CN102627312A - Preparation method of zinc oxide microsphere with nanoflower-shaped microstructure - Google Patents
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Abstract
The invention relates to a preparation method of a zinc oxide microsphere with a nanoflower-shaped microstructure. The method comprises the following steps of: (1) preparing a solution, to be specific, preparing a soluble zinc salt into an aqueous solution, and preparing a soluble alkali into an aqueous solution; (2) mixing the solutions, to be specific, mixing the soluble zinc salt aqueous solution with the soluble alkali aqueous solution at the room temperature in the volume ratio of 1:10-10:1, slowly pouring an aqueous solution of a soluble zinc salt into the aqueous solution of the soluble alkali, and stirring to obtain a clarifying solution; and (3) preparing a product, to be specific, pouring a weakly-acid solution into the clarifying solution obtained in the step (2), wherein the volume ratio of the weakly-acid solution to the clarifying solution is 1:10-10:1, stirring to obtain a turbid solution containing a large quantity of products, repeatedly washing with deionized water and absolute ethyl alcohol, and drying in a baking oven to obtain a final product. Compared with the prior art, the method has the advantages of capability of rapidly, easily and conveniently preparing a product under the room temperature condition, high yield, low cost, environmental friendliness, wide raw material selection range and contribution to industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of oxide semiconductor material, specifically is a kind of preparation method with zinc oxide microballoon of nano flower-like microstructure.
Background technology
Zinc oxide is the semiconductor material with wide forbidden band of 3.37eV as a kind of energy gap, and is nontoxic, and low in raw material cost is easy to get, and it has excellent piezoelectricity, photoelectricity and dielectric characteristics.Wherein nano zine oxide has a wide range of applications in fields such as air-sensitive, photochemical catalysis, antibiotic and photovaltaic materials; But its nano level size range; Bring difficulty to recovery; Be unfavorable for recycling, hope thus to find a kind ofly can keep the most of character of nano material, be beneficial to the zinc oxide product of recycle again.
The ZnO nanometer sheet is a kind of facile nanostructure, and under this existence form, ZnO has bigger surface-area and extraordinary photochemical activity.But in this case, solid-liquid separation is very difficult.In addition, the hydraulic conductivity that ZnO is low makes that the nanometer ZnO powder material can not be directly in practical applications, must powdered material be processed into certain shape after (generally being particulate state) just can be used for treatment of industrial water such as filtering layer absorption method.But traditional moulding process is a cost with the specific surface area of sacrificing ZnO and catalytic activity often.If therefore can synthesize a kind of zinc oxide microballoon with multiple dimensioned structure, promptly microstructure is a nano level, and integral body is micron or millimetre-sized material, might address the above problem.At present, has only a spot of report for the preparation of this special construction zinc oxide micrometer ball.Reported a kind of water-bath preparation method of prickly sphere zinc oxide like Chinese patent (CN101249979B); This water-bath synthesis method needs ultrasonic activation to handle, and solution needs thin up, and bath temperature will reach boiling point and need and stir; Therefore process is comparatively complicated, and through engineering approaches is amplified difficult; Document (Journal of Crystal Growth 282 (2005) 165-172) has been reported similar ZnO nanostructure, and it is the solvent-thermal method of media that this method adopts absolute ethyl alcohol, 190 ℃ of solvent temperatures; Chinese patent (CN102249286A) has been reported a kind of normal pressure water-bath preparation method of zinc oxide micrometer ball; Need in 70 ℃ water-bath, be incubated 10～24 hours through mixed solution; Gained micron ball has only the surface that laminated structure is arranged, and extensibility is limited, can not maximize its specific surface area; Chinese patent (CN102303896A) has been reported a kind of preparation method of Pearly-shining Maesa type micrometer structure zinc oxide in addition, and this method need stir 0.1～2h with mixing solutions, after 40 ℃ to the 60 ℃ preheatings, also need react 1～48h down at 60 ℃～200 ℃.Though above method can be prepared more qualified zinc oxide micrometer ball; Yet there is following shortcoming in aforesaid method: preparation slowly; Technology is complicated, and the influence that brings thus is exactly time-consuming, preparation expensive; If go on the road of industrialization, the environmental protection economic strategy of just being advocated with country is disagreed.
Summary of the invention
The object of the invention be exactly provide in order to overcome the defective that above-mentioned prior art exists a kind of fast and convenient, power consumption is little, plant and instrument is simple, productive rate is high, good reproducibility, be easy to the preparation method of the zinc oxide microballoon with nano flower-like microstructure of suitability for industrialized production.
The object of the invention can be realized through following technical scheme: a kind of preparation method with zinc oxide microballoon of nano flower-like microstructure is characterized in that this method may further comprise the steps:
(1) preparation of solution: soluble zinc salt is mixed with the aqueous solution that the zine ion volumetric molar concentration is 0.01～0.5mol/L, water soluble alkali is mixed with the aqueous solution that the hydroxide ion volumetric molar concentration is 0.1～5mol/L;
(2) solution mixes: at room temperature, the soluble Zn salt brine solution and the water soluble alkali aqueous solution are 1: 10～10: 1 according to volume ratio, and the aqueous solution of soluble zinc salt is slowly poured in the aqueous solution of water soluble alkali, follow stirring, obtain clear liquor;
(3) product preparation: weakly acid soln is poured into fast in the clear liquor of step (2) gained; The volume ratio of weakly acid soln and clear liquor is 1: 10～10: 1; Follow stirring; Obtain containing the turbid solution of a large amount of products, with deionized water and absolute ethyl alcohol repetitive scrubbing, and drying obtains the finished product in baking oven.
Described soluble zinc salt can be several kinds of mixtures of the one or any combination of zinc acetate, zinc sulfate, zinc nitrate or zinc chloride; Perhaps being hydrate a kind of of above-mentioned zinc salt, perhaps is the mixture of any one or a few zinc salt and any one or a few zinc salt hydrate.
Described water soluble alkali is the miscellany of a kind of in sodium hydroxide, the Pottasium Hydroxide or two kinds.
The temperature of described room temperature is meant 0～37 ℃.
Described weakly acid soln is meant that the concentration range of acid is between 0.025g/mL～0.1g/mL; Weak acid is meant one or more in pentanedioic acid, oleic acid, toluene-4-sulfonic acid, oxalic acid, monohydrate potassium, boric acid, the glycocoll.
When described weak acid is oleic acid, adopt anhydrous alcohol solution, and oleic acid and absolute ethyl alcohol are according to mixing in 1: 10～10: 1 the scope of volume ratio.
Described temperature of oven is 40～200 ℃, and the exsiccant time is 2～48h in baking oven.
Compared with prior art; The present invention is the zinc source with the soluble zinc salt; With alkali and weak acid is auxiliary material, be mixed with certain density solution respectively after, zinc salt solution mixed according to a certain volume obtaining settled solution with alkaline solution; Utilize the weakly acid soln of finite concentration scope to change system balance, the fast and convenient zinc oxide microballoon product that obtains having the nano flower-like microstructure.Need not ultrasonic activation, extra preheating, and this method is fast and convenient, with short production cycle, need not expensive equipment input, pollution-free, environmental protection, convenient post-treatment only needs to use weak acid, and is selectable in extensive range.Reaction environment is gentle, the suitability for industrialized production of being more convenient for.
Description of drawings
Fig. 1 uses boric acid to make the SEM figure of zinc oxide micrometer ball;
Fig. 2 uses oleic acid to make the SEM figure of zinc oxide micrometer ball;
Fig. 3 uses zinc nitrate to make the SEM figure of zinc oxide micrometer ball;
Fig. 4 uses oleic acid to make the TEM figure of zinc oxide micrometer ball;
Fig. 5 uses oleic acid to make the XRD figure of zinc oxide micrometer ball.
Embodiment
Elaborate in the face of embodiments of the invention down: present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1
At room temperature; 1g boric acid is dissolved in the 20mL deionized water; The zinc acetate aqueous solution 15mL of preparation zine ion volumetric molar concentration 0.5mol/L, the sodium hydroxide solution 10mL of volumetric molar concentration 5mol/L is accompanied by glass stick then and stirs; Slowly the 15mL zinc salt solution is poured in the sodium hydroxide solution, will be obtained the clarifying aqueous solution.Then the 20mL BAS is poured in the clear liquor that obtains fast into the static deposition that obtains white.To precipitate eccentric cleaning, putting into oven temperature is 80 ℃, and the time is the 4h oven dry, can obtain the zinc oxide microballoon by the nanometer sheet structure, and its SEM figure is as shown in Figure 1.
Embodiment 2
At room temperature; 5ml oleic acid is dissolved in the 15mL absolute ethyl alcohol; The zinc acetate aqueous solution 15mL of preparation zine ion volumetric molar concentration 0.5mol/L, the sodium hydroxide solution 10mL of volumetric molar concentration 5mol/L is accompanied by glass stick then and stirs; Slowly the 15mL zinc salt solution is poured in the sodium hydroxide solution, will be obtained the clarifying aqueous solution.Then 20mL oleic acid absolute ethyl alcohol mixing solutions is poured in the clear liquor that obtains fast into the static deposition that obtains white.To precipitate eccentric cleaning, putting into the baking oven temperature is 90 ℃, and the time is 3.5h, can obtain the zinc oxide microballoon by the nanometer sheet structure, and its SEM figure is as shown in Figure 2, and its TEM figure is as shown in Figure 4, and XRD figure is as shown in Figure 5.
Embodiment 3
At room temperature; 1g boric acid is dissolved in the 20mL deionized water; The zinc nitrate aqueous solution 15mL of preparation zine ion volumetric molar concentration 0.5mol/L, the sodium hydroxide solution 10mL of volumetric molar concentration 5mol/L is accompanied by glass stick then and stirs; Slowly the 15mL zinc salt solution is poured in the sodium hydroxide solution, will be obtained the clarifying aqueous solution.Then the 20mL BAS is poured in the clear liquor that obtains fast into the static deposition that obtains white.To precipitate eccentric cleaning, putting into the baking oven temperature is 70 ℃, and the time is 5h, can obtain the zinc oxide microballoon by the nanometer sheet structure, and its SEM figure is like Fig. 3.
Embodiment 4
Under 0 ℃; 10ml oleic acid is dissolved in the 100mL absolute ethyl alcohol; The zinc sulfate solution 10mL of preparation zine ion volumetric molar concentration 0.01mol/L, the sodium hydroxide solution 30mL of volumetric molar concentration 0.1mol/L is accompanied by glass stick then and stirs; Slowly the 10mL zinc salt solution is poured in the 30mL potassium hydroxide solution, will be obtained the clarifying aqueous solution.Then 110mL oleic acid absolute ethyl alcohol mixing solutions is poured in the clear liquor that obtains fast into the static deposition that obtains white.To precipitate eccentric cleaning, putting into the baking oven temperature is 40 ℃, and the time is 48h, can obtain the zinc oxide microballoon that is made up by nanometer sheet.
Embodiment 5
Under 37 ℃ of room temperatures; 100ml oleic acid is dissolved in the 20mL absolute ethyl alcohol; Zinc chloride and the zinc acetate mixed aqueous solution 30mL of preparation zine ion volumetric molar concentration 0.5mol/L, the potassium hydroxide solution 10mL of volumetric molar concentration 5mol/L is accompanied by glass stick then and stirs; Slowly the 30mL zinc salt solution is poured in the 10mL potassium hydroxide solution, will be obtained the clarifying aqueous solution.Then 120mL oleic acid absolute ethyl alcohol mixing solutions is poured in the clear liquor that obtains fast into the static deposition that obtains white.To precipitate eccentric cleaning, putting into the baking oven temperature is 200 ℃, and the time is 2h, can obtain the zinc oxide microballoon that is made up by nanometer sheet.
Claims (7)
1. preparation method with zinc oxide microballoon of nano flower-like microstructure is characterized in that this method may further comprise the steps:
(1) preparation of solution: soluble zinc salt is mixed with the aqueous solution that the zine ion volumetric molar concentration is 0.01～0.5mol/L, water soluble alkali is mixed with the aqueous solution that the hydroxide ion volumetric molar concentration is 0.1～5mol/L;
(2) solution mixes: at room temperature, soluble Zn salt brine solution and the water soluble alkali aqueous solution are to mix in 1: 10～10: 1 according to volume ratio, and the aqueous solution of soluble zinc salt is slowly poured in the aqueous solution of water soluble alkali, follow stirring, obtain clear liquor;
(3) product preparation: weakly acid soln is poured in the clear liquor of step (2) gained; The volume ratio of weakly acid soln and clear liquor is 1: 10～10: 1, follows stirring, obtains containing the turbid solution of a large amount of products; With deionized water and absolute ethyl alcohol repetitive scrubbing, and drying obtains the finished product in baking oven.
2. a kind of preparation method according to claim 1 with zinc oxide microballoon of nano flower-like microstructure; It is characterized in that; Described soluble zinc salt can be several kinds of mixtures of the one or any combination of zinc acetate, zinc sulfate, zinc nitrate or zinc chloride; Perhaps being hydrate a kind of of above-mentioned zinc salt, perhaps is the mixture of any one or a few zinc salt and any one or a few zinc salt hydrate.
3. a kind of preparation method with zinc oxide microballoon of nano flower-like microstructure according to claim 1 is characterized in that, described water soluble alkali is the mixture of a kind of in sodium hydroxide, the Pottasium Hydroxide or two kinds.
4. a kind of preparation method with zinc oxide microballoon of nano flower-like microstructure according to claim 1 is characterized in that the temperature of described room temperature is meant 0～37 ℃.
5. a kind of preparation method with zinc oxide microballoon of nano flower-like microstructure according to claim 1 is characterized in that the concentration range of described weakly acid soln is between 0.025g/mL～0.1g/mL; Weak acid is meant one or more in pentanedioic acid, oleic acid, toluene-4-sulfonic acid, oxalic acid, monohydrate potassium, boric acid, the glycocoll.
6. a kind of preparation method according to claim 5 with zinc oxide microballoon of nano flower-like microstructure; It is characterized in that; When described weak acid is oleic acid, adopt anhydrous alcohol solution, and oleic acid and absolute ethyl alcohol are according to mixing in 1: 10～10: 1 the scope of volume ratio.
7. a kind of preparation method with zinc oxide microballoon of nano flower-like microstructure according to claim 1 is characterized in that described temperature of oven is 40～200 ℃, and the exsiccant time is 2～48h in baking oven.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104118901A (en) * | 2014-07-23 | 2014-10-29 | 西安工程大学 | Preparation method of flower-like nano zinc oxide |
| CN104264281A (en) * | 2014-09-17 | 2015-01-07 | 句容亿格纳米材料厂 | Preparation method of nanofibers |
| CN105565366A (en) * | 2016-01-21 | 2016-05-11 | 山东科技大学 | Method for preparing porous zinc oxide with three-dimensional structure |
| CN106830052A (en) * | 2017-04-12 | 2017-06-13 | 济南大学 | The preparation method and products obtained therefrom of three-dimensional flower-shaped nano zinc oxide material |
| CN109485088A (en) * | 2019-01-09 | 2019-03-19 | 安徽工程大学 | A kind of flower shape zinc oxide nanometer sheet aggregate material and preparation method thereof, application |
| CN110052272A (en) * | 2019-04-23 | 2019-07-26 | 北京化工大学 | The preparation method and applications of Co doping zinc oxide nanometer floral material |
| CN110124654A (en) * | 2019-05-22 | 2019-08-16 | 天津大学 | A kind of nanoscale flower-like zinc oxide photochemical catalyst and its preparation method and application |
| CN110342568A (en) * | 2019-08-09 | 2019-10-18 | 陕西科技大学 | A kind of silk ball flower shape zinc oxide copper sulfide and preparation method thereof |
| CN110526228A (en) * | 2019-09-12 | 2019-12-03 | 北京工业大学 | The preparation method of one type petal-shaped carbon nanosheet |
| US11325839B2 (en) | 2018-01-11 | 2022-05-10 | Imam Abdulrahman Bin Faisal University | Zinc oxide particle preparation and methods of use |
| CN116332222A (en) * | 2023-03-23 | 2023-06-27 | 河南科技大学 | Preparation method of ZnO micron flower laminated by nano-sheets |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104118901A (en) * | 2014-07-23 | 2014-10-29 | 西安工程大学 | Preparation method of flower-like nano zinc oxide |
| CN104118901B (en) * | 2014-07-23 | 2016-12-07 | 西安工程大学 | The preparation method of flower-like nanometer zinc oxide |
| CN104264281A (en) * | 2014-09-17 | 2015-01-07 | 句容亿格纳米材料厂 | Preparation method of nanofibers |
| CN104264281B (en) * | 2014-09-17 | 2016-06-29 | 句容亿格纳米材料厂 | A kind of preparation method of nanofiber |
| CN105565366A (en) * | 2016-01-21 | 2016-05-11 | 山东科技大学 | Method for preparing porous zinc oxide with three-dimensional structure |
| CN106830052B (en) * | 2017-04-12 | 2018-03-27 | 济南大学 | The preparation method and products obtained therefrom of three-dimensional flower-shaped nano zinc oxide material |
| CN106830052A (en) * | 2017-04-12 | 2017-06-13 | 济南大学 | The preparation method and products obtained therefrom of three-dimensional flower-shaped nano zinc oxide material |
| US11325839B2 (en) | 2018-01-11 | 2022-05-10 | Imam Abdulrahman Bin Faisal University | Zinc oxide particle preparation and methods of use |
| CN109485088A (en) * | 2019-01-09 | 2019-03-19 | 安徽工程大学 | A kind of flower shape zinc oxide nanometer sheet aggregate material and preparation method thereof, application |
| CN110052272A (en) * | 2019-04-23 | 2019-07-26 | 北京化工大学 | The preparation method and applications of Co doping zinc oxide nanometer floral material |
| CN110124654A (en) * | 2019-05-22 | 2019-08-16 | 天津大学 | A kind of nanoscale flower-like zinc oxide photochemical catalyst and its preparation method and application |
| CN110342568A (en) * | 2019-08-09 | 2019-10-18 | 陕西科技大学 | A kind of silk ball flower shape zinc oxide copper sulfide and preparation method thereof |
| CN110526228A (en) * | 2019-09-12 | 2019-12-03 | 北京工业大学 | The preparation method of one type petal-shaped carbon nanosheet |
| CN110526228B (en) * | 2019-09-12 | 2021-03-30 | 北京工业大学 | Preparation method of petal-like carbon nanosheets |
| CN116332222A (en) * | 2023-03-23 | 2023-06-27 | 河南科技大学 | Preparation method of ZnO micron flower laminated by nano-sheets |
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Application publication date: 20120808 |