CN105692686B - A kind of preparation method of nanometer Zinc oxide powder - Google Patents
A kind of preparation method of nanometer Zinc oxide powder Download PDFInfo
- Publication number
- CN105692686B CN105692686B CN201610274054.6A CN201610274054A CN105692686B CN 105692686 B CN105692686 B CN 105692686B CN 201610274054 A CN201610274054 A CN 201610274054A CN 105692686 B CN105692686 B CN 105692686B
- Authority
- CN
- China
- Prior art keywords
- oxide powder
- zinc oxide
- preparation
- zinc
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The present invention provides a kind of preparation method of nanometer Zinc oxide powder, and specific steps include, using water soluble polymer and soluble zinc salt as raw material, first by the mixture aqueous solution of certain high polymer and zinc source quality than prepared polymer zinc salt；Then the water in mixture aqueous solution is removed using Vacuum Freezing ＆ Drying Technology, obtains the white foam solid of polymer zinc salt；Finally solid is calcined, obtains product nano Zinc oxide powder.The flow of the preparation technology is simple, and raw material is easy to get, preparation process cleanliness without any pollution；Using Vacuum Freezing ＆ Drying Technology, the nanometer Zinc oxide powder size being prepared is small, and particle diameter distribution is uniform, good dispersion, and purity and crystallinity are high, can be widely used for the multiple fields such as photocatalysis, rubber, medicine, magnetic material.
Description
Technical field
The invention belongs to field of inorganic nano-material preparation, and in particular to a kind of preparation method of nanometer Zinc oxide powder.
Background technology
Zinc oxide is a kind of important broad stopband direct band-gap semicondictor material, and energy gap is 3.37eV at normal temperatures,
Sent out with larger exciton bind energy (60meV), and with its unique photoelectric properties in photocatalysis, opto-electronic conversion, sensor, field
The neighborhoods such as emitter part have important application prospect.Nano zine oxide is zinc oxide of the particle size in 1~100nm, due to crystalline substance
The granular of grain, its Electronic Structure and crystal structure change, and generate the surface effect that conventional oxidation zinc does not have
Should, bulk effect, quantum size effect and macroscopical tunnel-effect, have than general zinc oxide product more in magnetic, light, electricity etc.
For excellent performance, the fields such as rubber, daily-use chemical industry, medicine, magnetic material are widely used at present.
The preparation method of nano zine oxide is a lot, can be divided into according to the reset condition of raw material：Solid phase method, liquid phase method and gas phase
Method.Such as Chinese patent 201210517113.X and Chinese patent 201310117783.7 disclose one kind using lignin amine as template
The method that molecule solid phase prepares nano zine oxide；Chinese patent 200710139450.9 discloses one kind and uses homogeneous precipitation legal system
The technique of standby high dispersity nano zinc oxide；Chinese patent 201110110071.3 discloses a kind of sol-gal process and prepares nanometer
The technique of zinc oxide；Chinese patent 201210144198.1 discloses a kind of side of plasma (orifice) gas phase reaction production nano zine oxide
Method and device.Although the above method can successfully prepare nano zine oxide, organic solvent be present and use more, tedious process, behaviour
Make the problems such as condition is unmanageable, while prepare that cost is high and preparation process easily causes pollution.Therefore, a kind of technological process is developed
Simply, the inexpensive and free of contamination method for preparing nano zine oxide is for promoting it to be more widely applied with important meaning
Justice.
The content of the invention
In view of the deficienciess of the prior art, it is an object of the invention to provide a kind of technological process is simple, low cost, nothing
Pollution and the new preparation process for being suitable to the nanometer Zinc oxide powder of industrialized production.
A kind of preparation method of nanometer Zinc oxide powder, it is characterised in that comprise the following steps：
(1) water soluble polymer of certain mass is dissolved in deionized water, obtains the polymer water of certain mass concentration
Solution；
(2) soluble zinc salt is added into step (1) described aqueous solution by certain polymer and zinc source mass ratio, is gathered
The mixture aqueous solution of compound-zinc salt；
(3) it will be put into vacuum freeze drier and be freeze-dried after the abundant pre-freeze of the aqueous solution described in step (2),
Obtain the white foam solid of polymer-zinc salt compound；
(4) solid described in step (3) is put into Muffle furnace and calcined, obtain nanometer Zinc oxide powder.
All contain hydrophilic and hydrophobic grouping in the molecule of water soluble polymer, therefore many water soluble polymer molecules have
Preferable surface-active, this is scattered highly beneficial in the aqueous solution of water soluble polymer to particle.It is meanwhile water-soluble high poly-
The polymer mesh structure that thing molecule is formed in aqueous can fetter the particle in solution, make the movement of ion in the solution by
To limitation, more it is intended to be evenly dispersed among network structure.In addition, suction of the water soluble polymer molecule to the surface of solids
The bulk shield ability that attached effect and its hydrophilicity are formed, the particle for making to disperse in solution have preferable stably dispersing
Property.
In the step of above method (1), water soluble polymer polyvinyl alcohol (PVA) and polyethylene pyrrole selected by the present invention
Pyrrolidone (PVP) has stable peptizaiton to the zinc salt in the aqueous solution, and small to forming average grain diameter, particle diameter distribution is uniform
Nano-powder is highly beneficial.
For the drying process that the present invention uses for Vacuum Freezing ＆ Drying Technology, the technology should field prepared by nano-powder
With having reached its maturity at present.Traditional drying means is directly to evaporate the solvent in solution to remove, the later stage meeting of solvent evaporation
" liquid bridge " is formed between particles of solute, finally easily makes to produce hard aggregation between powder.Vacuum Freezing ＆ Drying Technology is first by solution
Solid-state is frozen into, then allows the solvent in solution directly to distil removing, the material dried is made while avoiding " liquid bridge " from producing
Itself stay among the solid frame of ice state when freezing.
Vacuum Freezing ＆ Drying Technology is used in the step of above-mentioned preparation method (3), the mixture of polymer-zinc salt is water-soluble
Liquid is dried to obtain foaming solid, and particle is easily reunited simultaneously in solving the problems, such as drying process, remains the network of polymer
Structure, polymeric is set to be fully used particle-stabilised peptizaiton.In calcination process afterwards, this spy
The polymer of different foam-like-zinc salt solid structure effectively inhibits the phenomenon that powder easily lumps during calcined crystalline, carries
The dispersiveness of high nano-powder product.
In the step of above-mentioned preparation method (1), when the water soluble polymer of selection is polyvinyl alcohol, the mass concentration is
1%~5%, when mass concentration is less than 1%, the solid not easily collecting after freezing, when mass concentration is more than 5%, polyethylene
The easy gelation of alcohol solution, causes sample to be difficult to freeze；When the water soluble polymer of selection is polyvinylpyrrolidone, the matter
Concentration is measured as the suitable concn more than 1%.
In the step of above-mentioned preparation method (2), the soluble zinc salt is zinc nitrate hexahydrate [Zn cheap and easy to get
(NO3)2·6H2O] and zinc acetate [Zn (CH3COO)2]。
In the step of above-mentioned preparation method (2), the water-soluble polymer is 4 with zinc source mass ratio:1~1:8.Test table
It is bright, when mass ratio is less than 4:When 1, the obtained nanometer Zinc oxide powder particle diameter distribution uniformity declines, and when mass ratio is more than 1:8
When, obtained nanometer Zinc oxide powder is easily reunited, and product dispersiveness reduces.The mass ratio is preferably 1:1~1:6.
In the step of above-mentioned preparation method (4), the calcining heat is 450~650 DEG C, and the calcination time is 4~7 small
When.
Compared with prior art, the invention has the advantages that：
(1) the method for the invention preparation technology flow is simple, and reaction condition is gently easily-controllable, simple to operate；
(2) the method for the invention is raw materials used cheap and easy to get and nontoxic；Operating process does not use any organic molten
Agent, the security and the feature of environmental protection of production are ensure that, is advantageously implemented industrialized production；
(3) nanometer Zinc oxide powder that the method for the invention is prepared is six side wurtzite structures, no any impurity,
Purity and crystallinity are high；Particle diameter distribution is 60-80nm, good dispersion.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram (XRD) of nano zine oxide in the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of nano zine oxide in the embodiment of the present invention 1.
Embodiment
The preparation method of nanometer Zinc oxide powder of the present invention is described further below by embodiment.
Embodiment 1
4.0g polyvinyl alcohol (PVA) is weighed in 500ml flasks, 200ml deionized waters is added, flask is then put into 70
Heating stirring 30min in DEG C water-bath, obtains the PVA aqueous solution of clear.16.0g is added to the PVA aqueous solution after cooling
Zinc nitrate hexahydrate [Zn (NO3)2·6H2O], obtain polyvinyl alcohol-zinc nitrate (PVA-Zn) mixed aqueous solution.By above-mentioned water
Solution is poured into the sample disc of freeze dryer, carries out abundant pre-freeze at low temperature；Condenser temperature is subsequently placed in as -55 DEG C, work pressure
10h is freeze-dried in the strong freeze dryer for 10Pa, obtains polyvinyl alcohol-zinc nitrate (PVA-Zn) white foam solid.Will be upper
State solid to be put into Muffle furnace, nanometer Zinc oxide powder is obtained after 6h is calcined at 550 DEG C.
The X-ray diffractogram (XRD) of nano zinc oxide photocatalyst prepared by the present embodiment is as shown in Figure 1.Can by Fig. 1
To find out, the powder body material of preparation is the nano zine oxide of six side wurtzite structures, and product purity and crystallinity are high.
The scanning electron microscope (SEM) photograph (SEM) of nano zinc oxide photocatalyst prepared by the present embodiment is as shown in Figure 2.Can by Fig. 2
To find out average grain diameter as 70nm, and particle diameter distribution is uniform, without obvious agglomeration.
Embodiment 2
4.0g polyvinyl alcohol (PVA) is weighed in 500ml flasks, 200ml deionized waters is added, flask is then put into 70
Heating stirring 30min in DEG C water-bath, obtains the PVA aqueous solution of clear.16.0g is added to the PVA aqueous solution after cooling
Zinc acetate [Zn (CH3COO)2], obtain polyvinyl alcohol-zinc acetate (PVA-Zn) mixed aqueous solution.The above-mentioned aqueous solution is poured into jelly
In the sample disc of dry machine, abundant pre-freeze is carried out at low temperature；Condenser temperature is subsequently placed in as -55 DEG C, operating pressure is 10Pa's
10h is freeze-dried in freeze dryer, obtains polyvinyl alcohol-zinc acetate (PVA-Zn) white foam solid.Above-mentioned solid is put into
In Muffle furnace, nanometer Zinc oxide powder is obtained after 5h is calcined at 450 DEG C.
Embodiment 3
10.0g polyvinylpyrrolidones (PVP) are weighed in 500ml flasks, add 200ml deionized waters, stir 30min
The PVP aqueous solution of clear is obtained afterwards.40.0g zinc nitrate hexahydrates [Zn (NO are added to the PVP aqueous solution3)2·6H2O], obtain
To polyvinylpyrrolidone-zinc nitrate (PVP-Zn) mixed aqueous solution.The above-mentioned aqueous solution is poured into the sample disc of freeze dryer,
Abundant pre-freeze is carried out at low temperature；Condenser temperature is subsequently placed in as -55 DEG C, operating pressure is to be freeze-dried in 10Pa freeze dryer
10h, obtain polyvinyl alcohol-zinc nitrate (PVP-Zn) white foam solid.Above-mentioned solid is put into Muffle furnace, at 550 DEG C
Nano-zinc oxide powder is obtained after lower calcining 6h.
Embodiment 4
10.0g polyvinylpyrrolidones (PVP) are weighed in 500ml flasks, add 200ml deionized waters, stir 30min
The PVP aqueous solution of clear is obtained afterwards.40.0g zinc acetates [Zn (CH are added to the PVP aqueous solution3COO)2], obtain polyethylene pyrrole
The mixed aqueous solution of pyrrolidone-zinc acetate (PVP-Zn).The above-mentioned aqueous solution is poured into the sample disc of freeze dryer, entered at low temperature
The abundant pre-freeze of row；Condenser temperature is subsequently placed in as -55 DEG C, operating pressure is to be freeze-dried 10h in 10Pa freeze dryer, is gathered
Vinyl alcohol-zinc acetate (PVP-Zn) white foam solid.Above-mentioned solid is put into Muffle furnace, after calcining 5h at 450 DEG C
Obtain nano-zinc oxide powder.
As can be seen from the above-described embodiment, preparation method of the invention has that pollution-free, inexpensive, technique is simple, operation
Conveniently, the features such as being easy to industrialization generation.The nanometer Zinc oxide powder of the preparation of the present invention has size small, and particle diameter distribution is equal
It is even, good dispersion, the features such as purity and high crystallinity, it is expected to obtain extensively in fields such as photocatalysis, rubber, medicine, magnetic materials
General application.
In addition, applicants have found that, it is each cupric oxide, iron oxide, titanium oxide etc. can also to be prepared using the inventive method
Kind metal oxide materials.Other modifications carried out according to technical solution of the present invention or equivalent substitution, all should cover in this hair
Among bright right.
Claims (6)
1. a kind of preparation method of nanometer Zinc oxide powder, it is characterised in that this method comprises the following steps：
(1) water soluble polymer of certain mass is dissolved in deionized water, obtains the aqueous solutions of polymers of certain mass concentration；
(2) soluble zinc salt is added into step (1) described aqueous solution by certain polymer and zinc source mass ratio, is polymerize
The mixture aqueous solution of thing-zinc salt；
(3) it will be put into vacuum freeze drier and be freeze-dried after the abundant pre-freeze of the aqueous solution described in step (2), obtained
The white foam solid of polymer-zinc salt compound；
(4) solid described in step (3) is put into Muffle furnace and calcined, obtain nanometer Zinc oxide powder；
The aqueous solutions of polymers of certain mass concentration is the polyvinylpyrrolidone that concentration is more than 1% wherein described in step (1)
(PVP) aqueous solution；And mass ratio described in step (2) is 4:1~1:8.
2. the preparation method of nanometer Zinc oxide powder according to claim 1, it is characterised in that zinc described in step (2)
Source is zinc nitrate hexahydrate [Zn (NO3)2·6H2O] and zinc acetate [Zn (CH3COO)2]。
3. the preparation method of nanometer Zinc oxide powder according to claim 1 or 2, it is characterised in that described in step (2)
Mass ratio is 1:1~1:6.
4. the preparation method of nanometer Zinc oxide powder according to claim 1 or 2, it is characterised in that used in step (3)
Drying process be Vacuum Freezing ＆ Drying Technology.
5. the preparation method of nanometer Zinc oxide powder according to claim 1 or 2, it is characterised in that forging in step (4)
It is 450~650 DEG C to burn temperature.
6. the preparation method of nanometer Zinc oxide powder according to claim 1 or 2, it is characterised in that forging in step (4)
It is 4~7 hours to burn the time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610274054.6A CN105692686B (en) | 2016-04-28 | 2016-04-28 | A kind of preparation method of nanometer Zinc oxide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610274054.6A CN105692686B (en) | 2016-04-28 | 2016-04-28 | A kind of preparation method of nanometer Zinc oxide powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105692686A CN105692686A (en) | 2016-06-22 |
| CN105692686B true CN105692686B (en) | 2017-11-17 |
Family
ID=56216674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610274054.6A Expired - Fee Related CN105692686B (en) | 2016-04-28 | 2016-04-28 | A kind of preparation method of nanometer Zinc oxide powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105692686B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106006711A (en) * | 2016-07-07 | 2016-10-12 | 安徽省含山县锦华氧化锌厂 | Preparing method for nanometer zinc oxide |
| CN107140605B (en) * | 2017-06-29 | 2019-05-28 | 东北师范大学 | A kind of porous oxide and preparation method thereof |
| CN107473261A (en) * | 2017-09-01 | 2017-12-15 | 北京化工大学 | A kind of preparation method of zinc oxide/redox graphene composite |
| CN107381618A (en) * | 2017-09-01 | 2017-11-24 | 北京化工大学 | A kind of preparation method of club shaped structure nano zine oxide |
| CN108002421A (en) * | 2017-12-25 | 2018-05-08 | 河南工业大学 | A kind of preparation method with fluorite type structure nano-powder |
| CN110404533A (en) * | 2018-04-26 | 2019-11-05 | 北京化工大学 | A kind of noble silver supported nano zinc oxide raw powder's production technology |
| CN112439371A (en) * | 2019-08-31 | 2021-03-05 | 北京化工大学 | Preparation method of submicron copper oxide-polymer carbon skeleton material with core-shell structure |
| CN114105184B (en) * | 2021-12-03 | 2023-10-24 | 江永县潇湘化工有限公司 | Method for preparing small-size zinc oxide from carbon dioxide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040237A (en) * | 2010-12-15 | 2011-05-04 | 中国铝业股份有限公司 | Method for preparing nano-alumina |
| CN102219252A (en) * | 2010-04-16 | 2011-10-19 | 沈斌斌 | Process for preparing nanometer zinc-oxide by ultrasonic emulsification method |
| CN103146387A (en) * | 2013-03-19 | 2013-06-12 | 山东大学 | Process for preparing porous rare-earth luminescent material by freeze-drying method |
| CN103351021A (en) * | 2013-08-02 | 2013-10-16 | 重庆大学 | Method for preparing nano zinc oxide |
| CN105036109A (en) * | 2015-06-26 | 2015-11-11 | 上海纳旭实业有限公司 | Preparation method of hierarchical pore carbon material and loaded nano-silver composite functional material |
-
2016
- 2016-04-28 CN CN201610274054.6A patent/CN105692686B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219252A (en) * | 2010-04-16 | 2011-10-19 | 沈斌斌 | Process for preparing nanometer zinc-oxide by ultrasonic emulsification method |
| CN102040237A (en) * | 2010-12-15 | 2011-05-04 | 中国铝业股份有限公司 | Method for preparing nano-alumina |
| CN103146387A (en) * | 2013-03-19 | 2013-06-12 | 山东大学 | Process for preparing porous rare-earth luminescent material by freeze-drying method |
| CN103351021A (en) * | 2013-08-02 | 2013-10-16 | 重庆大学 | Method for preparing nano zinc oxide |
| CN105036109A (en) * | 2015-06-26 | 2015-11-11 | 上海纳旭实业有限公司 | Preparation method of hierarchical pore carbon material and loaded nano-silver composite functional material |
Non-Patent Citations (1)
| Title |
|---|
| 真空冷冻干燥法制备无机功能纳米粉体的研究;刘军;《中国博士学位论文全文数据库工程科技I辑》;20061115;第7-16页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105692686A (en) | 2016-06-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105692686B (en) | A kind of preparation method of nanometer Zinc oxide powder | |
| CN109205567B (en) | Method for preparing metal oxide multilevel structure by utilizing MOF derived bimetallic oxide template | |
| CN101898749B (en) | Method for preparing metal oxide hollow particles or fibers | |
| CN103553023B (en) | Preparation method of nitrogen hybridized spherical mesoporous carbon | |
| Podlogar et al. | The role of hydrothermal pathways in the evolution of the morphology of ZnO crystals | |
| CN104986742A (en) | Bead-chain-like graphitized carbon nitride nano material and preparation method thereof | |
| CN100422084C (en) | Slice type nonporous nano magnesia and its preparation method | |
| Zhou et al. | Morphology-controlled synthesis of Co3O4 by one step template-free hydrothermal method | |
| Shahmiri et al. | Effect of pH on the synthesis of CuO nanosheets by quick precipitation method | |
| CN110976901A (en) | Preparation method of nano copper powder | |
| CN105540640A (en) | Preparation method of flower-shaped nanometer zinc oxide | |
| CN109879312A (en) | A kind of preparation method of photocatalyst of titanium dioxide nano-powder | |
| CN110181071A (en) | Nano-Ag particles and its preparation method and application | |
| CN100391845C (en) | Method for preparing nano-magnesia by utilizing self-spreading sol-gel method | |
| CN106186045A (en) | A kind of preparation method of flower shape zinc oxide nano-particle cluster | |
| Liu et al. | Fabrication and photocatalytic properties of flexible BiOI/SiO2 hybrid membrane by electrospinning method | |
| KR20130070092A (en) | Method for producing yttrium oxide powders and yttrium oxide powders prepared by the method | |
| CN107935047B (en) | A kind of control synthetic method of different-shape and the nano-manganese dioxide of size | |
| Ramesh et al. | A novel route for synthesis and characterization of green Cu2O/PVA nano composites | |
| CN109019694B (en) | Micro-nano structure spherical MnCO3Preparation method of (1) | |
| CN103833080A (en) | Preparation method for cadmium molybdate porous spheres | |
| CN107381618A (en) | A kind of preparation method of club shaped structure nano zine oxide | |
| CN100368281C (en) | Preparation method of nanometer metal oxide and composite metal oxide | |
| CN107777718B (en) | A kind of Y2O3Nano-powder and preparation method thereof | |
| CN103641176B (en) | Preparation method of lamellar spinelle type ferrite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171117 |