CN102786077A - Preparation method for submicron cuppy zinc oxide crystals - Google Patents
Preparation method for submicron cuppy zinc oxide crystals Download PDFInfo
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- CN102786077A CN102786077A CN2012102668738A CN201210266873A CN102786077A CN 102786077 A CN102786077 A CN 102786077A CN 2012102668738 A CN2012102668738 A CN 2012102668738A CN 201210266873 A CN201210266873 A CN 201210266873A CN 102786077 A CN102786077 A CN 102786077A
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Abstract
The invention discloses a preparation method for submicron cuppy zinc oxide crystals. The preparation method comprises the following steps: step 1, an ammonia solution is uniformly dripped in a zinc brine solution under the condition of reflux stirring at 75-100 DEG C, and the dripping is ended when the pH is 8-11; step 2, the solutions continue reacting at constant temperature to obtain a zinc oxide precipitate; and step 3, the zinc oxide precipitate obtained in the step 2 is washed with water, separated centrifugally and dried to obtain the submicron cuppy zinc oxide crystals. According to the preparation method provided by the invention, the products are submicron cuppy zinc oxide, which is uniform in size, high in crystallinity and excellent in performance and take the shape of a regular hexagonal prism; through the adoption of the preparation method, no special substrate is required, synthesis is directly performed in one step in the solutions, the cycle is short, and the production efficiency is high; and no contamination is produced, and the energy consumption is low.
Description
Technical field
The invention belongs to the inorganic functional material technical field, relate to the preparation method of the cup-shaped zincite crystal of a kind of submicron.
Background technology
Zinc oxide is generally hexagonal wurtzite structure under the normal temperature, belongs to the P63mc spacer, is a kind of polar crystal, and its energy gap is 3.37eV, is a kind of semiconductor material of excellence.Owing to have nano effects such as surface effects, small-size effect, quantum size effect, nano zine oxide is widely used in fields such as rubber, chemical industry, coating, pottery, glass, electronics and medical and health.In recent years; Cup-shaped, tubulose microstructure zinc oxide material with hollow be because of its huge specific surface area, mesoporous absorption and slow release characteristic, in electronics, photochemical catalysis, medical and health, support fields such as slow-release material and show application prospects and receive increasing concern.
The method of existing thermolysis growth cast zinc oxide, this method is added drop-wise to strong aqua in the liquor zinci chloridi earlier, with above-mentioned solution in confined conditions behind the supersound process 30min; Conductive substrates is put into wherein; Again with under the above-mentioned solution air tight condition 80 ~ 98 ℃ leave standstill 45 ~ 90min, ageing 5 ~ 9h at room temperature takes out substrate again; The water flushing promptly obtains nano-tube shaped zinc oxide on substrate.This preparation method need adopt substrate, and technology is complicated, and productive rate is low, is inappropriate for industrialization production.
The ultrasonic wet-chemical of existing employing prepares the method for zinc-oxide nano pipe.This method mixes zinc nitrate, sodium hydroxide, absolute ethyl alcohol, second diene diamines, deionized water etc. earlier, then mixed solution is carried out supersound process, promptly obtains having the Zinc oxide powder of certain pore characteristic.This method need adopt second diene diamines to be tensio-active agent, and is unfavorable to environment, and the products therefrom pattern is uneven, and size is wayward.
The preparation method of existing nano structure of zinc oxide.This method adopts chemical vapour deposition technique; Earlier a kind of substrate that contains metal level and catalyst layer and spelter or zinc powder are placed in the reaction chamber; Feed oxygen-containing gas and be heated to 500 ~ 1100 ℃ to reaction chamber again, promptly on substrate, obtain zinc oxide nano-crystal behind gas-phase reaction 10 ~ 90min.This method needs specific installation, and the product pattern is uneven, and CHI-pulse and CUN-pulse being irregular is uneven.
The preparation method of existing zinc oxide nano tube array.This method adopts membrane or magnetron sputtering technique on substrate, to prepare the zinc oxide crystal seed layer earlier, this substrate is changed in the encloses container that zinc salt and alkali mixed solution are housed carry out hydro-thermal reaction then.On substrate, obtain zinc oxide nano-wire array behind reaction 1 ~ 2h, again this substrate is carried out etching with alkali lye and promptly obtain zinc oxide nano tube array.This method complex process needs to adopt the chemical etching technology, and waste liquid is harmful to environment, is inappropriate for industrialization production.
The method of existing preparation zinc oxide nano tube array.This method earlier with zinc nitrate solution and vulkacit H drips of solution on conductive glass; Whirl coating carries out anneal after forming thin film; Film is decomposed to form the zinc oxide crystal seed film; Then this conductive glass is put into the encloses container hydro-thermal reaction 3 ~ 4 days that zinc nitrate and vulkacit H mixing solutions are housed, take out the nano-tube array that substrate promptly obtains zinc oxide.This method process cycle is long, and productive rate is low, and the tubular looks of gained zinc-oxide nano are uneven, and size differs, and is inappropriate for industrialization production.
Among the preparation method of the above tubulose zinc oxide, mostly need the crystal seed of on substrate, growing earlier, technology is complicated, and substrate has limited production efficiency, and resulting zinc oxide pattern is uneven, and the size of pore differs, and is unfavorable for extensive commercial application.
Summary of the invention
The preparation method who the purpose of this invention is to provide the cup-shaped zincite crystal of a kind of submicron; Having solved mostly needs the crystal seed of on substrate, growing earlier in the prior art, technology is complicated, and substrate has limited production efficiency; And resulting zinc oxide pattern is uneven, the problem that the size of pore differs.
The technical scheme that the present invention adopted is, the preparation method of the cup-shaped zincite crystal of a kind of submicron implements according to following steps:
Step 1) evenly is added drop-wise to the ammonia soln of 0.001 ~ 1mol/L in the zinc salt solution of 0.001 ~ 1mol/L under 75 ~ 100 ℃ of refluxing and stirring conditions, and the rate of addition of ammonia soln is controlled at 1 ~ 4mL/min, and dripping the pH of ending is 8 ~ 11;
Step 2) above-mentioned solution is continued isothermal reaction 2 ~ 8h under 75 ~ 100 ℃ of reflux conditionss, obtain the zinc oxide throw out;
Step 3) is used water washing with the zinc oxide throw out of step 2 gained, and spinning behind 40 ~ 100 ℃ of drying 12 ~ 24h, promptly gets the cup-shaped zincite crystal of submicron.
The invention has the beneficial effects as follows,
1) product that obtains of this method is a cup-shaped submicron zinc oxide, and its size is even, and percent crystallinity is high, and excellent performance has the hexagonal prism profile of rule, the about 400 ~ 800nm of diameter, and length is about 1 ~ 2um, and the inner chamber aperture is about 200 ~ 300nm.
2) this method does not need special substrate, direct one-step synthesis in solution, and the cycle is short, production efficiency is high.
3) this method adopts wet-chemical synthetic technology, and preparation technology is simple and direct, and pollution-free, less energy-consumption, production cost are low, need not use any tensio-active agent and organic additive, belong to " Green Chemistry " synthetic technology.
Description of drawings
Fig. 1 is the XRD figure spectrum of the cup-shaped submicron zinc oxide of the embodiment of the invention 1 preparation;
Fig. 2 is the stereoscan photograph of the cup-shaped submicron zinc oxide of the embodiment of the invention 1 preparation;
Fig. 3 is the stereoscan photograph of the cup-shaped submicron zinc oxide of the embodiment of the invention 2 preparations;
Fig. 4 is the stereoscan photograph of the cup-shaped submicron zinc oxide of the embodiment of the invention 3 preparations;
Fig. 5 is the stereoscan photograph of the cup-shaped submicron zinc oxide of the embodiment of the invention 4 preparations;
Fig. 6 is the stereoscan photograph of the cup-shaped submicron zinc oxide of the embodiment of the invention 5 preparations.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is elaborated.
The preparation method of the cup-shaped zincite crystal of submicron of the present invention, implement according to following steps:
Step 1) evenly is added drop-wise to the ammonia soln of 0.001 ~ 1mol/L in the zinc salt solution of 0.001 ~ 1mol/L under 75 ~ 100 ℃ of refluxing and stirring conditions, and the rate of addition of ammonia soln is controlled at 1 ~ 4mL/min, and dripping the pH of ending is 8 ~ 11;
Step 2) above-mentioned solution is continued isothermal reaction 2 ~ 8h under 75 ~ 100 ℃ of reflux conditionss, obtain the zinc oxide throw out;
Step 3) is used water washing with the zinc oxide throw out of step 2 gained, and spinning behind 40 ~ 100 ℃ of drying 12 ~ 24h, promptly gets the cup-shaped zincite crystal of submicron, and its inner chamber is 200 ~ 300nm, and external diameter is 400 ~ 800nm, and length is 1 ~ 2um.
Described zinc salt is selected zinc chloride (ZnCl for use
2), zinc nitrate (Zn (NO
3)
2), zinc sulfate (ZnSO
4), zinc acetate (ZnAc
2) or its hydrate (like Zn (NO
3)
26H
2O, ZnSO
47H
2O, ZnAc
22H
2One of O).
The water that adopts in the said preparation process is deionized water, pure water or zero(ppm) water.
The reaction principle of the inventive method is: under the condition of water solvent system pH >=7; Zine ion and hydroxide ion are under >=75 ℃ of temperature of drop microenvironment neutralization; Through dehydration reaction, directly form ZnO solid phase core, and the oriented growth through this ZnO core; Formation has the ZnO crystal of cup-shaped shape characteristic, and its chemical reaction process is suc as formula shown in (1), the formula (2):
Embodiment 1
Under 100 ℃ of refluxing and stirring conditions, the ammonia soln of 1mol/L evenly is added drop-wise in zinc acetate (or the hydration zinc acetate) aqueous solution of 0.7mol/L, the control rate of addition is 1mL/min, it is 9 that control drips the end of a period pH value of solution;
Continue back flow reaction 8h at 75 ℃ then; (control condition is 40 ℃ to the gained throw out through deionized water wash, spinning, negative pressure drying; Promptly get the cup-shaped zincite crystal of submicron 24h); (XRD) is as shown in Figure 1 for the X-ray diffracting spectrum of products therefrom zincite crystal, and its ESEM pattern (SEM) is as shown in Figure 2.
Embodiment 2
Under 90 ℃ of refluxing and stirring conditions, the ammonia soln of 0.84mol/L evenly is added drop-wise in zinc nitrate (or the nitric hydrate zinc) aqueous solution of 0.25mol/L, the control rate of addition is 2mL/min, dripping the pH value of solution of ending is 10;
Then above-mentioned solution is continued back flow reaction 6h at 80 ℃; (control condition is 85 ℃ to the gained throw out, promptly gets the cup-shaped zincite crystal of submicron after 18h), and the ESEM pattern (SEM) of products therefrom is as shown in Figure 3 through pure water washing, spinning, drying.
Embodiment 3
Under 85 ℃ of refluxing and stirring conditions, the ammonia soln of 0.001mol/L evenly is added drop-wise in the liquor zinci chloridi of 1mol/L, the control rate of addition is 3mL/min, and the pH that drips end of a period solution is 8;
Continue back flow reaction 4h at 90 ℃ then; (control condition is 100 ℃ to the gained throw out, promptly gets the cup-shaped zincite crystal of submicron after 12h), and the ESEM pattern (SEM) of products therefrom zincite crystal is as shown in Figure 4 through distilled water wash, spinning, drying.
Embodiment 4
Under 90 ℃ of refluxing and stirring conditions, the ammonia soln of 0.024mol/L evenly is added drop-wise in zinc sulfate (or zinc sulphate hydrate) solution of 0.08mol/L, the control rate of addition is 4mL/min, the pH that drips end of a period solution is 11;
Continue back flow reaction 2h at 100 ℃ then; (control condition is 75 ℃ to the gained throw out, promptly gets the cup-shaped zincite crystal of submicron after 20h), and the ESEM pattern (SEM) of products therefrom zincite crystal is as shown in Figure 5 through deionized water wash, spinning, drying.
Embodiment 5
Under 85 ℃ of refluxing and stirring conditions, the ammonia soln of 0.09mol/L evenly is added drop-wise in zinc acetate (or the hydration zinc acetate) solution of 0.001mol/L, the control rate of addition is 2.5mL/min, the pH that drips end of a period solution is 9;
Continue back flow reaction 6h at 85 ℃ then; (control condition is 90 ℃ to the gained throw out through deionized water wash, spinning, drying; Promptly get the cup-shaped zincite crystal of submicron 10h), the ESEM pattern (SEM) of products therefrom zincite crystal is as shown in Figure 6.
Claims (4)
1. the preparation method of the cup-shaped zincite crystal of submicron is characterized in that: implement according to following steps:
Step 1) evenly is added drop-wise to the ammonia soln of 0.001 ~ 1mol/L in the zinc salt solution of 0.001 ~ 1mol/L under 75 ~ 100 ℃ of refluxing and stirring conditions, and the rate of addition of ammonia soln is controlled at 1 ~ 4mL/min, and dripping the pH of ending is 8 ~ 11;
Step 2) above-mentioned solution is continued isothermal reaction 2 ~ 8h under 75 ~ 100 ℃ of reflux conditionss, obtain the zinc oxide throw out;
Step 3) is used water washing with the zinc oxide throw out of step 2 gained, and spinning behind the dry 12 ~ 24h of 40 ~ 100 ° of C, promptly gets the cup-shaped zincite crystal of submicron.
2. the preparation method of the cup-shaped zincite crystal of submicron according to claim 1 is characterized in that: described zinc salt is selected zinc chloride, zinc nitrate, zinc sulfate, zinc acetate, Zn (NO for use
3)
26H
2O, ZnSO
47H
2O or ZnAc
22H
2One of O.
3. the preparation method of the cup-shaped zincite crystal of submicron according to claim 1 is characterized in that: described wet concentration is with deionized water, pure water or zero(ppm) water.
4. the preparation method of the cup-shaped zincite crystal of submicron according to claim 1 is characterized in that: the cup-shaped zincite crystal of the submicron in the described step 3, inner chamber are 200 ~ 300nm, and external diameter is 400 ~ 800nm, and length is 1 ~ 2um.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101379772B1 (en) | 2012-10-29 | 2014-04-01 | 재단법인대구경북과학기술원 | Manufacturing method for simonkolleite and thereby made simonkolleite |
| CN103966656A (en) * | 2014-04-22 | 2014-08-06 | 郑州轻工业学院 | Preparation method for zinc oxide super crystalline material |
| CN106006706A (en) * | 2016-05-19 | 2016-10-12 | 青岛大学 | Preparation method of dumbbell-shaped ZnO micro-ring gas-sensitive material |
| CN107029696A (en) * | 2017-05-12 | 2017-08-11 | 济南大学 | A kind of method that use green solvent prepares zinc oxide mesopore material at room temperature |
| CN111960458A (en) * | 2020-07-17 | 2020-11-20 | 杭州电子科技大学 | Preparation method of zinc oxide |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101249979A (en) * | 2008-04-01 | 2008-08-27 | 西南交通大学 | Atmospheric preparation method of prickly sphere zinc oxide |
| CN101475726A (en) * | 2009-01-12 | 2009-07-08 | 浙江理工大学 | Polymethyl methacryate microsphere coating zinc oxide composite material and preparation thereof |
| CN102070183A (en) * | 2011-01-27 | 2011-05-25 | 西北工业大学 | Method for preparing three-dimensional multistage microstructural zinc oxide |
-
2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101249979A (en) * | 2008-04-01 | 2008-08-27 | 西南交通大学 | Atmospheric preparation method of prickly sphere zinc oxide |
| CN101475726A (en) * | 2009-01-12 | 2009-07-08 | 浙江理工大学 | Polymethyl methacryate microsphere coating zinc oxide composite material and preparation thereof |
| CN102070183A (en) * | 2011-01-27 | 2011-05-25 | 西北工业大学 | Method for preparing three-dimensional multistage microstructural zinc oxide |
Non-Patent Citations (4)
| Title |
|---|
| ANA PAULA A. OLIVEIRA ET AL.: "Controlled Precipitation of Zinc Oxide Particles at Room Temperature", 《CHEM. MATER.》, vol. 15, no. 16, 18 July 2003 (2003-07-18), pages 3202 - 3207 * |
| QIPING ZHONG ET AL.: "Preparation of uniform zinc oxide colloids by controlled double-jet precipitation", 《J. MATER. CHEM.》, vol. 6, no. 3, 31 December 1996 (1996-12-31), pages 443 - 447 * |
| 贺全林等: "沸腾回流法制备不同形貌ZnO微粉", 《河北师范大学学报（自然科学版）》, vol. 28, no. 5, 30 September 2004 (2004-09-30), pages 488 - 490 * |
| 郝红静: "低温溶液法制备ZnO：Co纳米粉体及性质研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 09, 15 September 2011 (2011-09-15) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101379772B1 (en) | 2012-10-29 | 2014-04-01 | 재단법인대구경북과학기술원 | Manufacturing method for simonkolleite and thereby made simonkolleite |
| CN103966656A (en) * | 2014-04-22 | 2014-08-06 | 郑州轻工业学院 | Preparation method for zinc oxide super crystalline material |
| CN106006706A (en) * | 2016-05-19 | 2016-10-12 | 青岛大学 | Preparation method of dumbbell-shaped ZnO micro-ring gas-sensitive material |
| CN107029696A (en) * | 2017-05-12 | 2017-08-11 | 济南大学 | A kind of method that use green solvent prepares zinc oxide mesopore material at room temperature |
| CN111960458A (en) * | 2020-07-17 | 2020-11-20 | 杭州电子科技大学 | Preparation method of zinc oxide |
| CN111960458B (en) * | 2020-07-17 | 2022-07-12 | 杭州电子科技大学 | Preparation method of zinc oxide |
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