CN105692686A - Preparation method of nanometer zinc oxide powder - Google Patents
Preparation method of nanometer zinc oxide powder Download PDFInfo
- Publication number
- CN105692686A CN105692686A CN201610274054.6A CN201610274054A CN105692686A CN 105692686 A CN105692686 A CN 105692686A CN 201610274054 A CN201610274054 A CN 201610274054A CN 105692686 A CN105692686 A CN 105692686A
- Authority
- CN
- China
- Prior art keywords
- oxide powder
- zinc oxide
- preparation
- polymer
- nanometer zinc
- 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.)
- Granted
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 invention provides a preparation method of nanometer zinc oxide powder.The method particularly comprises the steps that a water-soluble polymer and dissolvable zinc salt serve as the raw materials, and a polymer-zinc salt mixture aqueous solution is prepared according to certain mass ratio of the polymer and a zinc source; water in the mixture aqueous solution is removed by means of a vacuum freezing drying technology, and a polymer-zinc salt white foamed solid is obtained; at last, the solid is subjected to calcination, and the product nanometer zinc oxide powder is obtained.The preparation technology is simple in process, the raw materials are easy to obtain, and the preparation process is clean and free of pollution; by means of the vacuum freezing drying technology, the prepared nanometer zinc oxide powder is small in size, uniform in particle size distribution, good in dispersity, high in purity and crystallinity and capable of being widely applied to multiple fields of photocatalysis, rubber, medicine, magnetic materials and the like.
Description
Technical field
The invention belongs to field of inorganic nano-material preparation, the preparation method being specifically related to a kind of nanometer Zinc oxide powder。
Background technology
Zinc oxide is a kind of important broad stopband direct band-gap semicondictor material, energy gap is 3.37eV at normal temperatures, there is bigger exciton bind energy (60meV), and at neighborhoods such as photocatalysis, opto-electronic conversion, sensor, feds, there is important application prospect with the photoelectric properties of its uniqueness。Nano zine oxide is the particle size zinc oxide at 1～100nm, granular due to crystal grain, its Electronic Structure and crystal structure change, create skin effect, bulk effect, quantum size effect and macroscopic view tunnel-effect that conventional oxidation zinc does not have, magnetic, optical, electrical etc. in there is the performance more more excellent than general zinc oxide product, be widely used in the fields such as rubber, daily-use chemical industry, medicine, magnetic material at present。
The preparation method of nano zine oxide is a lot, can be divided into according to the initial condition of raw material: solid phase method, liquid phase method and vapor phase method。Such as Chinese patent 201210517113.X and Chinese patent 201310117783.7 disclose a kind of method preparing nano zine oxide for template molecule solid phase with lignin amine；Chinese patent 200710139450.9 discloses a kind of technique adopting sluggish precipitation to prepare high dispersity nano zinc oxide；Chinese patent 201110110071.3 discloses the technique that a kind of sol-gal process prepares nano zine oxide；Chinese patent 201210144198.1 discloses the method and apparatus that a kind of plasma (orifice) gas phase reaction produces nano zine oxide。Although said method can successfully prepare nano zine oxide, but there is organic solvent and use the problems such as many, operation is loaded down with trivial details, operating condition is difficult to control to, preparation cost height and preparation process easily cause pollution simultaneously。Therefore, develop that a kind of technological process is simple, low cost and the free of contamination method preparing nano zine oxide significant for promoting that it is widely applied more。
Summary of the invention
For the deficiency that prior art exists, it is an object of the invention to provide that a kind of technological process is simple, low cost, pollution-free and be suitable to the new preparation process of nanometer Zinc oxide powder of industrialized production。
The preparation method of a kind 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 aqueous solutions of polymers of certain mass concentration；
(2) add soluble zinc salt by certain polymer and zinc source quality than in the described aqueous solution of step (1), obtain the mixture aqueous solution of polymer-zinc salt；
(3) by putting into after the abundant pre-freeze of aqueous solution described in step (2), vacuum freeze drier carries out lyophilization, obtain the white foam solid of polymer-zinc salt compound；
(4) solid described in step (3) is put in Muffle furnace calcine, obtain nanometer Zinc oxide powder。
All containing hydrophilic and hydrophobic group in the molecule of water soluble polymer, therefore a lot of water soluble polymer molecules have good surface activity, and this is highly beneficial to particle dispersion in the aqueous solution of water soluble polymer。Meanwhile, the polymer mesh structure that water soluble polymer molecule is formed in aqueous can fetter the particle in solution, makes ion movement in the solution be restricted, more trends towards being evenly dispersed in the middle of network structure。Additionally, the bulk shield ability that adsorption and the hydrophilicity thereof of the surface of solids are formed by water soluble polymer molecule, divided particles in solution is made to have good dispersion stabilization。
In the step (1) of said method, zinc salt in aqueous solution is had stable peptizaiton by water soluble polymer polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP) selected by the present invention, to being formed, mean diameter is little, and the nano-powder of even particle size distribution is highly beneficial。
The drying process that the present invention adopts is Vacuum Freezing & Drying Technology, and the application in field prepared by nano-powder of this technology reaches its maturity at present。Traditional drying means is directly to evaporate the solvent in solution to remove, and the later stage of solvent evaporation can constitute " liquid bridge " between particles of solute, finally easily makes generation hard aggregation between powder body。Vacuum Freezing & Drying Technology is that solution is first frozen into solid-state, then allows the solvent in solution directly distil removing, makes the material being dried itself stay in the middle of the solid frame of ice state when freezing while avoiding " liquid bridge " to produce。
The step (3) of above-mentioned preparation method adopts Vacuum Freezing & Drying Technology, the mixture aqueous solution of polymer-zinc salt is dried and obtains foaming solid, the problem that granule is easily reunited in solving dry run is simultaneously, remain the network structure of polymer, make polymeric that particle-stabilised peptizaiton to be fully used。In calcination process later, this special foamed polymer-zinc salt solid structure effectively inhibits the phenomenon that powder body easily lumps in calcined crystalline process, improves the dispersibility of nano-powder product。
In the step (1) of above-mentioned preparation method, when the water soluble polymer selected is polyvinyl alcohol, described mass concentration is 1%～5%, when mass concentration is less than 1%, solid after lyophilizing not easily collecting, when mass concentration is more than 5%, the easy gelation of polyvinyl alcohol water solution, cause that sample is difficult to lyophilizing；When the water soluble polymer selected is polyvinylpyrrolidone, described mass concentration is the suitable concn more than 1%。
In the step (2) of above-mentioned preparation method, described soluble zinc salt is zinc nitrate hexahydrate [Zn (NO cheap and easy to get3)2·6H2O] and zinc acetate [Zn (CH3COO)2]。
In the step (2) of above-mentioned preparation method, described water-soluble polymer and zinc source quality are than for 4:1～1:8。Experiments show that, when mass ratio is less than 4:1, the nanometer Zinc oxide powder even particle size distribution degree obtained declines, and when mass ratio is more than 1:8, the nanometer Zinc oxide powder obtained easily is reunited, and product dispersibility reduces。
In the step (4) of above-mentioned preparation method, described calcining heat is 450～650 DEG C, and described calcination time is 4～7 hours。
Compared with prior art, the method have the advantages that
(1) the method for the invention preparation technology flow process is simple, and reaction condition gentleness is 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 adopt any organic solvent, it is ensured that the safety of production and the feature of environmental protection, is advantageously implemented industrialized production；
(3) nanometer Zinc oxide powder that the method for the invention prepares is six limit wurtzite structures, high without any impurity, purity and degree of crystallinity；Particle size distribution is 60-80nm, good dispersion。
Accompanying drawing explanation
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。
Detailed description of the invention
By the examples below the preparation method of nanometer Zinc oxide powder of the present invention is described further。
Embodiment 1
Weigh 4.0g polyvinyl alcohol (PVA) in 500ml flask, add 200ml deionized water, then flask is put into heated and stirred 30min in 70 DEG C of water-baths, obtains the PVA aqueous solution of clear。16.0g zinc nitrate hexahydrate [Zn (NO is added to the PVA aqueous solution after cooling3)2·6H2O], obtain the mixed aqueous solution of polyvinyl alcohol-zinc nitrate (PVA-Zn)。Above-mentioned aqueous solution is poured in the specimen disc of freeze dryer, carry out abundant pre-freeze at low temperatures；Be subsequently placed in condenser temperature and be-55 DEG C, operating pressure be 10Pa freeze dryer in lyophilization 10h, obtain polyvinyl alcohol-zinc nitrate (PVA-Zn) white foam solid。Above-mentioned solid is put in Muffle furnace, after calcining 6h at 550 DEG C, namely obtains nanometer Zinc oxide powder。
The X-ray diffractogram (XRD) of the nano zinc oxide photocatalyst prepared by the present embodiment is as shown in Figure 1。As seen from Figure 1, the powder body material of preparation is the nano zine oxide of six limit wurtzite structures, and product purity and degree of crystallinity are high。
The scanning electron microscope (SEM) photograph (SEM) of the nano zinc oxide photocatalyst prepared by the present embodiment is as shown in Figure 2。Mean diameter is 70nm as seen from Figure 2, and even particle size distribution, without obvious agglomeration。
Embodiment 2
Weigh 4.0g polyvinyl alcohol (PVA) in 500ml flask, add 200ml deionized water, then flask is put into heated and stirred 30min in 70 DEG C of water-baths, obtains the PVA aqueous solution of clear。16.0g zinc acetate [Zn (CH is added to the PVA aqueous solution after cooling3COO)2], obtain the mixed aqueous solution of polyvinyl alcohol-zinc acetate (PVA-Zn)。Above-mentioned aqueous solution is poured in the specimen disc of freeze dryer, carry out abundant pre-freeze at low temperatures；Be subsequently placed in condenser temperature and be-55 DEG C, operating pressure be 10Pa freeze dryer in lyophilization 10h, obtain polyvinyl alcohol-zinc acetate (PVA-Zn) white foam solid。Above-mentioned solid is put in Muffle furnace, after calcining 5h at 450 DEG C, namely obtains nanometer Zinc oxide powder。
Embodiment 3
Weigh 10.0g polyvinylpyrrolidone (PVP) in 500ml flask, add 200ml deionized water, after stirring 30min, obtain the PVP aqueous solution of clear。40.0g zinc nitrate hexahydrate [Zn (NO is added to PVP aqueous solution3)2·6H2O], obtain the mixed aqueous solution of polyvinylpyrrolidone-zinc nitrate (PVP-Zn)。Above-mentioned aqueous solution is poured in the specimen disc of freeze dryer, carry out abundant pre-freeze at low temperatures；Be subsequently placed in condenser temperature and be-55 DEG C, operating pressure be 10Pa freeze dryer in lyophilization 10h, obtain polyvinyl alcohol-zinc nitrate (PVP-Zn) white foam solid。Above-mentioned solid is put in Muffle furnace, after calcining 6h at 550 DEG C, namely obtains nano-zinc oxide powder。
Embodiment 4
Weigh 10.0g polyvinylpyrrolidone (PVP) in 500ml flask, add 200ml deionized water, after stirring 30min, obtain the PVP aqueous solution of clear。40.0g zinc acetate [Zn (CH is added to PVP aqueous solution3COO)2], obtain the mixed aqueous solution of polyvinylpyrrolidone-zinc acetate (PVP-Zn)。Above-mentioned aqueous solution is poured in the specimen disc of freeze dryer, carry out abundant pre-freeze at low temperatures；Be subsequently placed in condenser temperature and be-55 DEG C, operating pressure be 10Pa freeze dryer in lyophilization 10h, obtain polyvinyl alcohol-zinc acetate (PVP-Zn) white foam solid。Above-mentioned solid is put in Muffle furnace, after calcining 5h at 450 DEG C, namely obtains nano-zinc oxide powder。
As can be seen from the above-described embodiment, the preparation method of the present invention have pollution-free, low cost, technique are simple, easy to operate, be prone to the features such as industrialization generation。It is little that the nanometer Zinc oxide powder of the preparation of the present invention has size, even particle size distribution, good dispersion, purity and degree of crystallinity high, is expected to be used widely in fields such as photocatalysis, rubber, medicine, magnetic materials。
It addition, applicant studies discovery, utilize the inventive method can also prepare the various metal oxide materials such as copper oxide, ferrum oxide, titanium oxide。Other amendment carried out according to technical solution of the present invention or equivalent replace, all should be encompassed in the middle of scope of the presently claimed invention。
Claims (8)
1. the preparation method of a nanometer Zinc oxide powder, it is characterised in that the 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) add soluble zinc salt by certain polymer and zinc source quality than in the described aqueous solution of step (1), obtain the mixture aqueous solution of polymer-zinc salt；
(3) by putting into after the abundant pre-freeze of aqueous solution described in step (2), vacuum freeze drier carries out lyophilization, obtain the white foam solid of polymer-zinc salt compound；
(4) solid described in step (3) is put in Muffle furnace calcine, obtain nanometer Zinc oxide powder。
2. the preparation method of the nanometer Zinc oxide powder according to claim 1, it is characterised in that water soluble polymer described in step (1) includes but not limited to polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP)。
3. the preparation method of the nanometer Zinc oxide powder according to claim 1 or 2, it is characterised in that zinc source described in step (2) is zinc nitrate hexahydrate [Zn (NO3)2·6H2O] and zinc acetate [Zn (CH3COO)2]。
4. the preparation method according to the nanometer Zinc oxide powder one of claims 1 to 3 Suo Shu, it is characterised in that mass ratio described in step (2) is 4:1～1:8, it is preferred to 1:1～1:6。
5. the preparation method according to the nanometer Zinc oxide powder one of Claims 1-4 Suo Shu, it is characterised in that the drying process adopted in step (3) is Vacuum Freezing & Drying Technology。
6. the preparation method according to the nanometer Zinc oxide powder one of claim 1 to 5 Suo Shu, it is characterised in that the calcining heat in step (4) is 450～650 DEG C。
7. the preparation method according to the nanometer Zinc oxide powder one of claim 1 to 6 Suo Shu, it is characterised in that the calcination time in step (4) is 4～7 hours。
8. the nanometer Zinc oxide powder that prepared by a method described in claim 1 to 7。
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 true CN105692686A (en) | 2016-06-22 |
| CN105692686B 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) |
Cited By (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 |
| CN107140605A (en) * | 2017-06-29 | 2017-09-08 | 东北师范大学 | A kind of porous oxide and preparation method thereof |
| 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 |
| 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 |
| 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 |
| CN114105184A (en) * | 2021-12-03 | 2022-03-01 | 江永县潇湘化工有限公司 | Method for preparing small-size zinc oxide by using 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 (2)
| Title |
|---|
| 刘军: "真空冷冻干燥法制备无机功能纳米粉体的研究", 《中国博士学位论文全文数据库工程科技I辑》 * |
| 曾令可: "《陶瓷工业使用干燥技术与实例》", 31 August 2008 * |
Cited By (9)
| 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 |
| CN107140605A (en) * | 2017-06-29 | 2017-09-08 | 东北师范大学 | A kind of porous oxide and preparation method thereof |
| 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 |
| 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 |
| 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 |
| CN114105184A (en) * | 2021-12-03 | 2022-03-01 | 江永县潇湘化工有限公司 | Method for preparing small-size zinc oxide by using carbon dioxide |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105692686B (en) | 2017-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105692686A (en) | Preparation method of nanometer zinc oxide powder | |
| CN107376971B (en) | Synthetic method of graphite-like carbon nitride/molybdenum disulfide nano composite material | |
| CN104118908B (en) | A kind of regulation and control preparation method of orderly titanium dioxide nano material | |
| KR20200015640A (en) | Mesoporous titanium dioxide nanoparticles and process for their production | |
| CN103949193A (en) | Universal method for preparation of inorganic hollow microspheres | |
| Shahmiri et al. | Effect of pH on the synthesis of CuO nanosheets by quick precipitation method | |
| KR100843190B1 (en) | Method of fabrication of zinc oxide by freeze drying at low temperature | |
| Liu et al. | Synthesis of ZnO nano-powders via a novel PVA-assisted freeze-drying process | |
| Alaei et al. | Preparation of high surface area ZrO2 nanoparticles | |
| CN104439276B (en) | A kind of quick method and product preparing hollow porous silica/argentum nano composite material | |
| CN103623799A (en) | Preparation method of titanium dioxide mesoporous microspheres | |
| Liu et al. | Microwave-assisted hydrothermal synthesis of cellulose/ZnO composites and its thermal transformation to ZnO/carbon composites | |
| Mahmoudabad et al. | Synthesis and characterization of PbO nanostructure and NiO doped with PbO through combustion of citrate/nitrate gel | |
| Liu et al. | Fabrication and photocatalytic properties of flexible BiOI/SiO2 hybrid membrane by electrospinning method | |
| Chang et al. | Effect of post-heat treatment on the photocatalytic activity of titanium dioxide nanowire membranes deposited on a Ti substrate | |
| CN103833080B (en) | A kind of preparation method of molybdic acid cadmium porous ball | |
| CN110227517B (en) | CuBi2O4/BiPO4P-n type heterojunction photocatalyst, preparation method and application thereof | |
| CN109019694B (en) | Micro-nano structure spherical MnCO3Preparation method of (1) | |
| CN107337233A (en) | A kind of method of one step vulcanization method synthesis of titanium dioxide and titanium disulfide composite | |
| CN108264069B (en) | Preparation method of monodisperse nano magnesium oxide | |
| CN101113016A (en) | Preparation method of starfish-shaped cadmium sulfide nanostructure | |
| CN105110362A (en) | Preparation method of flower cluster-shaped zinc oxide hybrid material based on cellulose nanosphere crystal as template | |
| CN107381618A (en) | A kind of preparation method of club shaped structure nano zine oxide | |
| Gandhi et al. | Facile and green synthesis of ZnO nanostructures using ionic liquid assisted banana stem extract route | |
| Boran et al. | Synthesis optimization of ZrO2 nanostructures for photocatalytic applications |
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 |
Granted publication date: 20171117 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |