CN101311119A - Reticular nano hole zinc oxide micron hollow ball and preparation method thereof - Google Patents
Reticular nano hole zinc oxide micron hollow ball and preparation method thereof Download PDFInfo
- Publication number
- CN101311119A CN101311119A CNA2007100227195A CN200710022719A CN101311119A CN 101311119 A CN101311119 A CN 101311119A CN A2007100227195 A CNA2007100227195 A CN A2007100227195A CN 200710022719 A CN200710022719 A CN 200710022719A CN 101311119 A CN101311119 A CN 101311119A
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- zinc
- hollow ball
- oxide micron
- nano hole
- 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
Images
Abstract
The invention discloses a reticulate nanopore zinc-oxide micron hollow sphere and a preparation method thereof. The hollow sphere of the invention comprises the following materials: the surface of the zinc-oxide micron hollow sphere is provided with reticulate nanopore, wherein, the diameter of the hollow sphere is 1 to 10mum and the aperture of the nanopore is 50 to 100nm; the method of the invention comprises a liquid-phase chemical method, particularly (a) according to the mole ratio that zinc salt: chelating agent: sodium citrate: water is equal to 1:(0.5-1.5):(0.05-0.15):(50-150), the materials are weighted, then put into a vessel, stirred, dissolved and kept warm for three hours at the temperature of 70 to 100 DEG C under the sealing state to obtain a product; (b) the obtained product is filtrated, washed more than one time and heated for 1 to 3 hours at the temperature of 300 to 500 temperature, and the reticulate nanopore zinc-oxide micron hollow sphere is obtained; the zinc salt is zinc nitrate or zinc acetate or zinc chloride or zinc sulfate, and the chelating agent is urea or ammonia or hexamethylene tetramine or ammonium hydroxide. The hollow sphere can be widely applied to the fields of drug transportation, chemical reaction carrier, cosmetics, coating material, catalytic and photocatalysis material, etc.
Description
Technical field
The present invention relates to a kind of Zinc oxide hollow spheres and method for making, especially a kind of reticular nano hole zinc oxide micron hollow ball and preparation method thereof.
Background technology
Along with the develop rapidly of modern industry, people have also tasted disastrous effect-environmental pollution that industrialization is left us in the benefit that the enjoyment modern science and technology is brought.Since having found semiconductor material since can catalyze and degrade organic pollutants after the illumination, seek efficient, nontoxic catalyzer is the target that people make great efforts always, and has obtained very plentiful and substantial research and application achievements.Semiconductor material, especially wide band gap semiconducter have all demonstrated wide application prospect as titanium dioxide, zinc oxide etc. at aspects such as wastewater treatment, purifying air, photogalvanic cells.An essential condition that improves light-catalyzed reaction efficient is exactly that catalytic material has than higher specific surface area, and nano material just in time satisfies this requirement.But be reduced to a dimensioning when material, nano particle especially is because the agglomeration that its surperficial electrostatic interaction produces is a difficult problem that hampers the nano-powder material application always.The nano material of hollow ball structure has characteristics such as light specific gravity, specific surface area is big, perviousness is strong, at aspects such as drug delivery carrier, chemical reaction carrier, makeup, coating, catalysis and photocatalyst materials important application prospects is arranged, particularly, can further overcome the problem of nanoparticle agglomerates at catalytic field.At present, people are in order to obtain the nano-powder material of hollow ball structure, some trials and effort have been done, as a kind of " is the preparation method of the Zinc oxide hollow spheres of raw material with the zinc powder " that in the Chinese invention patent specification sheets CN 1305803C of bulletin on March 21st, 2007, discloses.It adopts wet chemical method, promptly is raw material with the zinc powder, with the surface of the excessive zinc powder of acid treatment, makes precipitation agent with ammoniacal liquor, forms Zn nuclear/Zn (OH) in liquid phase earlier
2Shell composite particles throw out, throw out again through 600～950 ℃ of calcinings, make Zn (OH) after separation, washing and drying
2Shell is decomposed into ZnO, volatilization of zinc nuclear or oxidation simultaneously, thus form the zinc oxide hollow spherical structure.But this preparation method exists weak point, at first, can not make its surface and be the zinc oxide micron hollow ball of mesh nano size vesicular structure; Secondly, it is to be starting raw material with the zinc powder, the shape of the Zinc oxide hollow spheres of therefore preparing and quality the place one's entire reliance upon shape and the quality of raw material zinc powder, the diameter of its final Zinc oxide hollow spheres that generates and the sizableness of initial zinc powder size, as obtaining the uniform Zinc oxide hollow spheres of size, just must screen zinc powder, this will make production cost strengthen; Once more, the forerunner's product that obtains in the preparation is Zn/Zn (OH)
2Core/shell structure, need make surperficial Zn (OH) in the calcining down of 600～900 ℃ of higher temperature
2Change into zinc oxide, make the zinc evaporation and the oxidation of the inside simultaneously, so the difficult control of the shape and size of ball hollow core part; At last, need ethanol with an organic solvent in the preparation, not only increased cost, also easily environment is polluted.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of ball surface to be the reticular nano hole zinc oxide micron hollow ball of mesh nano size vesicular structure for overcoming weak point of the prior art.
Another technical problem that the present invention will solve is for providing a kind of shape of raw material and preparation method of the reticular nano hole zinc oxide micron hollow ball that quality restricts, sintering temperature is low of not being subjected to.
For solving technical problem of the present invention, the technical scheme that is adopted is: reticular nano hole zinc oxide micron hollow ball comprises Zinc oxide hollow spheres, particularly said Zinc oxide hollow spheres is a zinc oxide micron hollow ball, the surface of said zinc oxide micron hollow ball is a reticular nano hole, wherein, the sphere diameter of zinc oxide micron hollow ball is 1～10 μ m, and the aperture of reticular nano hole is 50～100nm.
As the further improvement of reticular nano hole zinc oxide micron hollow ball, the sphere diameter of described zinc oxide micron hollow ball is 4～6 μ m.
For solving another technical problem of the present invention, another technical scheme that is adopted is: the preparation method of reticular nano hole zinc oxide micron hollow ball comprises liquid chemical method, particularly it is finished according to the following steps: (a) according to zinc salt: chela and agent: Trisodium Citrate: the molar ratio of water=1: 0.5～1.5: 0.05～0.15: 50～150, weighing is placed on the container for stirring dissolving, obtains product in 3～10 hours in 70～100 ℃ of insulations under sealed state; (b) earlier product is filtered, and more than the water cleaning once, again it was heated 1～3 hour down in 300～500 ℃, make reticular nano hole zinc oxide micron hollow ball.
As the preparation method's of reticular nano hole zinc oxide micron hollow ball further improvement, described zinc salt is zinc nitrate or zinc acetate or zinc chloride or zinc sulfate; Described chela and agent are urea or ammoniacal liquor or hexamethylenetetramine or aqua ammonia; Described water is deionized water or distilled water; Described product is a white depositions; Described to after the white depositions filtration, the number of times that water cleans is≤5 times.
Beneficial effect with respect to prior art is, one, use field emission scanning electron microscope and transmission electron microscope to characterize respectively to intermediate product and the hollow ball that makes, stereoscan photograph explanation intermediate product is fairly regular micron ball, the porous network structure that its surface is formed by connecting for nanometer sheet.Through 500 ℃ of hollow balls that obtained behind the heating anneal in two hours, its structure is intact, just the surface more rough porous that becomes.Transmission electron microscope photo explanation intermediate product is a hollow structure.The sphere diameter of intermediate product and hollow ball is 1～10 μ m, and the aperture of the reticular nano hole that it is surperficial is 50～100nm; They are two years old, use power spectrum tester and x-ray diffractometer to characterize respectively to intermediate product and the hollow ball that makes, scanning can contain carbon, zinc, three kinds of elements of oxygen in the spectrogram demonstration intermediate product, has only zinc and oxygen element behind the heating anneal, shows that intermediate product has changed into zinc oxide fully.By X-ray diffracting spectrum as can be known, intermediate product is a non-crystalline material, and two weak diffraction peaks wherein are from the organism in the material.Heating anneal is after two hours in 300 ℃ of air atmosphere, and intermediary material begins crystallization and becomes the zinc oxide polycrystalline structure; Its three, the raw materials used chemical reagent that is of preparation method is reflected in the solution and carries out with the atom contact condition, so the steady quality of product, each parameter be easy to control.By adjusting, realized the inside and outside footpath size and the global shape of product are effectively controlled to the reaction times; Its four, the temperature of heating anneal is low, the power consumption few, causes production cost lower; Its five, neither need to handle raw material with acid, also not with an organic solvent, belong to green synthesis techniques; Its six, method is easy, production efficiency is high, the utmost point is suitable for suitability for industrialized production.
Further embodiment as beneficial effect, the one, zinc salt is selected zinc nitrate or zinc acetate or zinc chloride or zinc sulfate for use, and urea or ammoniacal liquor or hexamethylenetetramine or aqua ammonia are selected in chela and agent for use, makes the selection of raw material that bigger leeway be arranged, not only convenient flexibly, also be beneficial to suitability for industrialized production; The 2nd, be after white depositions is filtered to product, the number of times that water cleans is preferably≤and 5 times, make the less wash number of its need just can reach the purpose of cleaning.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 be to middle product take the photograph after with the observation of Japanese JEOL 6700 type field emission scanning electron microscopes (SEM) 4 SEM photos, can find out that by these SEM photos intermediate product is the powder of globe, the surface of globe is netted vesicular structure;
Fig. 2 be to the hollow ball that makes take the photograph after with Japanese JEOL 6700 type field emission scanning electron microscopes (SEM) observation 2 SEM photos, can find out by these 2 SEM photos, hollow ball also is the powder of globe, the surface of globe also is netted vesicular structure, and just the surface of globe is more coarse;
Fig. 3 be to middle product with take the photograph after JEM-200CX type transmission electron microscope (TEM) observation the TEM photo, by the TEM photo as can be known, intermediate product is a hollow ball;
Fig. 4 is the incidental power spectrum test of Sirion200FEG type field emission scanning electron microscope (EDS) instrument of respectively middle product and the hollow ball that makes being used U.S. FEI Co. to its EDS that scans back gained figure as a result, wherein, (a) figure is the EDS figure as a result that middle product is scanned the back gained, and (b) figure is the EDS figure as a result that hollow ball is scanned back gained;
Fig. 5 is the XRD figure that obtains after the hollow ball that makes is tested with Japanese X-ray diffraction of science (XRD) instrument, wherein, ordinate zou is a relative intensity, and X-coordinate is a diffraction angle, by the position of each diffraction peak in the XRD figure and relative intensity as can be known, this micrometre hollow sphere is to be made of zinc oxide.
Embodiment
At first make or buy zinc nitrate, zinc acetate, zinc chloride and zinc sulfate, urea, ammoniacal liquor, hexamethylenetetramine and aqua ammonia as chela and agent as zinc salt from market with ordinary method, and Trisodium Citrate and deionized water, distilled water.Then,
Embodiment 1: finish preparation according to the following steps successively: a) according to zinc salt: chela and agent: Trisodium Citrate: water=1: 0.5: 0.15: 50 molar ratio, weighing are placed on the container for stirring dissolving, obtain product in 10 hours in 70 ℃ of insulations under sealed state; Wherein, zinc salt selects for use zinc nitrate, chela and agent to select urea, wet concentration deionized water for use.The product that obtains is a white depositions.B) earlier white depositions is filtered, and water cleans 1 time, obtain as shown in figures 1 and 3 and the reticular nano hole micrometre hollow sphere shown in curve among (a) figure of Fig. 4, again with it in 300 ℃ of down heating 3 hours, make as shown in Figure 2 and as (b) of Fig. 4 schemes and Fig. 5 in the reticular nano hole zinc oxide micron hollow ball shown in the curve.
Embodiment 2: finish preparation according to the following steps successively: a) according to zinc salt: chela and agent: Trisodium Citrate: water=1: 0.8: 0.13: 75 molar ratio, weighing are placed on the container for stirring dissolving, obtain product in 9 hours in 77 ℃ of insulations under sealed state; Wherein, zinc salt selects for use zinc nitrate, chela and agent to select urea, wet concentration deionized water for use.The product that obtains is a white depositions.B) earlier white depositions is filtered, and water cleans 2 times, obtain as shown in figures 1 and 3 and the reticular nano hole micrometre hollow sphere shown in curve among (a) figure of Fig. 4, again with it in 350 ℃ of down heating 2.5 hours, make as shown in Figure 2 and as (b) of Fig. 4 schemes and Fig. 5 in the reticular nano hole zinc oxide micron hollow ball shown in the curve.
Embodiment 3: finish preparation according to the following steps successively: a) according to zinc salt: chela and agent: Trisodium Citrate: water=1: 1: 0.1: 100 molar ratio, weighing are placed on the container for stirring dissolving, obtain product in 7 hours in 85 ℃ of insulations under sealed state; Wherein, zinc salt selects for use zinc nitrate, chela and agent to select urea, wet concentration deionized water for use.The product that obtains is a white depositions.B) earlier white depositions is filtered, and water cleans 3 times, obtain as shown in figures 1 and 3 and the reticular nano hole micrometre hollow sphere shown in curve among (a) figure of Fig. 4, again with it in 400 ℃ of down heating 2 hours, make as shown in Figure 2 and as (b) of Fig. 4 schemes and Fig. 5 in the reticular nano hole zinc oxide micron hollow ball shown in the curve.
Embodiment 4: finish preparation according to the following steps successively: a) according to zinc salt: chela and agent: Trisodium Citrate: water=1: 1.3: 0.08: 125 molar ratio, weighing are placed on the container for stirring dissolving, obtain product in 5 hours in 93 ℃ of insulations under sealed state; Wherein, zinc salt selects for use zinc nitrate, chela and agent to select urea, wet concentration deionized water for use.The product that obtains is a white depositions.B) earlier white depositions is filtered, and water cleans 4 times, obtain as shown in figures 1 and 3 and the reticular nano hole micrometre hollow sphere shown in curve among (a) figure of Fig. 4, again with it in 450 ℃ of down heating 1.5 hours, make as shown in Figure 2 and as (b) of Fig. 4 schemes and Fig. 5 in the reticular nano hole zinc oxide micron hollow ball shown in the curve.
Embodiment 5: finish preparation according to the following steps successively: a) according to zinc salt: chela and agent: Trisodium Citrate: water=1: 1.5: 0.05: 150 molar ratio, weighing are placed on the container for stirring dissolving, obtain product in 3 hours in 100 ℃ of insulations under sealed state; Wherein, zinc salt selects for use zinc nitrate, chela and agent to select urea, wet concentration deionized water for use.The product that obtains is a white depositions.B) earlier white depositions is filtered, and water cleans 5 times, obtain as shown in figures 1 and 3 and the reticular nano hole micrometre hollow sphere shown in curve among (a) figure of Fig. 4, again with it in 500 ℃ of down heating 1 hour, make as shown in Figure 2 and as (b) of Fig. 4 schemes and Fig. 5 in the reticular nano hole zinc oxide micron hollow ball shown in the curve.
Select zinc acetate or zinc chloride or zinc sulfate in the zinc salt more respectively for use, ammoniacal liquor in chela and the agent or hexamethylenetetramine or aqua ammonia, distilled water in the water, repeat the foregoing description 1～5, make reticular nano hole micrometre hollow sphere and reticular nano hole zinc oxide micron hollow ball shown in the curve among Fig. 1～3 and Fig. 4 and Fig. 5 equally.
Obviously, those skilled in the art can carry out various changes and modification to reticular nano hole zinc oxide micron hollow ball of the present invention and preparation method thereof and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (8)
1, a kind of reticular nano hole zinc oxide micron hollow ball, comprise Zinc oxide hollow spheres, it is characterized in that said Zinc oxide hollow spheres is a zinc oxide micron hollow ball, the surface of said zinc oxide micron hollow ball is a reticular nano hole, wherein, the sphere diameter of zinc oxide micron hollow ball is 1～10 μ m, and the aperture of reticular nano hole is 50～100nm.
2, reticular nano hole zinc oxide micron hollow ball according to claim 1, the sphere diameter that it is characterized in that zinc oxide micron hollow ball are 4～6 μ m.
3, the preparation method of reticular nano hole zinc oxide micron hollow ball according to claim 1 comprises liquid chemical method, it is characterized in that finishing according to the following steps:
(a) according to zinc salt: chela and agent: Trisodium Citrate: the molar ratio of water=1: 0.5～1.5: 0.05～0.15: 50～150, weighing are placed on the container for stirring dissolving, obtain product in 3～10 hours in 70～100 ℃ of insulations under sealed state;
(b) earlier product is filtered, and more than the water cleaning once, again it was heated 1～3 hour down in 300～500 ℃, make reticular nano hole zinc oxide micron hollow ball.
4, the preparation method of reticular nano hole zinc oxide micron hollow ball according to claim 3 is characterized in that zinc salt is zinc nitrate or zinc acetate or zinc chloride or zinc sulfate.
5, the preparation method of reticular nano hole zinc oxide micron hollow ball according to claim 3 is characterized in that chela and agent are urea or ammoniacal liquor or hexamethylenetetramine or aqua ammonia.
6, the preparation method of reticular nano hole zinc oxide micron hollow ball according to claim 3 is characterized in that water is deionized water or distilled water.
7, the preparation method of reticular nano hole zinc oxide micron hollow ball according to claim 3 is characterized in that product is a white depositions.
8, the preparation method of reticular nano hole zinc oxide micron hollow ball according to claim 7 is characterized in that the number of times that water cleans is≤5 times to after the white depositions filtration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100227195A CN101311119B (en) | 2007-05-25 | 2007-05-25 | Reticular nano hole zinc oxide micron hollow ball and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100227195A CN101311119B (en) | 2007-05-25 | 2007-05-25 | Reticular nano hole zinc oxide micron hollow ball and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101311119A true CN101311119A (en) | 2008-11-26 |
| CN101311119B CN101311119B (en) | 2010-09-08 |
Family
ID=40099976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100227195A Expired - Fee Related CN101311119B (en) | 2007-05-25 | 2007-05-25 | Reticular nano hole zinc oxide micron hollow ball and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101311119B (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101767814A (en) * | 2010-03-09 | 2010-07-07 | 黑龙江大学 | Multilevel-structure zinc oxide constructed by three dimension units and preparation method thereof |
| CN101559974B (en) * | 2009-05-14 | 2010-08-18 | 浙江理工大学 | Method for preparing zinc oxide hollow microspheres |
| CN101863518A (en) * | 2010-07-01 | 2010-10-20 | 上海应用技术学院 | Co3O4 nano hollow sphere material and preparation method and application thereof |
| CN101948130A (en) * | 2010-10-11 | 2011-01-19 | 厦门大学 | Zinc oxide hollow microspheres and preparation method thereof |
| CN102398916A (en) * | 2010-09-07 | 2012-04-04 | 中国科学院上海硅酸盐研究所 | Low-temperature synthesis method of zinc oxide hollow ball |
| CN101723437B (en) * | 2009-12-22 | 2012-05-30 | 聊城大学 | Method for preparing porous laminated zinc oxide sphere |
| CN102515246A (en) * | 2011-12-02 | 2012-06-27 | 南京林业大学 | Preparation method of porous nano zinc oxide (ZnO) |
| CN102897825A (en) * | 2012-09-25 | 2013-01-30 | 江苏大学 | Method for preparing nano-hollow spherical shell zinc oxide by hydrothermal-calcinating method |
| CN103145113A (en) * | 2011-12-07 | 2013-06-12 | 中国科学院合肥物质科学研究院 | Micro-nano structure zinc oxide-carbon composite pellet and preparation method thereof |
| CN103182301A (en) * | 2011-12-29 | 2013-07-03 | 吉林师范大学 | Controllable growing method of hamburger shaped ZnO nano-photocatalyst |
| CN103739003A (en) * | 2014-01-28 | 2014-04-23 | 扬州大学 | Synthesizing method for zinc oxide nanometer materials |
| CN103771486A (en) * | 2014-01-28 | 2014-05-07 | 扬州大学 | Synthetic method of hollow copper oxide nanometer material |
| CN104164176A (en) * | 2014-08-04 | 2014-11-26 | 陕西科技大学 | Method for enhancing water resistance of water-based polyurethane for synthetic leather by using zinc oxide |
| CN104971708A (en) * | 2015-07-03 | 2015-10-14 | 陕西科技大学 | Ce-doped spherical ZnO photocatalyst applicable to treatment of dye wastewater and preparation method thereof |
| CN106497246A (en) * | 2016-11-17 | 2017-03-15 | 闻承岳 | A kind of enhanced chloro-sulfonated polyethylene anti-corrosive coating of modified zinc oxide antibacterial and mouldproof |
| CN107572578A (en) * | 2017-09-07 | 2018-01-12 | 东南大学 | A kind of method that no template prepares zinc oxide spherical shell |
| CN110540229A (en) * | 2019-09-10 | 2019-12-06 | 安徽锦华氧化锌有限公司 | production method of hollow shell nano zinc oxide for rubber tire |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102390862A (en) * | 2011-08-15 | 2012-03-28 | 天津理工大学 | Liquid-phase precipitation preparation method of zinc oxide porous hollow balls |
| CN107582415B (en) * | 2017-08-03 | 2020-08-04 | 南昌大学 | Whitening toothpaste with visible light excited oxidation-reduction reaction and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305803C (en) * | 2005-05-13 | 2007-03-21 | 中国科学院上海硅酸盐研究所 | Prepn process of hollow zinc oxide balls with zinc powder as material |
| CN100357186C (en) * | 2006-01-26 | 2007-12-26 | 徐志兵 | Zinc oxide hollow microsphere preparation method |
-
2007
- 2007-05-25 CN CN2007100227195A patent/CN101311119B/en not_active Expired - Fee Related
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559974B (en) * | 2009-05-14 | 2010-08-18 | 浙江理工大学 | Method for preparing zinc oxide hollow microspheres |
| CN101723437B (en) * | 2009-12-22 | 2012-05-30 | 聊城大学 | Method for preparing porous laminated zinc oxide sphere |
| CN101767814A (en) * | 2010-03-09 | 2010-07-07 | 黑龙江大学 | Multilevel-structure zinc oxide constructed by three dimension units and preparation method thereof |
| CN101863518A (en) * | 2010-07-01 | 2010-10-20 | 上海应用技术学院 | Co3O4 nano hollow sphere material and preparation method and application thereof |
| CN102398916B (en) * | 2010-09-07 | 2013-10-30 | 中国科学院上海硅酸盐研究所 | Low-temperature synthesis method of zinc oxide hollow ball |
| CN102398916A (en) * | 2010-09-07 | 2012-04-04 | 中国科学院上海硅酸盐研究所 | Low-temperature synthesis method of zinc oxide hollow ball |
| CN101948130A (en) * | 2010-10-11 | 2011-01-19 | 厦门大学 | Zinc oxide hollow microspheres and preparation method thereof |
| CN102515246A (en) * | 2011-12-02 | 2012-06-27 | 南京林业大学 | Preparation method of porous nano zinc oxide (ZnO) |
| CN102515246B (en) * | 2011-12-02 | 2013-12-04 | 南京林业大学 | Preparation method of porous nano zinc oxide (ZnO) |
| CN103145113A (en) * | 2011-12-07 | 2013-06-12 | 中国科学院合肥物质科学研究院 | Micro-nano structure zinc oxide-carbon composite pellet and preparation method thereof |
| CN103182301A (en) * | 2011-12-29 | 2013-07-03 | 吉林师范大学 | Controllable growing method of hamburger shaped ZnO nano-photocatalyst |
| CN102897825A (en) * | 2012-09-25 | 2013-01-30 | 江苏大学 | Method for preparing nano-hollow spherical shell zinc oxide by hydrothermal-calcinating method |
| CN102897825B (en) * | 2012-09-25 | 2014-05-28 | 江苏大学 | Method for preparing nano-hollow spherical shell zinc oxide by hydrothermal-calcinating method |
| CN103771486A (en) * | 2014-01-28 | 2014-05-07 | 扬州大学 | Synthetic method of hollow copper oxide nanometer material |
| CN103739003A (en) * | 2014-01-28 | 2014-04-23 | 扬州大学 | Synthesizing method for zinc oxide nanometer materials |
| CN103771486B (en) * | 2014-01-28 | 2015-03-25 | 扬州大学 | Synthetic method of hollow copper oxide nanometer material |
| CN103739003B (en) * | 2014-01-28 | 2015-03-25 | 扬州大学 | Synthesizing method for zinc oxide nanometer materials |
| CN104164176A (en) * | 2014-08-04 | 2014-11-26 | 陕西科技大学 | Method for enhancing water resistance of water-based polyurethane for synthetic leather by using zinc oxide |
| CN104971708A (en) * | 2015-07-03 | 2015-10-14 | 陕西科技大学 | Ce-doped spherical ZnO photocatalyst applicable to treatment of dye wastewater and preparation method thereof |
| CN106497246A (en) * | 2016-11-17 | 2017-03-15 | 闻承岳 | A kind of enhanced chloro-sulfonated polyethylene anti-corrosive coating of modified zinc oxide antibacterial and mouldproof |
| CN107572578A (en) * | 2017-09-07 | 2018-01-12 | 东南大学 | A kind of method that no template prepares zinc oxide spherical shell |
| CN110540229A (en) * | 2019-09-10 | 2019-12-06 | 安徽锦华氧化锌有限公司 | production method of hollow shell nano zinc oxide for rubber tire |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101311119B (en) | 2010-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101311119B (en) | Reticular nano hole zinc oxide micron hollow ball and preparation method thereof | |
| Le et al. | Mechanisms of removal of heavy metal ions by ZnO particles | |
| Nasirian et al. | Enhancement of photocatalytic activity of titanium dioxide using non-metal doping methods under visible light: a review | |
| Li et al. | Hierarchical photocatalysts | |
| CN110918126B (en) | Preparation method of flower-shaped molybdenum disulfide combined UiO-66 photocatalyst | |
| RU2194666C2 (en) | Nanostructural oxides and hydroxides and methods of their synthesis | |
| Li et al. | Fabricating yolk–shell structured CoTiO3@ Co3O4 nanoreactor via a simple self-template method toward high-performance peroxymonosulfate activation and organic pollutant degradation | |
| CN111545192B (en) | MOFs-derived perovskite catalyst, preparation method thereof and application of MOFs-derived perovskite catalyst in catalytic degradation of organic pollutants | |
| CN109205567B (en) | Method for preparing metal oxide multilevel structure by utilizing MOF derived bimetallic oxide template | |
| CN105129835B (en) | Hexacosahedral cuprous oxide nanometer particle preparation method | |
| Zeng et al. | Bioprocess-inspired synthesis of hierarchically porous nitrogen-doped TiO 2 with high visible-light photocatalytic activity | |
| US20120309617A1 (en) | Method of Production of Photocatalytic Powder Comprising Titanium Dioxide and Manganese Dioxide Active Under Ultraviolet and Visible Light | |
| CN103172030A (en) | Oxide powder and preparation method thereof as well as catalyst and carrier thereof | |
| CN101519223A (en) | One-step template-free method for preparing a great amount of monodisperse ZnS hollow nanospheres | |
| Hussain et al. | Factors affecting the growth formation of nanostructures and their impact on electrode materials: A systematic review | |
| CN102199004A (en) | Preparation method of hollow glass microspheres with directional titanium dioxide nano-rods growths on surface | |
| CN1190947A (en) | Spheroidally agglomerated basic cobalt (II) carbonate and spheroidally agglomerated cobalt (II) hydroxide, process for their production and their use | |
| CN111099650A (en) | CeO2Molten salt method for synthesizing nano spherical particles | |
| Wang et al. | Tuning the morphological structure and photocatalytic activity of nitrogen-doped (BiO) 2CO3 by the hydrothermal temperature | |
| Khurram et al. | α-Fe 2 O 3-based nanocomposites: Synthesis, characterization, and photocatalytic response towards wastewater treatment | |
| Cai et al. | CuS hierarchical hollow microcubes with improved visible-light photocatalytic performance | |
| Lee et al. | Template-sacrificial conversion of MnCO3 microspheres to fabricate Mn-doped TiO2 visible light photocatalysts | |
| CN105883910B (en) | A kind of perovskite SrTiO3The preparation method and product of porous nano particle | |
| CN108212187B (en) | Fe doped Bi2O2CO3Preparation method of photocatalyst and Fe-doped Bi2O2CO3Photocatalyst and process for producing the same | |
| CN101759232B (en) | Porous manganese dioxide of nanofibre texture and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100908 Termination date: 20150525 |
|
| EXPY | Termination of patent right or utility model |