CN102070182B - Porous zinc oxide micro powder and preparation method and application thereof - Google Patents
Porous zinc oxide micro powder and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses porous zinc oxide micro powder and a preparation method and application thereof. According to the powder, granular zinc oxide with granule diameter of 50 to 100 nanometers forms a porous micro block, the diameter of pores on the porous micro block is 20 to 70 nanometers, the length of the porous micro block is 5 to 10 microns, the width of the block is 5 to 10 microns, the height of the block is 10 to 20 microns, and the specific surface area of the block is 8 to 9m<2>/g. The method comprises the following steps of: dripping 0.01 to 0.03M zinc chloride solution into saturated oxalic acid solution of 70 to 90 DEG C with stirring to obtain white sediment, repeatedly washing the white sediment by using water and ethanol in turn, drying the white sediment to obtain a zinc oxalate dihydrate precursor, and then baking the zinc oxalate dihydrate precursor for at least 1 hour at the temperature of between 480 and 520 DEG C to obtain the porous zinc oxide micro powder. The porous zinc oxide micro powder can be widely applied to qualitative and semi-quantitative detection of polychlorinated biphenyl in air, water and soil.
Description
Technical field
The present invention relates to a kind of micro-powder and preparation method and application, especially a kind of porous zinc bloom micro-powder.
Background technology
Nano zine oxide with surface effects, small-size effect and quantum effect has shown many exceptional functions at aspects such as catalysis, optics, magnetic, electricity and mechanics, makes it have important use to be worth in pottery, chemical industry, electronics, optics, biology and medicine and other fields.At present; People are in order to explore and expand the range of application of nano zine oxide; Some trials and effort have been done, like " a kind of stephanoporate zinc oxide nano-powder and preparation method thereof " that discloses among the disclosed Chinese invention patent Shen Qing Publication specification sheets CN 101318690A on December 10th, 2008.It is intended to provide a kind of stephanoporate zinc oxide nano-powder with high catalytic activity and preparation method thereof; Wherein, the size distribution of stephanoporate zinc oxide nano-powder is 10～250nm, and the inside of nano particle is vesicular structure, and its pore size distribution is 5～120nm; The preparation method in stirring mixing after wherein adding PEG400 down, is dissolved in bicarbonate of ammonia in deionized water and/or the absolute ethyl alcohol earlier for earlier zinc nitrate hexahydrate being dissolved in absolute ethyl alcohol or the deionized water more then; Again zinc nitrate ethanolic soln or the aqueous solution are added drop-wise in bicarbonate of ammonia deionized water and/or the ethanol solution and obtain precursor, afterwards, after the spinning; Earlier wash precursor with ammonium bicarbonate aqueous solution, use absolute ethanol washing again, dry back adds propyl carbinol; After being uniformly dispersed,, last in 115～120 ℃ of 1～2h that reflux; Propyl carbinol is reclaimed in elder generation's underpressure distillation, utilizes waste heat evaporate to dryness solid again, obtains stephanoporate zinc oxide nano-powder.But, no matter be stephanoporate zinc oxide nano-powder, or its preparation method; With and uses thereof; All exist weak point, at first, the size distribution of stephanoporate zinc oxide nano-powder and be nano level as its inner pore size distribution of particle of powder; Though this nano level size makes the porous zinc bloom powder that high catalytic activity arranged, make it not possess other functions also; Secondly, the used raw material of preparation method is many, and technology is numerous and diverse, during energy charge, is difficult to large-scale industrial production; Once more, stephanoporate zinc oxide nano-powder only can be used for catalytic field, and is not suitable for the detection to the pollutent polychlorobiphenyl.
Summary of the invention
The technical problem that the present invention will solve is for overcoming weak point of the prior art, and it is the porous zinc bloom micro-powder that contains nano-scale particle in porous micron block, the piece that a kind of powder is provided.
Another technical problem that the present invention will solve is the preparation method that a kind of porous zinc bloom micro-powder is provided.
Technical problem in addition that the present invention will solve is the application that a kind of porous zinc bloom micro-powder is provided.
For solving technical problem of the present invention, the technical scheme that is adopted is: the porous zinc bloom micro-powder is that the particulate state zinc oxide of 50～100nm constitutes by particle diameter, particularly,
Said particulate state zinc oxide constitutes the porous micron block, and the bore dia in the hole on the said porous micron block is 20～70nm;
The block length of said porous micron block be 5～10 μ m, piece wide be that 5～10 μ m, piece height are 10～20 μ m;
The specific surface area of said porous micron block is 8～9m
2/ g.
Further improvement as the porous zinc bloom micro-powder; The bore dia in the hole on the described porous micron block is on the bore dia and block length direction on the high direction of piece, the diplopore of the bore dia on the piece cross direction directly distributes; Bore dia on the high direction of piece in said diplopore footpath is 40～70nm, and the bore dia on the block length direction, on the piece cross direction is 20～50nm.
For solving another technical problem of the present invention, another technical scheme that is adopted is: the preparation method of porous zinc bloom micro-powder comprises solution method, and particularly completing steps is following:
Step 1; Be that dropping concentration is the liquor zinci chloridi of 0.01～0.03M in 70～90 ℃ the saturated oxalic acid solution to stirring temperature down earlier, obtain white depositions, water and ethanol are successively after the repetitive scrubbing white depositions again; It is carried out drying treatment, obtain two oxalic acid hydrate zinc precursor things;
Step 2, it is 480～520 ℃ of following roastings 1h at least that two oxalic acid hydrate zinc precursor things are placed temperature, makes the porous zinc bloom micro-powder.
As the preparing method's of porous zinc bloom micro-powder further improvement, the described speed that in saturated oxalic acid solution, drips liquor zinci chloridi is 2ml/min; Described water and the ethanol number of times of repetitive scrubbing white depositions successively are more than 3 times; Temperature during described drying treatment is 70～90 ℃, and the time is 1～3h.
For solving the technical problem that also has of the present invention, the technical scheme that also has that is adopted is: the application of porous zinc bloom micro-powder comprises the porous zinc bloom powder that receives pollution by polychlorinated biphenyles, particularly,
Step 1 places the porous zinc bloom micro-powder earlier to clamp between two conductive glass and fix, and is under the monochromatic ray irradiation of 400～550nm at wavelength, records the surface photovoltage V of porous zinc bloom micro-powder
1Again the porous zinc bloom micro-powder that receives pollution by polychlorinated biphenyles of same amount is placed and clamp and be fixed into identical density between two conductive glass; Under the monochromatic ray irradiation of identical wavelength and light intensity, record the surface photovoltage V of the porous zinc bloom micro-powder that receives pollution by polychlorinated biphenyles
2, then, use formula s=(V
1-V
2) * 100/V
1Calculate the reduction rate s of surface photovoltage;
Step 2 is with the reduction rate s substitution regression equation of surface photovoltage
Calculate the content m of polychlorobiphenyl to be measured, wherein,
M in the formula, s is respectively m, and the MV of s, n are the number of the s that records, and the unit of m is a milligram.
As the further improvement of the application of porous zinc bloom micro-powder, described monochromatic light intensity is 100mW/cm
2Described surface measurements photovoltage V
1And V
2The time, be the MV of measuring 3 minutes; Described polychlorobiphenyl is any among PCB1～PCB127.
Beneficial effect with respect to prior art is that one of which uses x-ray diffractometer and field emission scanning electron microscope to carry out the sign of composition, form and structure respectively to the product that makes, and can be known that by its result product is a zinc oxide.It is that the particulate state zinc oxide of 50～100nm constitutes the porous micron block by particle diameter.The block length of porous micron block be 5～10 μ m, piece wide be that 5～10 μ m, piece height are 10～20 μ m.The bore dia in the hole on the porous micron block is on the bore dia and block length direction on the high direction of piece, the diplopore of the bore dia on the piece cross direction directly distributes; Bore dia on the high direction of piece in this diplopore footpath is 40～70nm, and the bore dia on the block length direction, on the piece cross direction is 20～50nm.The specific surface area of porous micron block is 8～9m
2/ g; They are two years old; The preparation method adopts the mode that in saturated oxalic acid solution, drips lower concentration chlorination zinc solution to make its reaction and obtains the presoma of small particle size; Utilize oxalic acid to do pore-forming material simultaneously, under calcination condition, formed the micron blocks of forming by nano particle, thereby both obtained a kind of Zinc oxide powder of micro-nano structure; The advantage of few, the easy and simple to handle and energy-and time-economizing of materials is arranged again, make its utmost point be suitable for large-scale industrial production; Its three, through a large amount of tests, product is low to moderate 10 to concentration
-4The pollutent polychlorobiphenyl of M all can detect effectively.The basis of its detection and mechanism does, product constitutes the porous micron block by nano level particulate state zinc oxide, and the aperture in the hole that forms between nano granular of zinc oxide wherein is a nano level; The piece that nano granular of zinc oxide constitutes is a micron order, and the micro-nano structure that this perfect match forms had been to connect to a micron block by nano particle because of its micron grade blocky both, and makes electronics be able to be easy to migration at bigger body in mutually; Thereby make its surface photovoltage signal stronger; Again because of it has nano level vesicular structure, and make its adsorptivity strong, realized enrichment pollutent to be detected; Thereby the decrease that makes its surface photovoltage signal is easy to surveyed; Also construct and vesicular structure, and make it have abundant surface state, thereby make its surface photovoltage signal strong in radiation of visible light lower surface attitude transition of electron generation because of the nano particle of powder; So can under radiation of visible light, detect, avoid the unfavorable factors such as signal attenuation that cause under the UV-irradiation to pollutent.When product wavelength be 400～550nm monochromatic ray irradiation down, the abundant surface state transition of electron in product surface makes the surface potential reduction of product, the generation surface photovoltage to the conduction band (this transition is called as " transition of subzone crack ") of zinc oxide.When pcb molecule is adsorbed to the product surface; Pcb molecule plays the constraint effect because of it has the characteristic that attracts electronics to the electronics of surface state; Hindered the transition of surface state electronics, suppressed the reduction of surface potential, made the surface photovoltage of its surface photovoltage less than the product that does not adsorb polychlorobiphenyl; Be zinc oxide behind the absorption polychlorobiphenyl, its surface photovoltage can produce a decrease.Through measurement, can obtain to adsorb the decrease of front and rear surfaces photovoltage to the surface photovoltage before and after the product absorption polychlorobiphenyl.The size of decrease is relevant with the quantity of limited surface state transition of electron, and is promptly relevant with the amount of the polychlorobiphenyl of surface adsorption.The surface photovoltage decrease of the zinc oxide through the absorption polychlorobiphenyl comes the amount of reflection absorption polychlorobiphenyl indirectly, has realized the purpose of polychlorobiphenyl in the testing environment.
Further embodiment as beneficial effect; The one, the bore dia in the hole on the porous micron block is preferably on the bore dia and block length direction on the high direction of piece, the diplopore of the bore dia on the piece cross direction directly distributes; Bore dia on the high direction of piece in diplopore footpath is preferably 40～70nm; Bore dia on the block length direction, on the piece cross direction all is preferably 20～50nm, is beneficial to the sensitivity that raising detects polychlorobiphenyl; The 2nd, the speed that in saturated oxalic acid solution, drips liquor zinci chloridi is preferably 2ml/min, and the reaction that is beneficial to precursor generates; The 3rd, water and the ethanol number of times of repetitive scrubbing white depositions successively are preferably more than 3 times, are beneficial to the removal fully of impurity in the throw out; The 4th, the temperature during drying treatment is preferably 70～90 ℃, and the time is preferably 1～3h, can be under lower temperature, so that the time of weak point makes product; The 4th, monochromatic light intensity is preferably 100mW/cm
2, the photon energy that can make it can excite product to produce subzone crack transition again to greatest extent, thereby make it be easy under monochromatic irradiation, excited both less than the band-gap energy of zinc oxide, produces surface photovoltage; The 5th, surface measurements photovoltage V
1And V
2The time, all be preferably the MV of measuring 3 minutes, be beneficial to the minimizing error, promote the accuracy of measuring; The 6th, polychlorobiphenyl is preferably any among PCB1～PCB127, is to belong to common polychlorobiphenyl isomer owing to these 127 kinds.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 uses one of result that X-ray diffraction (XRD) appearance and field emission scanning electron microscope (SEM) characterize respectively to the product that makes.Wherein, Fig. 1 a is an XRD spectra, can be known by it, and product is a zinc oxide; Fig. 1 b is the SEM photo of product, can be found out by it, and product is micron-sized block; Fig. 1 c and Fig. 1 d are respectively the xsect and the lateral high power SEM photo of product, can be found out by these two SEM photos, and product is that nano level granular substance constitutes by particle diameter, and the bore dia in the hole that forms between the granular substance also is nano level.
Fig. 2 uses it for one of result who detects pollution by polychlorinated biphenyles according to the application of product.Wherein, polychlorobiphenyl to be detected is one of its isomer, promptly PCB101 (2,2 ', 4,5,5 '-pentachlorodiphenyl), its concentration is>=10
-4M.Can find out that by this figure product is low to moderate 10 to concentration
-4The PCB101 of M also can detect effectively.
Embodiment
At first make or buy oxalic acid, zinc chloride and ethanol from market with ordinary method, as the PCB1～PCB127 of polychlorobiphenyl, totally 127 kinds.Then,
Embodiment 1
The concrete steps of preparation are:
Step 1 is that dropping concentration is the liquor zinci chloridi of 0.01M in 70 ℃ the saturated oxalic acid solution to stirring temperature down earlier; Wherein, the speed that in saturated oxalic acid solution, drips liquor zinci chloridi is 2ml/min, obtains white depositions.Water and ethanol after the repetitive scrubbing white depositions, carry out drying treatment to it successively again; Wherein, water and the ethanol number of times of repetitive scrubbing white depositions successively are 3 times, and the temperature during drying treatment is 70 ℃, and the time is 3h, obtain two oxalic acid hydrate zinc precursor things.
Step 2, it is 480 ℃ of following roasting 2h that two oxalic acid hydrate zinc precursor things are placed temperature, makes shown in the curve among Fig. 1 a, and is similar to the porous zinc bloom micro-powder shown in Fig. 1 b, Fig. 1 c and Fig. 1 d.
Embodiment 2
The concrete steps of preparation are:
Step 1 is that dropping concentration is the liquor zinci chloridi of 0.015M in 75 ℃ the saturated oxalic acid solution to stirring temperature down earlier; Wherein, the speed that in saturated oxalic acid solution, drips liquor zinci chloridi is 2ml/min, obtains white depositions.Water and ethanol after the repetitive scrubbing white depositions, carry out drying treatment to it successively again; Wherein, water and the ethanol number of times of repetitive scrubbing white depositions successively are 3 times, and the temperature during drying treatment is 75 ℃, and the time is 2.5h, obtain two oxalic acid hydrate zinc precursor things.
Step 2, it is 490 ℃ of following roasting 1.5h that two oxalic acid hydrate zinc precursor things are placed temperature, makes shown in the curve among Fig. 1 a, and is similar to the porous zinc bloom micro-powder shown in Fig. 1 b, Fig. 1 c and Fig. 1 d.
Embodiment 3
The concrete steps of preparation are:
Step 1 is that dropping concentration is the liquor zinci chloridi of 0.02M in 80 ℃ the saturated oxalic acid solution to stirring temperature down earlier; Wherein, the speed that in saturated oxalic acid solution, drips liquor zinci chloridi is 2ml/min, obtains white depositions.Water and ethanol after the repetitive scrubbing white depositions, carry out drying treatment to it successively again; Wherein, water and the ethanol number of times of repetitive scrubbing white depositions successively are 4 times, and the temperature during drying treatment is 80 ℃, and the time is 2h, obtain two oxalic acid hydrate zinc precursor things.
Step 2, it is 500 ℃ of following roasting 1.5h that two oxalic acid hydrate zinc precursor things are placed temperature, make shown in the curve among Fig. 1 a, and the porous zinc bloom micro-powder shown in Fig. 1 b, Fig. 1 c and Fig. 1 d.
Embodiment 4
The concrete steps of preparation are:
Step 1 is that dropping concentration is the liquor zinci chloridi of 0.025M in 85 ℃ the saturated oxalic acid solution to stirring temperature down earlier; Wherein, the speed that in saturated oxalic acid solution, drips liquor zinci chloridi is 2ml/min, obtains white depositions.Water and ethanol after the repetitive scrubbing white depositions, carry out drying treatment to it successively again; Wherein, water and the ethanol number of times of repetitive scrubbing white depositions successively are 4 times, and the temperature during drying treatment is 85 ℃, and the time is 1.5h, obtain two oxalic acid hydrate zinc precursor things.
Step 2, it is 510 ℃ of following roasting 1h that two oxalic acid hydrate zinc precursor things are placed temperature, makes shown in the curve among Fig. 1 a, and is similar to the porous zinc bloom micro-powder shown in Fig. 1 b, Fig. 1 c and Fig. 1 d.
Embodiment 5
The concrete steps of preparation are:
Step 1 is that dropping concentration is the liquor zinci chloridi of 0.03M in 90 ℃ the saturated oxalic acid solution to stirring temperature down earlier; Wherein, the speed that in saturated oxalic acid solution, drips liquor zinci chloridi is 2ml/min, obtains white depositions.Water and ethanol after the repetitive scrubbing white depositions, carry out drying treatment to it successively again; Wherein, water and the ethanol number of times of repetitive scrubbing white depositions successively are 5 times, and the temperature during drying treatment is 90 ℃, and the time is 1h, obtain two oxalic acid hydrate zinc precursor things.
Step 2, it is 520 ℃ of following roasting 1h that two oxalic acid hydrate zinc precursor things are placed temperature, makes shown in the curve among Fig. 1 a, and is similar to the porous zinc bloom micro-powder shown in Fig. 1 b, Fig. 1 c and Fig. 1 d.
Being applied as of porous zinc bloom micro-powder:
The PCB101 that one of selects for use among polychlorobiphenyl isomer PCB1～PCB127 (2,2 ', 4,5,5 '-pentachlorodiphenyl), earlier it being mixed with concentration is>=10
-4The solution of M; Again the porous zinc bloom micro-powder is soaked in the PCB101 solution, or the PCB101 drips of solution is added on the porous zinc bloom micro-powder, after waiting to contain the porous zinc bloom micro-powder drying of PCB101 solution; Promptly obtain to receive the porous zinc bloom powder (only being to be) of PCB101 pollution here for the porous zinc bloom micro-powder that obtains polluted by PCB101; Then, accomplish detection according to following steps
Step 1 places the porous zinc bloom micro-powder earlier to clamp between two conductive glass and fix, and is that wherein, monochromatic light intensity is 100mW/cm under the monochromatic ray irradiation of 400～550nm at wavelength
2, record the surface photovoltage V of porous zinc bloom micro-powder
1Again the porous zinc bloom micro-powder that polluted by PCB101 of same amount is placed and clamp and be fixed into identical density between two conductive glass; Under the monochromatic ray irradiation of identical wavelength and light intensity, record the surface photovoltage V of the porous zinc bloom micro-powder that receives the PCB101 pollution
2Wherein, surface measurements photovoltage V
1And V
2The time, be the MV of measuring 3 minutes.Then, use formula s=(V
1-V
2) * 100/V
1Calculate the reduction rate s of surface photovoltage.
Step 2 is with the reduction rate s substitution regression equation of surface photovoltage
Calculate the content m of the PCB101 to be measured shown in the curve among Fig. 2, wherein,
M in the formula, s is respectively m, and the MV of s, n are the number of the s that records, and the unit of m is a milligram.
Select for use respectively again as among the PCB1～PCB127 of polychlorobiphenyl any, repeat to implement the application of porous zinc bloom micro-powder, obtained equally as or be similar to the detected result of the content of the polychlorobiphenyl to be measured shown in the curve among Fig. 2.
Obviously, those skilled in the art can to porous zinc bloom micro-powder of the present invention and its production and application carry out various changes and modification and do not break away from the spirit and scope of the present invention.Like this, belong within the scope of claim of the present invention and equivalent technologies thereof if of the present invention these are revised with modification, then the present invention also is intended to comprise these changes and modification interior.
Claims (10)
1. porous zinc bloom micro-powder is that the particulate state zinc oxide of 50～100nm constitutes by particle diameter, it is characterized in that:
Said particulate state zinc oxide constitutes the porous micron block, and the bore dia in the hole on the said porous micron block is 20～70nm;
The block length of said porous micron block be 5～10 μ m, piece wide be that 5～10 μ m, piece height are 10～20 μ m;
The specific surface area of said porous micron block is 8～9m
2/ g.
2. porous zinc bloom micro-powder according to claim 1; The bore dia that it is characterized in that the hole on the porous micron block is on the bore dia and block length direction on the high direction of piece, the diplopore of the bore dia on the piece cross direction directly distributes; Bore dia on the high direction of piece in said diplopore footpath is 40～70nm, and the bore dia on the block length direction, on the piece cross direction is 20～50nm.
3. the preparation method of the said porous zinc bloom micro-powder of claim 1 comprises solution method, it is characterized in that completing steps is following:
Step 1; Be that dropping concentration is the liquor zinci chloridi of 0.01～0.03M in 70～90 ℃ the saturated oxalic acid solution to stirring temperature down earlier, obtain white depositions, water and ethanol are successively after the repetitive scrubbing white depositions again; It is carried out drying treatment, obtain two oxalic acid hydrate zinc precursor things;
Step 2, it is 480～520 ℃ of following roastings 1h at least that two oxalic acid hydrate zinc precursor things are placed temperature, makes the porous zinc bloom micro-powder.
4. the preparation method of porous zinc bloom micro-powder according to claim 3 is characterized in that the speed of dropping liquor zinci chloridi in saturated oxalic acid solution is 2mL/min.
5. the preparation method of porous zinc bloom micro-powder according to claim 3, it is characterized in that water and ethanol successively the number of times of repetitive scrubbing white depositions be more than 3 times.
6. the preparation method of porous zinc bloom micro-powder according to claim 3, the temperature when it is characterized in that drying treatment are 70～90 ℃, and the time is 1～3h.
7. the application of the said porous zinc bloom micro-powder of claim 1 comprises the porous zinc bloom micro-powder that receives pollution by polychlorinated biphenyles, it is characterized in that:
Step 1 places the porous zinc bloom micro-powder earlier to clamp between two conductive glass and fix, and is under the monochromatic ray irradiation of 400～550nm at wavelength, records the surface photovoltage V of porous zinc bloom micro-powder
1Again the porous zinc bloom micro-powder that receives pollution by polychlorinated biphenyles of same amount is placed and clamp and be fixed into identical density between two conductive glass; Under the monochromatic ray irradiation of identical wavelength and light intensity, record the surface photovoltage V of the porous zinc bloom micro-powder that receives pollution by polychlorinated biphenyles
2, then, use formula s=(V
1-V
2) * 100/V
1Calculate the reduction rate s of surface photovoltage;
Step 2; The reduction rate s substitution regression equation
of surface photovoltage is calculated the content m of polychlorobiphenyl to be measured; Wherein
8. the application of porous zinc bloom micro-powder according to claim 7 is characterized in that monochromatic light intensity is 100mW/cm
2
9. the application of porous zinc bloom micro-powder according to claim 8 is characterized in that surface measurements photovoltage V
1And V
2The time, be the MV of measuring 3 minutes.
10. the application of porous zinc bloom micro-powder according to claim 9 is characterized in that polychlorobiphenyl is any among PCB1～PCB127.
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| CN103134753A (en) * | 2011-11-29 | 2013-06-05 | 中国科学院合肥物质科学研究院 | Zinc oxide composite material modified by phthalocyanines copper and producing method and function thereof |
| CN105271363B (en) * | 2015-08-14 | 2017-12-22 | 南京华狮化工有限公司 | A kind of preparation method of super fine zinc oxide powder |
| CN112110476B (en) * | 2020-09-24 | 2022-10-21 | 安徽省含山县锦华氧化锌厂 | Zinc oxide preparation method based on zinc chloride concentrated solution |
| CN113801527A (en) * | 2021-09-16 | 2021-12-17 | 长沙民德消防工程涂料有限公司 | Water-based transparent glass heat-insulating coating and preparation method thereof |
| CN115057464A (en) * | 2022-03-25 | 2022-09-16 | 华南理工大学 | Three-dimensional porous ZnO/SnO 2 Composite material, preparation method thereof and application thereof in nickel-zinc battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1418818A (en) * | 2002-12-23 | 2003-05-21 | 崔春芳 | Tech. for prepn. of nano zinc oxide powder |
| CN101318690A (en) * | 2008-07-16 | 2008-12-10 | 武汉大学 | Stephanoporate zinc oxide nano-powder and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1418818A (en) * | 2002-12-23 | 2003-05-21 | 崔春芳 | Tech. for prepn. of nano zinc oxide powder |
| CN101318690A (en) * | 2008-07-16 | 2008-12-10 | 武汉大学 | Stephanoporate zinc oxide nano-powder and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2005-296864A 2005.10.27 |
| 贾志刚等.纳米晶构筑一维多孔氧化锌的合成与表征.《无机化学学报》.2007,第23卷(第7期),第1277-1281页. * |
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