CN101332999A - Method for preparing Cu2O or CuO hollow submicrospheres with particle diameter controllable by water phase soft template method - Google Patents
Method for preparing Cu2O or CuO hollow submicrospheres with particle diameter controllable by water phase soft template method Download PDFInfo
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- CN101332999A CN101332999A CNA200810021521XA CN200810021521A CN101332999A CN 101332999 A CN101332999 A CN 101332999A CN A200810021521X A CNA200810021521X A CN A200810021521XA CN 200810021521 A CN200810021521 A CN 200810021521A CN 101332999 A CN101332999 A CN 101332999A
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Abstract
The invention relates to a method for preparing Cu2O or CuO hollow submicron particles with controllable particle sizes by a water phase soft-template method, belonging to the technical field of the preparation of inorganic functional materials. In the invention, necklace-shaped soft matter clusters formed by sodium dodecyl sulfate and polyvinylpyrrolidone are taken as templates, cupric salt solution is added in soft clusters solution, after the pH value of the mixed solution is adjusted, hydrazine hydrate is taken as a reducing agent to quickly reduce copper ions by a one-pot method and assemble the copper ions into the Cu2O hollow submicron particles with controllable grain diameters and narrow particle size distribution; or further temperature programmed baking is carried out to oxidize the Cu2O hollow submicron particles to obtain CuO hollow submicron particles, the particle size and particle size distribution of which are similar to that of the Cu2O hollow submicron particles. The method of the invention has the advantages that: the products, Cu2O or CuO hollow submicron particles, have small particle sizes, narrow particle size distribution and good controllable property, the preparing technique is simple, the reaction at normal temperature and normal pressure is mild, the one-pot synthesis is easy to operate and repeat, and the method has low cost and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind ofly be equipped with by the aqueous phase soft mould plate legal system that particle diameter is controlled, the Cu of the narrow distribution of particle diameter
2O hollow sub-micro ball, or further its roasting is prepared the method for CuO hollow sub-micro ball by temperature programming, belong to the preparing technical field of inorganic functional material.
Background technology
Red copper oxide (Cu
2O) be a kind of P-type semiconductor, energy gap is 2.2eV only, has special optics, photoelectricity and catalytic performance, all has a wide range of applications in fields such as transmitter, catalyzer, electronic component, antifouling coating, electrode materials and tinting materials.CuO is widely used in fields such as catalysis, superconduction, pottery as a kind of important inorganic materials.Its useful as catalysts or support of the catalyst and electrode active material also can be used as the burningrate catalyst of rocket propellant.
Compare with macroscopic material, the micro-/ nano material has excellent physical chemistry characteristic, at numerous areas such as biology, optics, transmitter, semi-conductor, microelectronics and catalysis very big using value is arranged all.Characteristics such as the inorganic oxide hollow micro-/ nano ball with Novel Topology structure has that density is low, heat and mechanical stability height, can be used as light filler, high-selectivity catalyst or support of the catalyst, the slowly-releasing of medicine, dyestuff, makeup, controlled-release material, and also have extremely important value at aspects such as medicine equipment, biological diagnosises.
In many preparation methods, advantages such as technology is simple, with low cost because of having for the liquid phase chemical reduction method, the easy control of process are comparatively commonly used.But single surfactant system or macromolecular system only play the effect of stablizer, dispersion agent in reaction process, have defectives such as aggregate metamorphosis pattern is limited, structural controllability difference.This patent part contriver in earlier stage applied for about the Chinese invention patent of " the aqueous phase cluster soft mold plates legal system is equipped with single Red copper oxide hollow sub-micro ball that disperses " and open (CN 101041456A), obtained the Cu of particle diameter littler (150-350nm) with the present invention
2O hollow sub-micro ball is compared, and patent CN 101041456A adopts lower mantoquita concentration and lower reductive agent hydrazine hydrate concentration, obtains the Cu of big (400-550nm) of particle diameter
2O hollow sub-micro ball.
Summary of the invention
The object of the invention is: provide a kind of aqueous phase soft mould plate one kettle way to prepare fast that particle diameter is controlled, the Cu of the narrow distribution of particle diameter
2The method of O or CuO hollow sub-micro ball.The soft material cluster of item chain that this method utilizes sodium lauryl sulphate and polyvinylpyrrolidone to form is template, by simple reduction reaction with cupric ion through the one kettle way fast restore and be assembled into that particle diameter is controlled, the Cu of the narrow distribution of particle diameter
2O hollow sub-micro ball; Or further can make Cu by temperature-programmed calcination
2The oxidation of O hollow sub-micro ball obtains particle diameter and the similar CuO hollow sub-micro ball of size distribution.
Technical scheme of the present invention: a kind of aqueous phase soft mould plate legal system is equipped with the controlled Cu of particle diameter
2The method of O or CuO hollow sub-micro ball, the soft material cluster of item chain that forms with sodium lauryl sulphate and polyvinylpyrrolidone is a template, copper salt solution is joined in the described soft matter cluster aqueous solution, regulate the pH value back use hydrazine hydrate of mixing solutions and make reductive agent, with cupric ion through the one kettle way fast restore and be assembled into that particle diameter is controlled, the Cu of the narrow distribution of particle diameter
2O hollow sub-micro ball; Or further make Cu by temperature-programmed calcination
2The oxidation of O hollow sub-micro ball obtains particle diameter and size distribution and Cu
2The CuO hollow sub-micro ball that O hollow sub-micro ball is similar; Technology is:
1) a certain amount of sodium lauryl sulphate SDS and polyvinylpyrrolidone PVP are added in the deionized water, being heated to 40-60 ℃ fully dissolves it and is assembled into soft matter cluster, treat to mix with copper salt solution after solution is cooled to room temperature, make that each component ultimate density scope is respectively in the solution: cupric ion 10-30mmol/L, SDS 5-50mmol/L, PVP 1-10g/L;
2) with the sodium hydroxide solution regulating step 1 of 2.5mol/L) the pH scope of the mixing solutions that obtains is 8-12;
3) under agitation condition be that 50% hydrazine hydrate aqueous solution joins step 2 with mass concentration) in the mixing solutions that obtains, make that the final mol ratio of cupric ion and hydrazine hydrate is 1: 10-30, mix the back and under 40-60 ℃ condition, react 50-80min, obtain orange-yellow Cu
2Throw out that O colloidal solution, centrifugation obtain is with deionized water and absolute ethanol washing, be characterized by through Electronic Speculum have the narrow distribution of particle diameter, median size is at the controlled Cu of 150-350nm
2O hollow sub-micro ball;
Or 4) Cu that further step 3) is obtained
2O hollow sub-micro ball begins after 1 ℃/min temperature programming to 300 ℃ from room temperature, be rapidly heated again to 500 ℃ and roasting 1-5h to constant weight, obtain particle diameter and size distribution and described Cu
2The CuO hollow sub-micro ball that O hollow sub-micro ball is similar.
Used mantoquita is copper sulfate, cupric nitrate, neutralized verdigris or cupric chloride.
Beneficial effect of the present invention: the soft material cluster of item chain that the present invention utilizes sodium lauryl sulphate and polyvinylpyrrolidone to form is template, hydrazine hydrate be the reductive agent one kettle way fast with the mantoquita reduction and be assembled into that median size is controlled in the 150-350nm scope, the narrow distribution of particle diameter Cu
2O hollow sub-micro ball, in preparation process, this soft matter cluster template can be regulated and control the size distribution of product, obtains having the Cu of the narrow distribution of particle diameter
2O hollow sub-micro ball, technology is simple, the Cu that obtains
2Little, the pattern homogeneous in O hollow sub-micro spherolite footpath.By this Cu of temperature-programmed calcination
2O hollow sub-micro ball prepares particle diameter and the similar CuO hollow sub-micro ball of size distribution.
The Cu of the present invention's preparation
2O, CuO hollow sub-micro ball are the simple Cu that is about 8-14nm by particle diameter
2O, CuO nanocrystal assemble.
The product particle diameter of the present invention preparation is little, narrow diameter distribution and controllability are good, and preparation technology is simple, the normal temperature and pressure reaction temperature and, synthetic easy handling of one kettle way and repetition, cost is low, is convenient to suitability for industrialized production.
Description of drawings
The Cu of Fig. 1 embodiment 1 preparation
2The X-ray diffractogram of O hollow sub-micro ball.
The Cu of Fig. 2 embodiment 1 preparation
2The transmission electron microscope picture of O hollow sub-micro ball.
The X-ray diffractogram of the CuO hollow sub-micro ball of Fig. 3 embodiment 1 preparation.
The sem photograph of the CuO hollow sub-micro ball of Fig. 4 embodiment 1 preparation.
Embodiment
Embodiment 1
1) a certain amount of sodium lauryl sulphate and polyvinylpyrrolidone are added in the deionized water, being heated to 40 ℃ fully dissolves it and is self-assembled into soft matter cluster, treat to mix with copper sulfate solution after solution is cooled to room temperature, make that each component ultimate density scope is respectively in the solution: copper sulfate 20mmol/L, SDS 45mmol/L, PVP 10g/L;
2) with the sodium hydroxide solution regulating step 1 of 2.5mol/L) the pH value of the mixing solutions that obtains is 12;
3) under agitation condition be that 50% hydrazine hydrate aqueous solution joins step 2 with mass concentration) in the mixing solutions that obtains, make that the final mol ratio of cupric ion and hydrazine hydrate is 1: 20, mix the back and in 50 ℃ water bath with thermostatic control, react 55min, obtain orange-yellow Cu
2O colloidal solution obtains throw out after centrifugation, throw out obtains Cu behind deionized water and absolute ethanol washing
2O hollow sub-micro ball;
4) with the Cu that obtains through centrifugation in the step 3)
2O hollow sub-micro ball begins after 1 ℃/min temperature programming to 300 ℃ from room temperature, be rapidly heated again to 500 ℃ and roasting 1-5h to constant weight, obtain particle diameter and size distribution and Cu
2The CuO hollow sub-micro ball that O hollow sub-micro ball is similar.
Fig. 1 and Fig. 2 are respectively the Cu of embodiment 1 preparation
2The X-ray diffractogram and the transmission electron microscope picture of O hollow sub-micro ball, Cu
2The median size of O hollow sub-micro ball is 180nm; Fig. 3 and Fig. 4 are respectively the X-ray diffractogram and the sem photographs of the CuO hollow sub-micro ball of embodiment 1 preparation, and the median size of CuO hollow sub-micro ball is 200nm.
Embodiment 2
1) a certain amount of sodium lauryl sulphate and polyvinylpyrrolidone are added in the deionized water, being heated to 45 ℃ fully dissolves it and is self-assembled into soft matter cluster, treat to mix with copper nitrate aqueous solution after solution is cooled to room temperature, make that each component ultimate density scope is respectively in the solution: cupric nitrate 15mmol/L, SDS 25mmol/L, PVP 10g/L;
2) with the sodium hydroxide solution regulating step 1 of 2.5mol/L) the pH value of the mixing solutions that obtains is 11;
3) under agitation condition be that 50% hydrazine hydrate aqueous solution joins step 2 with mass concentration) in the mixing solutions that obtains, make that the final mol ratio of cupric ion and hydrazine hydrate is 1: 15, mix the back and in 50 ℃ water bath with thermostatic control, react 55min, obtain orange-yellow Cu
2O colloidal solution obtains throw out after centrifugation, throw out obtains Cu behind deionized water and absolute ethanol washing
2O hollow sub-micro ball;
4) with the Cu that obtains in the step 3)
2O hollow sub-micro ball begins after 1 ℃/min temperature programming to 300 ℃ from room temperature, be rapidly heated again to 500 ℃ and roasting 1-5h to constant weight.Gained Cu
2The median size of O hollow sub-micro ball is 200nm, and the median size of CuO hollow sub-micro ball is 220nm.
Embodiment 3
1) a certain amount of sodium lauryl sulphate and polyvinylpyrrolidone are added in the deionized water, being heated to 55 ℃ fully dissolves it and is self-assembled into soft matter cluster, treat that solution is cooled to after the room temperature and the neutralized verdigris aqueous solution, make that each component ultimate density scope is respectively in the solution: neutralized verdigris 15mmol/L, SDS 9mmol/L, PVP 8g/L;
2) with the sodium hydroxide solution regulating step 1 of 2.5mol/L) the pH value of the mixing solutions that obtains is 11;
3) under agitation condition be that 50% hydrazine hydrate aqueous solution joins step 2 with mass concentration) in the mixing solutions that obtains, make that the final mol ratio of cupric ion and hydrazine hydrate is 1: 15, mix the back and in 40 ℃ water bath with thermostatic control, react 65min, obtain orange-yellow Cu
2O colloidal solution obtains throw out after centrifugation, throw out obtains Cu behind deionized water and absolute ethanol washing
2O hollow sub-micro ball;
4) with the Cu that obtains in the step 3)
2O hollow sub-micro ball begins after 1 ℃/min temperature programming to 300 ℃ from room temperature, be rapidly heated again to 500 ℃ and roasting 1-5h to constant weight.Gained Cu
2The median size of O hollow sub-micro ball is 220nm, and the median size of CuO hollow sub-micro ball is 235nm.
Embodiment 4
1) a certain amount of sodium lauryl sulphate and polyvinylpyrrolidone are added in the deionized water, being heated to 40 ℃ fully dissolves it and is self-assembled into soft matter cluster, treat to mix with copper chloride solution after solution is cooled to room temperature, make that each component ultimate density scope is respectively in the solution: cupric chloride 10mmol/L, SDS 9mmol/L, PVP 4g/L;
2) with the sodium hydroxide solution regulating step 1 of 2.5mol/L) the pH value of the mixing solutions that obtains is 10;
3) under agitation condition be that 50% hydrazine hydrate aqueous solution joins step 2 with mass concentration) in the mixing solutions that obtains, make that the final mol ratio of cupric ion and hydrazine hydrate is 1: 15, mix the back and in 40 ℃ water bath with thermostatic control, react 70min, obtain orange-yellow Cu
2O colloidal solution obtains throw out after centrifugation, throw out obtains Cu behind deionized water and absolute ethanol washing
2O hollow sub-micro ball;
4) with the Cu that obtains in the step 3)
2O hollow sub-micro ball begins after 1 ℃/min temperature programming to 300 ℃ from room temperature, be rapidly heated again to 500 ℃ and roasting 1-5h to constant weight.Gained Cu
2The median size of O hollow sub-micro ball is 240nm, and the median size of CuO hollow sub-micro ball is 265nm.
Embodiment 5
1) a certain amount of sodium lauryl sulphate and polyvinylpyrrolidone are added in the deionized water, being heated to 40 ℃ fully dissolves it and is self-assembled into soft matter cluster, treat to mix with copper sulfate solution after solution is cooled to room temperature, make that each component ultimate density scope is respectively in the solution: copper sulfate 10mmol/L, SDS 5mmol/L, PVP 2g/L;
2) with the sodium hydroxide solution regulating step 1 of 2.5mol/L) the pH value of the mixing solutions that obtains is 9;
3) under agitation condition be that 50% hydrazine hydrate aqueous solution joins step 2 with mass concentration) in the mixing solutions that obtains, make that the final mol ratio of cupric ion and hydrazine hydrate is 1: 10, mix the back and in 40 ℃ water bath with thermostatic control, react 75min, obtain orange-yellow Cu
2O colloidal solution obtains throw out after centrifugation, throw out obtains Cu behind deionized water and absolute ethanol washing
2O hollow sub-micro ball;
4) with the Cu that obtains in the step 3)
2O hollow sub-micro ball begins after 1 ℃/min temperature programming to 300 ℃ from room temperature, be rapidly heated again to 500 ℃ and roasting 1-5h to constant weight.Gained Cu
2The median size of O hollow sub-micro ball is 265nm, and the median size of CuO hollow sub-micro ball is 290nm.
Embodiment 6
1) a certain amount of sodium lauryl sulphate and polyvinylpyrrolidone are added in the deionized water, being heated to 40 ℃ fully dissolves it and is self-assembled into soft matter cluster, treat to mix with copper sulfate solution after solution is cooled to room temperature, make that each component ultimate density scope is respectively in the solution: copper sulfate 25mmol/L, SDS 45mmol/L, PVP 10g/L;
2) with the sodium hydroxide solution regulating step 1 of 2.5mol/L) the pH value of the mixing solutions that obtains is 12;
3) under agitation condition be that 50% hydrazine hydrate aqueous solution joins step 2 with mass concentration) in the mixing solutions that obtains, make that the final mol ratio of cupric ion and hydrazine hydrate is 1: 25, mix the back and in 55 ℃ water bath with thermostatic control, react 55min, obtain orange-yellow Cu
2O colloidal solution obtains throw out after centrifugation, throw out obtains Cu behind deionized water and absolute ethanol washing
2O hollow sub-micro ball;
4) with the Cu that obtains in the step 3)
2O hollow sub-micro ball begins after 1 ℃/min temperature programming to 300 ℃ from room temperature, be rapidly heated again to 500 ℃ and roasting 1-5h to constant weight.Gained Cu
2The median size of O hollow sub-micro ball is 155nm, and the median size of CuO hollow sub-micro ball is 180nm.
Claims (2)
1. an aqueous phase soft mould plate legal system is equipped with the controlled Cu of particle diameter
2The method of O or CuO hollow sub-micro ball, it is characterized in that the soft material cluster of item chain of utilizing sodium lauryl sulphate and polyvinylpyrrolidone to form is template, copper salt solution is joined in the described soft matter cluster aqueous solution, regulate the pH value back use hydrazine hydrate of mixing solutions and make reductive agent, with cupric ion through the one kettle way fast restore and be assembled into that particle diameter is controlled, the Cu of the narrow distribution of particle diameter
2O hollow sub-micro ball; Or further make Cu by temperature-programmed calcination
2The oxidation of O hollow sub-micro ball obtains particle diameter and size distribution and Cu
2The CuO hollow sub-micro ball that O hollow sub-micro ball is similar; Technology is:
1) a certain amount of sodium lauryl sulphate SDS and polyvinylpyrrolidone PVP are added in the deionized water, being heated to 40-60 ℃ fully dissolves it and is assembled into soft matter cluster, treat to mix with copper salt solution after solution is cooled to room temperature, make that each component ultimate density scope is respectively in the solution: cupric ion 10-30mmol/L, SDS 5-50mmol/L, PVP 1-10g/L;
2) with the sodium hydroxide solution regulating step 1 of 2.5mol/L) the pH scope of the mixing solutions that obtains is 8-12;
3) under agitation condition be that 50% hydrazine hydrate aqueous solution joins step 2 with mass concentration) in the mixing solutions that obtains, make that the final mol ratio of cupric ion and hydrazine hydrate is 1: 10-30, mix the back and under 40-60 ℃ condition, react 50-80min, obtain orange-yellow Cu
2Throw out that O colloidal solution, centrifugation obtain is with deionized water and absolute ethanol washing, be characterized by through Electronic Speculum have the narrow distribution of particle diameter, median size is at the controlled Cu of 150-350nm
2O hollow sub-micro ball;
Or 4) Cu that further step 3) is obtained
2O hollow sub-micro ball begins after 1 ℃/min temperature programming to 300 ℃ from room temperature, be rapidly heated again to 500 ℃ and roasting 1-5h to constant weight, obtain particle diameter and size distribution and described Cu
2The CuO hollow sub-micro ball that O hollow sub-micro ball is similar.
2. method according to claim 1 is characterized in that used mantoquita is copper sulfate, cupric nitrate, neutralized verdigris or cupric chloride.
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| CN101722314A (en) * | 2009-11-20 | 2010-06-09 | 云南大学 | Method for preparing Cu2O-Cu composite microsphere by adopting bean flour as template |
| CN102139910A (en) * | 2011-03-28 | 2011-08-03 | 浙江理工大学 | Method for preparing dandelion-shaped copper oxide hollow micrometer balls |
| CN102180509A (en) * | 2011-03-28 | 2011-09-14 | 浙江理工大学 | Method for preparing hollow CuO/Cu2O spheres with controllable ingredients |
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| CN106698499B (en) * | 2017-01-20 | 2018-02-06 | 江苏先丰纳米材料科技有限公司 | A kind of nanosphere chain structure cupric oxide and preparation method thereof |
| CN110562955A (en) * | 2019-08-06 | 2019-12-13 | 河北大学 | Reed-based carbon dots, CDs-Cu2O/CuO composite material and preparation method thereof |
| CN110562955B (en) * | 2019-08-06 | 2020-12-18 | 河北大学 | Reed-based carbon dots, CDs-Cu2O/CuO composite material and preparation method thereof |
| CN111333099A (en) * | 2020-03-06 | 2020-06-26 | 合肥工业大学 | Method for preparing nano copper hydroxide from acidic copper chloride etching waste liquid |
| CN111333099B (en) * | 2020-03-06 | 2022-04-08 | 合肥工业大学 | Method for preparing nano copper hydroxide from acidic copper chloride etching waste liquid |
| CN113058600A (en) * | 2021-03-29 | 2021-07-02 | 蚌埠学院 | Controllable preparation method of copper oxide-cuprous oxide nano compound |
| CN114680136A (en) * | 2022-03-02 | 2022-07-01 | 陕西理工大学 | Cu2Preparation method of O/CuO @ Ag-tetracycline |
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Address after: 214014 Jiangsu province Wuxi chonganou mount a horse Pier Road No. 18 Chong Chong'an District Service Center Patentee after: Jiangnan University Address before: 1800 No. 214122 Jiangsu city of Wuxi Province Li Lake Avenue Patentee before: Jiangnan University |
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