CN105836793B - A kind of SnO2/ ZnO nano composite and preparation method thereof - Google Patents
A kind of SnO2/ ZnO nano composite and preparation method thereof Download PDFInfo
- Publication number
- CN105836793B CN105836793B CN201610298192.8A CN201610298192A CN105836793B CN 105836793 B CN105836793 B CN 105836793B CN 201610298192 A CN201610298192 A CN 201610298192A CN 105836793 B CN105836793 B CN 105836793B
- Authority
- CN
- China
- Prior art keywords
- sno
- zno
- solution
- microwave
- zno nanorod
- 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
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of SnO2/ ZnO nano composite and preparation method thereof, including ZnO nanorod and the SnO that is grown on ZnO nanorod2Nanometer rods, mainly the direct growth secondary structure SnO on trunk structure ZnO nanorod2Nanometer rods, by microwave radiation technology hydro-thermal method prepare wurtzite structure ZnO nanorod, then again on ZnO nanorod microwave radiation technology hydrothermal growth rutile structure SnO2Nanometer rods, without any template and catalyst in microwave radiation technology water-heat process, speed is fast, technique is simple, yield is high, and with low cost, is adapted to batch production, prepared nano composite material form is homogeneous, cladding is close, can be used as the infrared compatible camouflage materials of radar, photocatalysis, solar cell, gas sensor and lithium ion battery negative material.
Description
Technical field
The invention belongs to field of nanometer material technology, it is related to a kind of SnO2/ ZnO nano composite and preparation method thereof.
Background technology
ZnO and SnO2It is two kinds of important direct wide bandgap semiconductor functional materials.ZnO is that energy gap swashs for 3.37eV
Sub- binding energy is 60meV, SnO2Energy gap is 3.6eV, and exciton bind energy is 130meV, ZnO and SnO2Composite is extensive
Apply in gas sensor, solar cell, photocatalysis, lithium ion battery negative material and material obsorbing radar waves.By ZnO
With SnO2Both materials carry out compound composition SnO2/ ZnO material, is compared compared with homogenous material, in the side such as air-sensitive, photocatalysis performance
Face all increases significantly, therefore the preferably control ZnO and SnO in growth course2It is good that the growth of nano material obtains quality
And the nano composite material with particular hierarchy, it is upper significant in application.There are a large amount of research works at present
Person is engaged in ZnO and SnO2Material compound simultaneously achieves corresponding achievement, and such as Chinese patent CN200810116624 discloses one
Plant one-dimensional SnO2The preparation method of-ZnO alloplasm nanobranch, using gas transport, two step thermal evaporations are in Al2O3Substrate
Upper growth is obtained with SnO2For axle, ZnO is the SnO of branch2- ZnO alloplasm nanobranch, its preparation process is relatively cumbersome, needs
Want hot environment, and obtained SnO2- ZnO alloplasm nanobranch is unordered in a jumble, limits property and the application of material.
The content of the invention
For the defect and deficiency of existing technology of preparing, directly grown the invention provides a kind of on ZnO nanorod
SnO2Nano composite material preparation method, its preparation process is simple, aggregate velocity is fast, reaction temperature is low and of the invention prepares
Monocrystalline SnO2Nanometer rods are homogeneous, be fitly grown in ZnO nanorod surface, are conducive to improving the property of material.
To solve the above problems, the technical scheme that the present invention takes is:
A kind of SnO2/ ZnO nano composite, including ZnO nanorod and the SnO being grown on ZnO nanorod surface2Receive
Rice rod.
Further, including monomer, described monomer includes ZnO nanorod and raw in the SnO on ZnO nanorod2Receive
Rice rod.
Specifically, the draw ratio of described ZnO nanorod is 5~20, SnO2The draw ratio of nanometer rods is 5~60.
More specifically, the length of described ZnO nanorod is 5~10 μm, a diameter of 0.5~1 μm of ZnO nanorod;Institute
The SnO stated2The length of nanometer rods is 200~600nm, SnO2A diameter of 10~40nm of nanometer rods.
Prepare described SnO2The method of/ZnO nano composite, including received using microwave radiation technology hydro-thermal method preparation ZnO
Rice rod, then the microwave radiation technology Hydrothermal Growth SnO on ZnO nanorod2Nanometer rods.
Specifically, described microwave assisted aqueous extraction hot preparation ZnO nanorod includes:Strong base solution is added to zinc compound
As reaction source in solution, reaction source carries out hydro-thermal reaction under microwave condition, and microwave power is 400W, and microwave temperature is 200
DEG C, the microwave time is 15min, and by the product washing of hydro-thermal reaction be neutral and drying obtains ZnO nanorod.
More specifically, described zinc compound solution is Zn (CH3COOH)2Zn (CH in solution, reaction source3COOH)2It is molten
The concentration of liquid is 0.1mol/L, and described strong base solution is that the concentration of NaOH solution in NaOH solution, reaction source is 1.4mol/L.
Specifically, it is described that microwave radiation technology Hydrothermal Growth SnO is used on ZnO nanorod2Nanometer rods include:Will be stanniferous
Compound solution, which is added in strong base solution, obtains growth solution, and ZnO nanorod, which is added in growth solution, carries out microwave hydrothermal
Reaction, microwave power is 400W, and microwave temperature is 180~220 DEG C, and the microwave time is 15~60min, and microwave hydrothermal is reacted
Product washing is neutral and drying SnO2/ZnO nano composite materials.
More specifically, described sn-containing compound solution is SnCl4Solution, described strong base solution is NaOH solution, raw
NaOH and SnCl in long solution4Mol ratio be [NaOH]:[SnCl4]=6~10:1, SnCl in microwave hydrothermal reaction4With ZnO
Mol ratio be [SnCl4]:[ZnO]=4~7:1.
Advantages of the present invention is:
(1) SnO that the present invention is prepared2/ ZnO nano composite be length be 5~10 μm, diameter be about 0.5
~1 μm, draw ratio for 5~20 ZnO on grow SnO2Monocrystal nano rod, and SnO2Monocrystal nano rod along ZnO superficial growths,
SnO2The length of nanometer rods is 200~600nm, and a diameter of 10~40nm, its draw ratio is 5~60;From microstructure, SnO2/
ZnO nano composite has very big specific surface area, can be used as gas sensor, SnO2/ ZnO nano composite is present
Substantial amounts of hetero-junctions, photo-generated carrier is compound to be reduced, and electron hole pair is efficiently separated, so as to add life-span and the load of carrier
Flow sub- concentration so that SnO2/ ZnO nano composite can be used as photocatalysis, gas sensor and negative electrode of lithium ion battery material
Material.
(2) present invention is preparing SnO2During/ZnO nano composite, grown using microwave radiation technology hydro-thermal method on ZnO
SnO2Without any template and catalyst in monocrystal nano rod, water-heat process, speed is fast, and technique is simple, and yield is high, and cost is low
It is honest and clean, it is adapted to batch production;
(3) the direct growth SnO on ZnO2Nanometer rods, prepared nano composite material form is homogeneous, cladding is close.
Brief description of the drawings
Fig. 1 is the XRD spectrum of embodiment 1 in the present invention;
Fig. 2 is the XRD spectrum of embodiment 2 in the present invention;
Fig. 3 is the XRD spectrum of embodiment 3 in the present invention;
Fig. 4 is the SEM photograph of embodiment 1 in the present invention;
Fig. 5 is the SEM photograph of embodiment 2 in the present invention;
Fig. 6 is the SEM photograph of embodiment 3 in the present invention;
Fig. 7 is the XRD spectrum of embodiment 4 in the present invention;
Fig. 8 is the SEM photograph of embodiment 4 in the present invention
The present invention is illustrated below in conjunction with specification drawings and specific embodiments.
Embodiment
SnO prepared by the present invention2/ ZnO nano composite, is directly existed using simple microwave radiation technology hydro-thermal template-free method
SnO is grown on ZnO nanorod2Nanometer rods, using ZnO nanorod as trunk structure, SnO2For the sandwich of secondary structure.
It is of the invention main using microwave radiation technology hydro-thermal method, by controlling the concentration of pink salt in reaction system, alkali salt ratio, pink salt
A kind of SnO is obtained with the factor such as zinc salt concentration ratio, reaction temperature, reaction time2/ ZnO nano composite and prepare the material
Without any template or catalyst in the method for material, water-heat process, speed is fast, and technique is simple, and yield is high, and with low cost, fits
Close batch production;ZnO nanorod is used as trunk structure direct growth SnO2Nanometer rods, prepared monocrystalline SnO2Nanometer rods form is equal
One, it is evenly coated on ZnO.
In order that objects and advantages of the present invention are more clearly understood, the present invention is carried out below in conjunction with drawings and examples
It is further described.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to limit
The present invention.
Embodiment one:
Step one:1.4mol/L NaOH solution is poured into 0.1mol/L Zn (CH3COOH)2·2H2(body in O solution
Product is than being 1:1) precursor solution is obtained after, being sufficiently stirred for, 30ml precursor solutions are moved into the reactor (liner of TFM liners
Volume be 100ml), be sealed against being placed under 400W microwave power, 200 DEG C insulation 15min, question response terminate after will reaction
Processing is centrifuged in product, and is washed with deionized repeatedly, until the pH=7 of filtrate, is then placed in products therefrom
Dried in baking oven at 60 DEG C, obtain ZnO nanorod, length is 5~10 μm, diameter is about 0.5~1 μm.
Step 2, by 0.05mol/L SnCl4·5H2O solution is added dropwise in 0.3mol/L NaOH solution dropwise, titration
After the completion of one ZnO nanorod prepared and continue stirring 30min (three's mol ratio be the step of add 0.01mol/L
[SnCl4]:[NaOH]:[ZnO]=5:30:1) precursor solution is obtained, takes 30ml precursor solutions to move into the reaction of TFM liners
Kettle (volume of liner is 100ml), is placed under 400W microwave power, 15min, question response knot is incubated in 180 DEG C of baking ovens
Reaction product is centrifuged after beam, and is washed with deionized repeatedly, until the pH=7 of filtrate, is then produced gained
Thing is placed in baking oven at 60 DEG C and dried, and obtains SnO2/ ZnO nano composite.
The XRD spectrum of the product is as shown in figure 1, SEM photograph is as shown in Figure 4;Fig. 1 illustrates that the product of embodiment one is
SnO2/ ZnO compounds, Fig. 4 illustrates the product SnO of embodiment one2/ ZnO pattern, obtains SnO2The length of nanometer rods be 250~
300nm, a diameter of 15~20nm.
Embodiment two:
Step one:It is identical with embodiment one.
Step 2:By 0.1mol/L SnCl4·5H2O solution is added dropwise in 0.9mol/L NaOH solution dropwise, titration
After the completion of add 0.02mol/L ZnO and continue stirring 30min (three's mol ratio be [SnCl4]:[NaOH]:[ZnO]=5:
45:1) precursor solution is obtained, takes 30ml precursor solutions to move into the reactor (volume of liner is 100ml) of TFM liners, will
It is placed under 400W microwave power, and 30min is incubated in 200 DEG C of baking ovens, and reaction product is carried out centrifugation point by question response after terminating
From, and be washed with deionized repeatedly, until the pH=7 of filtrate, then products therefrom is placed in baking oven at 60 DEG C and dried, just
Obtain SnO2/ ZnO nano composite.
The X ray diffracting spectrum of the product is as shown in Fig. 2 electron scanning micrograph is as shown in Figure 5;Fig. 2 explanations are real
The product for applying example two is SnO2/ ZnO compounds, Fig. 5 illustrates the product SnO of embodiment two2/ appearance of ZnO, obtains SnO2Nanometer rods
Length be 200~300nm, a diameter of 10~20nm.
Embodiment three:
Step one:It is identical with embodiment one.
Step 2:By 0.3mol/L SnCl4·5H2O solution is added dropwise in 1.8mol/L NaOH solution dropwise, titration
After the completion of add 0.05mol/L ZnO and continue stirring 30min (three's mol ratio be [SnCl4]:[NaOH]:[ZnO]=6:
36:1) precursor solution is obtained, takes 30ml precursor solutions to move into the reactor (volume of liner is 100ml) of TFM liners, will
It is placed under 400W microwave power, and 60min is incubated in 220 DEG C of baking ovens, and reaction product is carried out centrifugation point by question response after terminating
From, and be washed with deionized repeatedly, until the pH=7 of filtrate, then products therefrom is placed in baking oven at 60 DEG C and dried, just
Obtain SnO2/ ZnO nano composite.
The X ray diffracting spectrum of the product is as shown in figure 3, electron scanning micrograph is as shown in Figure 6;Fig. 3 explanations are real
The product for applying example three is SnO2/ ZnO compounds, Fig. 6 illustrates the product SnO of embodiment three2/ appearance of ZnO, SnO2The length of nanometer rods
Spend for 300~600nm, a diameter of 20~40nm.
Example IV:Comparative example
Step one:It is identical with embodiment one.
Step 2:By 0.1mol/L SnCl4·5H2O solution is added dropwise in 0.9mol/L NaOH solution dropwise, titration
After the completion of add 0.025mol/L ZnO and continue stirring 30min (three's mol ratio be 4:36:1), by mixed solution, take
30ml precursor solutions move into the reactor (volume of liner is 100ml) of TFM liners, are placed on 400W microwave power
Under, 60min is incubated in 160 DEG C of baking ovens, reaction product is centrifuged after terminating for question response, and is washed with deionized many
It is secondary, until the pH=7 of filtrate, then products therefrom is placed in baking oven at 60 DEG C and dried.
The X ray diffracting spectrum of the product is as shown in fig. 7, electron scanning micrograph is as shown in Figure 8;Fig. 7 explanations are real
The product for applying example four is ZnSn (OH)6With ZnO compound, it is clear that without SnO2Generation.Fig. 8 illustrates the product shape of example IV
Looks, it is octahedral ZnSn (OH)6With bar-shaped ZnO.Obviously, in present case, SnO2/ ZnO structures can not at 160 DEG C shape
Into.
In summary, the present invention relates to a kind of SnO2The preparation method of/ZnO nano-structure compound, the hydro-thermal used
Preparation process technique is simple, and speed is fast, and controllability is strong, and yield is high, with low cost, is adapted to batch production.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (3)
1. one kind prepares SnO2The method of/ZnO nano composite, it is characterised in that including being prepared using microwave radiation technology hydro-thermal method
ZnO nanorod, then the microwave radiation technology Hydrothermal Growth SnO on ZnO nanorod2Nanometer rods;
Described microwave assisted aqueous extraction hot preparation ZnO nanorod includes:Strong base solution is added in zinc compound solution as
Reaction source, reaction source carries out hydro-thermal reaction under microwave condition, and microwave power is 400W, and microwave temperature is 200 DEG C, microwave time
For 15min, by the product washing of hydro-thermal reaction be neutral and drying obtains ZnO nanorod;
Described uses microwave radiation technology Hydrothermal Growth SnO on ZnO nanorod2Nanometer rods include:Sn-containing compound solution is added
Enter and growth solution is obtained into strong base solution, ZnO nanorod is added to progress microwave hydrothermal reaction, microwave power in growth solution
For 400W, microwave temperature is 180~220 DEG C, and the microwave time is 15~60min, in being by the product washing that microwave hydrothermal reacts
Property and drying SnO2/ ZnO nano composite;
Described SnO2/ ZnO nano composite includes ZnO nanorod and the SnO being grown on ZnO nanorod surface2Nanometer
Rod;
The draw ratio of described ZnO nanorod is 5~20, SnO2The draw ratio of nanometer rods is 5~60;
The length of described ZnO nanorod is 5~10 μm, a diameter of 0.5~1 μm of ZnO nanorod;Described SnO2Nanometer rods
Length be 200~600nm, SnO2A diameter of 10~40nm of nanometer rods.
2. SnO is prepared as claimed in claim 12The method of/ZnO nano composite, it is characterised in that described contains zinc impregnation
Polymer solution is Zn (CH3COOH)2Zn (CH in solution, reaction source3COOH)2The concentration of solution is 0.1mol/L, described highly basic
Solution is that the concentration of NaOH solution in NaOH solution, reaction source is 1.4mol/L.
3. SnO is prepared as claimed in claim 12The method of/ZnO nano composite, it is characterised in that described stanniferousization
Polymer solution is SnCl4Solution, described strong base solution is NaOH and SnCl in NaOH solution, growth solution4Mol ratio be
[NaOH]:[SnCl4]=6~10:1, SnCl in microwave hydrothermal reaction4Mol ratio with ZnO is [SnCl4]:[ZnO]=4~7:
1。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610298192.8A CN105836793B (en) | 2016-05-06 | 2016-05-06 | A kind of SnO2/ ZnO nano composite and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610298192.8A CN105836793B (en) | 2016-05-06 | 2016-05-06 | A kind of SnO2/ ZnO nano composite and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105836793A CN105836793A (en) | 2016-08-10 |
CN105836793B true CN105836793B (en) | 2017-11-03 |
Family
ID=56591657
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610298192.8A Expired - Fee Related CN105836793B (en) | 2016-05-06 | 2016-05-06 | A kind of SnO2/ ZnO nano composite and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN105836793B (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106517315B (en) * | 2016-08-17 | 2018-01-12 | 安徽建筑大学 | 1-dimention nano composite metal oxide gas-sensing material and preparation method thereof |
CN108205004A (en) * | 2016-12-16 | 2018-06-26 | 南京理工大学 | Enzyme-free glucose electrochemical sensing nanocomposite and preparation method thereof |
CN107352575B (en) * | 2017-05-24 | 2019-03-19 | 江苏时恒电子科技有限公司 | A kind of preparation method of the ZnO nanoparticle for gas sensor |
CN109694101B (en) * | 2019-02-14 | 2021-05-28 | 西北大学 | SnO (stannic oxide)2@ ZnO nano composite material and preparation method thereof |
CN109967075B (en) * | 2019-03-29 | 2021-12-03 | 昆明理工大学 | ZnO-SnO doped with metal platinum2Preparation method of composite photocatalytic material |
CN110040766B (en) * | 2019-04-02 | 2021-09-03 | 重庆大学 | Preparation method of high-humidity-resistance nano gas-sensitive material and gas-sensitive sensor |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100569654C (en) * | 2007-11-23 | 2009-12-16 | 陕西科技大学 | A kind of preparation method of ZnO nanometer rod |
CN102618849B (en) * | 2012-03-15 | 2013-07-10 | 中国科学院理化技术研究所 | Method for preparing one-dimensional ZnO/SnO2 core/shell structure nano heterojunction semiconductor material |
-
2016
- 2016-05-06 CN CN201610298192.8A patent/CN105836793B/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN105836793A (en) | 2016-08-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105836793B (en) | A kind of SnO2/ ZnO nano composite and preparation method thereof | |
CN105238349B (en) | A kind of Fe3O4ZnO nano composite and preparation method thereof | |
CN105948105B (en) | A kind of SnO2/ ZnO nano composite and preparation method thereof | |
CN107068872A (en) | One kind prepares perovskite Cs3Bi2I9The method of hull cell | |
CN105789339A (en) | Perovskite solar cell nano silicon dioxide coating liquid and application thereof | |
CN105293563B (en) | Zinc oxide nano sheet cluster and preparation method thereof | |
CN106986373A (en) | A kind of preparation method of ZnO nanorod | |
CN109694101B (en) | SnO (stannic oxide)2@ ZnO nano composite material and preparation method thereof | |
CN103920505B (en) | A kind of visible light photocatalysis highly effective hydrogen yield cadmium sulfide counter opal structure and preparation method thereof | |
CN103508484B (en) | Infrared low-emissivity nanocrystalline thin-film material SnO2 and preparation method thereof | |
CN105742080A (en) | Preparation method for one-dimensional ordered titanium dioxide nanorod array composite material | |
CN104192890A (en) | Method for preparing carbon-dope zinc oxide nanopillars | |
CN103466688B (en) | A kind of method for preparing ZnS nanosheet | |
CN105236472A (en) | Preparation method of SnO2 nano-wire array | |
CN108298582A (en) | One kind is by VO2The preparation method of hollow ball and film that nanoscale twins surround | |
CN102502776B (en) | Method for preparing Cu1.8S nanowire by microwave-hydrothermal method | |
CN102795665B (en) | Preparation method of titanium dioxide nanotube (rod) array | |
CN109650438A (en) | Nanometer witch culture tin dioxide powder and preparation method thereof | |
CN103241764B (en) | Preparation method of three-dimensional zinc oxide flower-like structure | |
CN108456921B (en) | A kind of preparation method of high length-diameter ratio zirconium oxide whisker | |
CN113637941A (en) | Preparation method of zinc-gallium oxide magnetron sputtering target material | |
CN102583554B (en) | Method for preparing hexagonal piece self-assembled gamma-MnS microcrystalline spheres | |
Yang et al. | Synthesis and characterization of sol-gel derived TiO 2 thin films: effect of different pretreatment process | |
CN108456488A (en) | A kind of photovoltaic coating and preparation method improving solar energy conversion | |
CN105502489B (en) | Method for preparing branched orderly titanium dioxide nano-rod array |
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: 20171103 Termination date: 20180506 |
|
CF01 | Termination of patent right due to non-payment of annual fee |