion is reduced into single Red copper oxide hollow sub-micro ball that disperses, technology is:
1) a certain amount of polyvinylpyrrolidone and sodium lauryl sulphate are joined in the deionized water, being heated to 40～60 ℃ fully dissolves it and is self-assembled into cluster, treat to mix with copper salt solution after solution is cooled to room temperature, make that each component ultimate density is respectively in the solution: cupric ion 1～10mmol/L, polyvinylpyrrolidone 1～10g/L, sodium lauryl sulphate 5～45mmol/L;
2) with aqueous sodium hydroxide solution regulating step 1) the pH value of the mixing solutions that obtains is 8.5～11.5;
3) in the stirring, with mass concentration is that 50% hydrazine hydrate aqueous solution joins step 2) in the mixing solutions that obtains, the mol ratio of cupric ion and hydrazine hydrate is 1: 10～30, behind the uniform mixing in 40～60 ℃ water bath with thermostatic control standing and reacting 50～80 minutes, obtain containing single colloidal solution that disperses Red copper oxide hollow sub-micro ball;
4) colloidal solution that step 3) is obtained carries out centrifugation, and precipitate with deionized water and dehydrated alcohol clean and obtain monodispersed Red copper oxide hollow sub-micro ball.
2. method according to claim 1 is characterized in that used mantoquita is copper sulfate or cupric chloride.
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| CN103043703A (en) * | 2013-01-05 | 2013-04-17 | 河北工业大学 | Preparation method of hollow Cu2O cubic box |
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| CN101722314B (en) * | 2009-11-20 | 2014-08-20 | 云南大学 | Method for preparing Cu2O-Cu composite microsphere by adopting bean flour as template |
| CN103771484B (en) * | 2014-01-14 | 2015-09-16 | 山东理工大学 | The preparation method of the regulatable Red copper oxide micron ball of a kind of particle diameter |
| CN104625085B (en) * | 2015-01-23 | 2017-01-11 | 中国矿业大学 | Method for simply and stably preparing micro-nano hollow copper |
| CN105417573B (en) * | 2015-12-10 | 2018-04-17 | 齐齐哈尔大学 | One kind prepares Cu using lauroylamidopropyl betaine2The method of O nanoparticles |
| CN105905936B (en) * | 2016-04-14 | 2017-11-14 | 青岛大学 | A kind of cuprous nano crystalline substance assembly |
| CN106745177A (en) * | 2016-11-11 | 2017-05-31 | 江南大学 | Flower-like nanometer Cu in a kind of ionic liquid2The preparation method of O |
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| CN103043703A (en) * | 2013-01-05 | 2013-04-17 | 河北工业大学 | Preparation method of hollow Cu2O cubic box |
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Assignee: Xinyi Ceramic (China) Co., Ltd. Assignor: Jiangnan University Contract fulfillment period: 2009.8.10 to 2027.3.1 contract change Contract record no.: 2009320001524 Denomination of invention: Method for preparing monodispersed copper-protoxide hollow microsphere by aqueous phase cluster soft mold plates process Granted publication date: 20090513 License type: Exclusive license Record date: 2009.8.14 |
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