CN102795659B - Method for preparing rod-like zinc oxide nano-crystals - Google Patents
Method for preparing rod-like zinc oxide nano-crystals Download PDFInfo
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- CN102795659B CN102795659B CN201210267047.5A CN201210267047A CN102795659B CN 102795659 B CN102795659 B CN 102795659B CN 201210267047 A CN201210267047 A CN 201210267047A CN 102795659 B CN102795659 B CN 102795659B
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Abstract
The invention discloses a method for preparing rod-like zinc oxide nano-crystals, comprising the following steps of: step 1, adding dropwise ammonia-water solution to zinc salt aqueous solution at the room temperature, and after thorough reaction, performing washing using water and centrifugal separation, thereby obtaining amorphous zinc hydroxide; and step 2, preparing the amorphous zinc hydroxide obtained through the step 1 into a dispersion system and then adding potassium hydroxide solution, arousing a constant-temperature reaction of the mixed solution, washing the obtained sediments using water, and centrifugally separating and drying the sediments, thereby obtaining the rod-like zinc oxide nano-crystals. The product prepared by the method disclosed by the invention is the rod-like zinc oxide nano-crystals which are small in size, large in specific surface area, obvious in nanometer effect, and excellent in properties such as photoluminescence, photocatalytic degradation and the like; and the method is simple in preparation process, high in yield, free of needs of any template or special substrate and any chemical additive, free of pollution, and low in energy consumption.
Description
Technical field
The invention belongs to inorganic functional material technical field, relate to a kind of preparation method of clavate zinc oxide nanocrystalline.
Background technology
Nano material is because nano effects such as having surface effects, small-size effect, macro quanta tunnel effect shows the Strange properties different from conventional body material, in industries such as national defence, aerospace, biological medicine, chemical industry, information, there is great application potential, thereby become research both domestic and external, application focus.Zinc oxide nano-crystal is a kind of novel high function fine inorganic product, along with reducing of size, it shows many specific functions at aspects such as optics, magnetics, mechanics, electricity, makes it in various fields such as function ceramics, electronics, photoluminescence, photocatalytic degradation, biological medicine, ultraviolet screeners, have great using value and cause people's research enthusiasm greatly.The pattern of zinc oxide nano-crystal and size have tremendous influence to its performance, the resulting zinc oxide nano-crystal of different preparation technologies has different patterns and size, differ each other very large, therefore the control of its pattern and size is also the focus that people pay close attention to.That the pattern of having reported at present has is flower-shaped, clavate, spherical, tubulose, sheet, ring-type etc., and the preparation method who adopts has Sol-gel method, thermal decomposition method, chemical Vapor deposition process, hydrothermal synthesis method, direct precipitation method, sluggish precipitation, physical pulverization method etc.
The preparation method of existing zinc oxide particle shape nano-powder, the method first under the condition of 6 ~ 15 ℃, sodium hydroxide solution is added to zinc salt solution in to prepare zinc hydroxide colloidal precipitation, after being put into toluene, the making beating of hexanaphthene equal solvent, zinc hydroxide colloid adds template, then with specific speed, be warming up to 160 ~ 200 ℃ or 360 ~ 400 ℃, cooling after isothermal reaction certain hour, washing, obtain particle shape zinc oxide nano-crystal.The method process is complicated, and temperature is wayward, needs to adopt the organic solvents such as toluene, unfavorable to environment.
The preparation method of existing zinc oxide nano-crystal, the method is adopted first ammonia soln is added drop-wise in solution of zinc sulfate, then adds ammonium bicarbonate soln in mixing solutions, by the ZnCO obtaining
3zn (OH)
2washing, at 150 ~ 600 ℃, calcine 1.5 ~ 2.5 hours after separated, dry, obtain zinc oxide nano-crystal powder.The method gained zinc oxide size and pattern are wayward, and need to adopt silane or stearic acid to make coating materials.
The preparation method of existing clavate zinc oxide nano-crystal, the method is first injected into a certain proportion of metallic zinc salts solution and alcohol amine compound solution in the water of 60 ~ 100 ℃ simultaneously, and after ageing certain hour, washing, separation obtain clavate zinc oxide nano-crystal.The method operation inconvenience, needs to adopt the organic solvents such as diethanolamine, and the product dimensional homogeneity of institute is difficult for assurance, process costs is high, unfavorable to environment protection.
The preparation method of existing zinc oxide nano-crystal powder, the method first adds the dispersion agents such as sodium stearate, sodium lauryl sulphate and in zinc solution, obtains mixing solutions, then under the stirring velocity of 2000 ~ 5000rpm, to mixed solution and dripping carbonate solution, carry out the hydrothermal synthesis reaction of presoma, by gained suspension filtered, filter cake washing, dry, calcining, obtain zinc oxide nano-crystal powder after grinding.The method process is complicated, needs to adopt organic dispersing agent, and products therefrom pattern is wayward, and dimensional homogeneity is difficult for ensureing.
The preparation method of the above zinc oxide nano-crystal, technological process generally more complicated, product pattern is inhomogeneous, size is wayward, simultaneously because the introducing of the compounds such as modifier, organic alcohol amine is unfavorable to environment protection, is unsuitable for industrialization and produces.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of clavate zinc oxide nanocrystalline; solved in prior art; technological process generally more complicated, product pattern is inhomogeneous, size is wayward, simultaneously because the introducing of the compounds such as modifier, organic alcohol amine to the disadvantageous problem of environment protection.
The technical solution adopted in the present invention is, a kind of preparation method of clavate zinc oxide nanocrystalline implements according to following steps:
Step 1, under the room temperature of≤25 ℃, the ammonia soln of 0.001 ~ 1mol/L is added drop-wise in the zinc salt solution of 0.001 ~ 1mol/L to pH=7 ~ 8, rate of addition is controlled at 2 ~ 4mL/min, fully reacts after 0.5 ~ 1h, washes with water, centrifugation, obtains amorphous zinc hydroxide;
Step 2, the amorphous zinc hydroxide of step 1 gained is mixed with to the dispersion system of 0.001 ~ 1mol/L, then adds the potassium hydroxide solution of 0.001 ~ 1mol/L, the mol ratio of mixing solutions is controlled as KOH:Zn (OH)
2=1:(0.5 ~ 6), the pH of mixing solutions control is 14; At 75 ~ 95 ℃, again by this mixing solutions isothermal reaction 2 ~ 8h, gained precipitation washes with water, centrifugation, after 40 ~ 100 ℃ of dry 8 ~ 24h, obtains clavate zinc oxide nano-crystal.
The invention has the beneficial effects as follows:
1) the method adopts wet-chemical synthetic technology, does not need to use any tensio-active agent and organic additive, pollution-free, environmentally friendly.
2) the method does not need special substrate and template, in solution, directly by chemical reaction, synthesizes.
3) product that the method obtains is clavate zinc oxide nano-crystal, 7 ~ 25nm, and length is about 12 ~ 100nm.
4) its photocatalytic degradation fuel (methyl orange aqueous solution) performance is significantly better than ZnO nano crystalline substance prepared by ordinary method, and photocatalytic speed constant is tested and improved more than 150 ~ 200% under same condition
5) its photoluminescence performance is significantly better than particle shape ZnO nano crystalline substance prepared by ordinary method, and its uv-absorbing wave band is about 300 ~ 400nm, and photoluminescence is the wide emission band of 380 ~ 620nm, and characteristic peak is positioned at about 384nm and 570nm.
Accompanying drawing explanation
Fig. 1 is the TEM electromicroscopic photograph of the embodiment of the present invention 1 products therefrom clavate zinc oxide nano-crystal;
Fig. 2 is the XRD figure spectrum of the embodiment of the present invention 1 products therefrom clavate zinc oxide nano-crystal;
Fig. 3 is the TEM electromicroscopic photograph of the embodiment of the present invention 2 products therefrom clavate zinc oxide nano-crystals;
Fig. 4 is the photoluminescence PL spectrum of the embodiment of the present invention 2 products therefrom clavate zinc oxide nano-crystals;
Fig. 5 is the TEM electromicroscopic photograph of the embodiment of the present invention 3 products therefrom clavate zinc oxide nano-crystals;
Fig. 6 is the photoluminescence PL spectrum of the embodiment of the present invention 3 products therefrom clavate zinc oxide nano-crystals;
Fig. 7 is the TEM electromicroscopic photograph of the embodiment of the present invention 4 products therefrom clavate zinc oxide nano-crystals;
Fig. 8 is the SEM electromicroscopic photograph of the embodiment of the present invention 4 products therefrom clavate zinc oxide nano-crystals.
Embodiment
The preparation method of clavate zinc oxide nanocrystalline of the present invention, implements according to following steps:
Step 1, under the room temperature of≤25 ℃, the ammonia soln of 0.001 ~ 1mol/L is added drop-wise in the zinc salt solution of 0.001 ~ 1mol/L to pH=7 ~ 8, rate of addition is controlled at 2 ~ 4mL/min, fully reacts after 0.5 ~ 1h, washes with water, centrifugation, obtains amorphous zinc hydroxide;
Step 2, the amorphous zinc hydroxide of step 1 gained is mixed with to the dispersion system of 0.001 ~ 1mol/L, then adds the potassium hydroxide solution of 0.001 ~ 1mol/L, the mol ratio of mixing solutions is controlled as KOH:Zn (OH)
2=1:(0.5 ~ 6), the pH of mixing solutions control is 14; At 75 ~ 95 ℃, again by this mixing solutions isothermal reaction 2 ~ 8h, gained precipitation washes with water, centrifugation, after 40 ~ 100 ℃ of dry 8 ~ 24h, obtains clavate zinc oxide nano-crystal, and excellent footpath is 15 ~ 30nm, and rod length is 50 ~ 100nm.
Described zinc salt is selected zinc chloride (ZnCl
2), zinc nitrate (Zn (NO
3)
2), zinc sulfate (ZnSO
4), zinc acetate (ZnAc
2one of), or its hydrate is (as Zn (NO
3)
26H
2o, ZnSO
47H
2o, ZnAc
22H
2one of O).
The water adopting in above-mentioned preparation process is deionized water, pure water or distilled water.
The reaction principle of the inventive method is, inorganic zinc salt reacts with ammoniacal liquor under atmosphere at room temperature condition, form unbodied zinc hydroxide precipitation, again by the constant temperature dehydration reaction under the potassium hydroxide strong alkaline aqueous solution environment under atmospheric condition, obtain having nanoscale clavate ZnO crystal, its chemical reaction process is suc as formula shown in (1), formula (2):
Embodiment 1
Under room temperature (≤25 ℃), the ammonia soln of 0.15mol/L is added drop-wise in zinc sulfate (or zinc sulphate hydrate) aqueous solution of 0.5mol/L to pH=7, rate of addition is controlled at 2mL/min, fully reacts washing, centrifugation after 0.5h and obtains amorphous zinc hydroxide; Adopt deionized water to disperse to make the dispersion system of 1mol/L the amorphous zinc hydroxide of gained, then (mol ratio is Zn (OH) to add the potassium hydroxide solution of 1mol/L
2: KOH=1:2), the pH of solution is about 14, and gained mixing solutions is isothermal reaction 2h at 95 ℃, and gained precipitation obtains clavate zinc oxide nano-crystal after deionized water wash, centrifugation, 80 ℃ of dry 16h.As shown in Figure 1, XRD diffracting spectrum as shown in Figure 2 for its stereoscan photograph.
Embodiment 2
Under room temperature (≤25 ℃), the ammonia soln of 0.001mol/L is added drop-wise in the solder(ing)acid of 1mol/L to pH=8, rate of addition is controlled at 3mL/min, fully reacts washing after 1h, centrifugation obtains amorphous zinc hydroxide; Adopt pure water to disperse to be mixed with the dispersion system of 0.3mol/L the amorphous zinc hydroxide of gained, then (mol ratio is Zn (OH) to add the potassium hydroxide solution of 0.001mol/L
2: KOH=1:6), the pH of mixed solution system is about 14, further isothermal reaction 4h at 80 ℃, and gained precipitation obtains clavate zinc oxide nano-crystal after pure water washing, centrifugation, 65 ℃ of dry 14h.As shown in Figure 3, photoluminescence spectrum as shown in Figure 4 for its TEM electromicroscopic photograph.
Embodiment 3
Under room temperature (≤25 ℃), the ammonia soln of 1mol/L is added drop-wise in zinc nitrate (or the nitric hydrate zinc) aqueous solution of 0.001mol/L to pH=7.5, rate of addition is controlled at 4mL/min, fully reacts washing, centrifugation after 0.75h and obtains amorphous zinc hydroxide; Adopt distilled water to disperse to be mixed with the dispersion system of 0.5mol/L the amorphous zinc hydroxide of gained, (mol ratio is Zn (OH) to add the potassium hydroxide solution of 0.5mol/L
2: KOH=1:4), gained mixing solutions is isothermal reaction 5h at 85 ℃, and gained precipitation obtains clavate zinc oxide nano-crystal through distilled water wash, centrifugation, 100 ℃ of dry 10h.As shown in Figure 5, photoluminescence spectrum as shown in Figure 6 for its TEM electromicroscopic photograph.
Embodiment 4
Under room temperature (≤25 ℃), the ammonia soln of 0.5mol/L is added drop-wise in zinc acetate (or the hydration zinc acetate) aqueous solution of 0.085mol/L to pH=7.8, rate of addition is controlled at 3mL/min, fully reacts washing, centrifugation after 1h and obtains amorphous zinc hydroxide; Add deionized water to be mixed with the dispersion system of 0.12mol/L the amorphous zinc hydroxide of gained, (mol ratio is Zn (OH) to add the potassium hydroxide solution of 0.02mol/L
2: KOH=1:0.5), gained mixing solutions is isothermal reaction 7h at 75 ℃, and gained precipitation obtains clavate zinc oxide nano-crystal after deionized water wash, centrifugation, 40 ℃ of negative pressure drying 24h.As shown in Figure 7, the degradation rate of photo-catalytic degradation of methyl-orange neutral aqueous solution is about 7 * 10 to its TEM electromicroscopic photograph
-3/ min, the rate of photocatalytic oxidation more nanocrystalline than particle shape 12 ~ 25nmZnO under same condition improves 220%.
Embodiment 5
Under room temperature (≤25 ℃), the ammonia soln of 0.25mol/L is added drop-wise in zinc acetate (or the hydration zinc acetate) aqueous solution of 0.2mol/L to pH=7.2, rate of addition is controlled at 2.5mL/min, fully reacts washing, centrifugation after 0.8h and obtains amorphous zinc hydroxide; Add deionized water to be mixed with the dispersion system of 0.5mol/L the amorphous zinc hydroxide of gained, (mol ratio is Zn (OH) to add the potassium hydroxide solution of 0.2mol/L
2: KOH=1:1), gained mixing solutions is isothermal reaction 7h at 90 ℃, and gained precipitation obtains clavate zinc oxide nano-crystal after deionized water wash, centrifugation, 80 ℃ of negative pressure drying 12h.As shown in Figure 8, the degradation rate constant of photo-catalytic degradation of methyl-orange neutral aqueous solution is about 5.6 * 10 to its SEM stereoscan photograph
-3/ min, improves approximately 150% than the nanocrystalline degradation rate constant of particle shape 12 ~ 25nmZnO under same condition.
The invention has the beneficial effects as follows, the method products therefrom is clavate zinc oxide nano-crystal, and its diameter is about 7 ~ 20nm, and length is about 12 ~ 100nm; Size is little, specific surface area is large, nano effect is remarkable, the excellent performances such as photoluminescence, photocatalytic degradation; Preparation technology is succinct, productive rate is high, and without any need for template or special substrate, without chemical additive, pollution-free, less energy-consumption, is a kind of Green Chemistry synthetic technology.
Claims (3)
1. a preparation method for clavate zinc oxide nanocrystalline, is characterized in that, according to following steps, implements:
Step 1, under the room temperature of≤25 ℃, the ammonia soln of 0.001～1mol/L is added drop-wise in the zinc salt solution of 0.001～1mol/L to pH=7～8, rate of addition is controlled at 2～4mL/min, fully reacts after 0.5～1h, washes with water, centrifugation, obtains amorphous zinc hydroxide;
Described zinc salt is selected one of zinc chloride, zinc nitrate, zinc sulfate, zinc acetate;
Step 2, the amorphous zinc hydroxide of step 1 gained is mixed with to the dispersion system of 0.001～1mol/L, then adds the potassium hydroxide solution of 0.001～1mol/L, the mol ratio of mixing solutions is controlled as KOH:Zn (OH)
2=1:(0.5～6), the pH of mixing solutions control is 14; At 75～95 ℃, again by this mixing solutions isothermal reaction 2～8h, gained precipitation washes with water, centrifugation, after 40～100 ℃ of dry 8～24h, obtains clavate zinc oxide nano-crystal.
2. the preparation method of clavate zinc oxide nanocrystalline according to claim 1, is characterized in that: described water is deionized water, pure water or distilled water.
3. the preparation method of clavate zinc oxide nanocrystalline according to claim 1, is characterized in that: the clavate zinc oxide nano-crystal in described step 2, and excellent footpath is 15～30nm, rod length is 50～100nm.
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| CN110143609B (en) * | 2019-05-30 | 2021-12-14 | 上海理工大学 | Preparation method for synthesizing nano zinc oxide with controllable shape based on direct precipitation method |
| CN111777094B (en) * | 2020-07-11 | 2022-11-22 | 河北博泰环保科技有限公司 | Preparation method of nanoscale zinc oxide with controllable pile ratio |
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|---|---|---|---|---|
| CN101182028A (en) * | 2007-11-23 | 2008-05-21 | 陕西科技大学 | Method for preparing ZnO nano rod |
| CN101407334A (en) * | 2007-10-12 | 2009-04-15 | 新疆大学 | Method for synthesizing rod-like nano-zinc oxide |
| CN101559973A (en) * | 2009-05-18 | 2009-10-21 | 清华大学 | Method for preparing nano zinc oxide and crystal whisker zinc oxide by using industrial zinc sulfate as raw material |
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| CN101407334A (en) * | 2007-10-12 | 2009-04-15 | 新疆大学 | Method for synthesizing rod-like nano-zinc oxide |
| CN101182028A (en) * | 2007-11-23 | 2008-05-21 | 陕西科技大学 | Method for preparing ZnO nano rod |
| CN101559973A (en) * | 2009-05-18 | 2009-10-21 | 清华大学 | Method for preparing nano zinc oxide and crystal whisker zinc oxide by using industrial zinc sulfate as raw material |
Non-Patent Citations (2)
| Title |
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| 从电池厂含锌废水中提取氧化锌;杨智宽等;《再生资源研究》;19951231(第1期);28-30 * |
| 杨智宽等.从电池厂含锌废水中提取氧化锌.《再生资源研究》.1995,(第1期),28-30. |
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