CN102134092A - Simple preparation method of hollow-spherical and flower-shaped indium oxide with secondary structure and application - Google Patents
Simple preparation method of hollow-spherical and flower-shaped indium oxide with secondary structure and application Download PDFInfo
- Publication number
- CN102134092A CN102134092A CN 201110039341 CN201110039341A CN102134092A CN 102134092 A CN102134092 A CN 102134092A CN 201110039341 CN201110039341 CN 201110039341 CN 201110039341 A CN201110039341 A CN 201110039341A CN 102134092 A CN102134092 A CN 102134092A
- Authority
- CN
- China
- Prior art keywords
- indium
- indium sesquioxide
- flower
- secondary structure
- shaped
- 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 provides a preparation method of indium oxide with new appearance, belonging to the technical field of synthesis and nano material of the indium oxide. The preparation method comprises the following steps: taking inorganic salt solution of the indium as an indium source, adopting N, N-dimethyl formamide (DMF) as an alkali source and anion active agents such as sodium dodecyl sulfate (SDS) and the like as an additive, using hydrothermal synthesis to prepare the novel hollow-microspherical and flower-shaped indium oxide with the secondary structure under the condition without adding any hard template, and controlling the appearance of the secondary structure by chemical means. In the preparation method provided by the invention, the technical process is simple, the promotion is easy, the selected reagent is low in price and environment-friendly, and the need on low-cost, large-scale and green production is met.
Description
Technical field
The present invention relates to a kind of preparation and have the hollow ball of secondary structure and the simple and easy method and the application thereof of flower-shaped Indium sesquioxide, belong to the synthetic and Application Areas of micrometer/nanometer control of material.
Background technology
As everyone knows, the character of inorganic micrometer/nanometer material is relevant with particulate size and shape.Present extensive work concentrates on the control of the micrometer/nanometer material of different shapes, size, dimension and structure and synthesizes.Especially to by nano structured unit; such as nano particle; nanometer rod/line/band or nanometer sheet make up the 3D micrometer/nanometer structured material that forms with level time or complex construction research oneself through becoming one of research focus of material; this is because the secondary structure of material can produce excellent more overall coordination character usually; the characteristic that not only can have structural unit; the coupling effect that also may have the nano structured unit combination results; thereby synergistic effect etc. make these materials show the physics and the chemical property of the uniqueness that is different from its construction unit and block materials, and this is that further design designs novel Nano/micron dimension transducer; device provides solid basis.Recently, people oneself through having reported many Nano/micron materials with level aggregated(particle) structure of different-shape, and set forth they catalysis, Conversion of energy and storage, environmental purification, transmitter and biological aspect potential application.（a)H.?Jiang,?J.?Q.?Hu,?F.?Gu,?W.?Shao?and?C.Z.?Li,?
Chem.?Commun.,?2009,?3618,?b)K.I.?Choi,?H.R.?Kim,?J.H.?Lee,?
Sens.?Actuators?B，2009,?138,?497.）
Indium sesquioxide is a kind of N-type semiconductor, belongs to III-VI family, has the direct band gap of 3.55 –, 3.75 eV, has high conductivity and visible light transmissivity.Nanostructure or the Indium sesquioxide that makes up by nano structured unit with secondary structure, show electricity, the optical property of many novelties owing to quantum confined effect with current carrier, can be used for fields such as solar cell, transparent conductor, window well heater, opto-electronic device, flat-panel monitor, UV, visible light (ultraviolet ray) laser apparatus, detector, Organic Light Emitting Diode and gas sensor application (a) I. Hamberg and C. G. Granqvist is very widely all arranged
J. Appl. Phys., 1986,60,123; B) H. Zhou, W. Cai and L. Zhang,
Appl. Phys. Lett., 1999,26,495; C) N. Pinna, G. Neri, M. Antonietti and M. Niederberger,
Angew. Chem., Int. Ed., 2004,43,4345).It is used widely and makes that the control of Indium sesquioxide is synthetic important Research Significance arranged, so the micrometer/nanometer Indium sesquioxide with secondary structure that is made up by nano structured unit is in the news successively.For example use sucrose as the synthetic hollow ball Indium sesquioxide with needle-like or shaft-like secondary structure of hard template (H. Jiang, J. Q. Hu, F. Gu, W. Shao and C.Z. Li,
Chem. Commun., 2009,3618) and synthesize hollow ball Indium sesquioxide with amino acid as additive with nano particle secondary structure, (K.I. Choi, H.R. Kim, J.H. Lee,
Sens. Actuators B, 2009,138,497) and use urea synthesis to have the flower-shaped microballoon Indium sesquioxide of shaft-like secondary structure, (H.Z., X.L. Wang, F. Yang, and X.R. Yang,
Crystal Growth ﹠amp; Design, 2008,8,950.) add the synthetic flower-shaped ball Indium sesquioxide with porous nano-sheet secondary structure of thiocarbamide (J.Y. Liu, T. Luo, F.L. Meng, K. Qian, Y.T. Wan, and J.H. Liu,
J. Phys. Chem. C2010,
114,4887) etc.But above-mentioned synthetic method existence condition harshness, cost is higher, complicated operation, problems such as Indium sesquioxide that can only synthesizing single shape, what have can not large batch of synthetic putting into production.
Summary of the invention
The objective of the invention is to solve technological deficiencies such as production cost height, experiment condition harshness, complicated operation in the above-mentioned Indium sesquioxide preparation process, a kind of simple method for preparing with secondary structure hollow spheres and flower-shaped Indium sesquioxide is provided, and with the sensitive material of synthetic material as gas sensor gas.
For achieving the above object, the present invention is by the following technical solutions:
(1) earlier a certain amount of indium salt and anion surfactant are added in the corresponding beaker that deionized water is housed, mix to dissolving then, again with a certain amount of N, dinethylformamide (DMF) adds in the middle of the above-mentioned solution, continue to stir and make its dissolving, changing the respective volume liner then over to is in the stainless steel autoclave of tetrafluoroethylene, and sealing back control autoclave temperature was 140～180 ℃ of hydro-thermal reactions 1～10 hour;
(2) after reaction finished, collecting reaction product obtained white precipitate, cleans the precursor of dry washed product Indium sesquioxide then repeatedly through deionized water, dehydrated alcohol;
(3) change precursor over to crucible and place retort furnace, under the certain temperature condition, calcine and promptly obtained Indium sesquioxide in 2～6 hours;
(4) with the sensitive material of synthetic Indium sesquioxide, hydrogen sulfide is tested as the catalytic luminescence transmitter.
Thereby wherein regularly can obtain the pattern of Indium sesquioxide by the amount control of control anion surfactant when these experiment conditions one of consumption, temperature of reaction and the hydro-thermal reaction time of indium salt; Thereby regularly can obtain the pattern of Indium sesquioxide when these experiment conditions one of consumption, temperature of reaction and anion surfactant consumption of indium salt by the control of control hydro-thermal reaction time.
A kind of in the inorganic salt that described indium salt is indiums such as indium chloride, indium sulfate and indium nitrate; Described anion surfactant is sodium laurylsulfonate (SDS) or Sodium dodecylbenzene sulfonate (SDBS).
Described step (3) hollow spheres Indium sesquioxide is being not less than that calcining obtains under 600 ℃ the condition being not less than 400 ℃, flower-shaped Indium sesquioxide.
Compared with prior art, the present invention has following beneficial effect:
A) raw material sources of the present invention are extensive, and experimental technique is simple, and preparation method's cost is low;
B) preparation method of the present invention does not need to add hard template in addition, and is simple to operation;
C) method provided by the present invention is synthesized by the control that two kinds of new patterns of reaction times realization of regulating and control different anion surfactant consumptions or system have the Indium sesquioxide of secondary structure;
D) can be as the sensitive material of catalytic luminescence gas sensor.
Description of drawings
Fig. 1 is scanning electronic microscope (SEM) figure of Indium sesquioxide of the present invention and precursor thereof, wherein schemes a and be to have the SEM figure of precursor of the hollow microsphere Indium sesquioxide of secondary structure; Figure b is the SEM figure with hollow microsphere Indium sesquioxide of secondary structure; Figure c is the SEM figure of the precursor of flower-shaped Indium sesquioxide; Figure d is the SEM figure of flower-shaped Indium sesquioxide;
Fig. 2 is X-ray diffraction (XRD) collection of illustrative plates of Indium sesquioxide of the present invention.Wherein, a is the XRD figure with hollow microsphere Indium sesquioxide of secondary structure; Figure b is the XRD figure of flower-shaped Indium sesquioxide;
Fig. 3 is X-ray diffraction (XRD) figure of the precursor of Indium sesquioxide of the present invention.A has the XRD figure of precursor of the hollow microsphere Indium sesquioxide of secondary structure; Figure b is the XRD figure of the precursor of flower-shaped Indium sesquioxide;
Fig. 4 is transmission electron microscope (TEM), high-resolution-ration transmission electric-lens (HRTEM) and selected diffraction (SAED) figure of Indium sesquioxide of the present invention.Wherein, figure a, b are the TEM figure with hollow microsphere Indium sesquioxide of secondary structure; Figure c has the HRTEM figure of the hollow microsphere Indium sesquioxide of secondary structure; Figure d is the SAED figure with hollow microsphere Indium sesquioxide of secondary structure.Figure e is the TEM figure of flower-shaped Indium sesquioxide; Figure f is that the XRD figure of flower-shaped Indium sesquioxide is the HRTEM figure of flower-shaped Indium sesquioxide; Figure g is the SAED figure of flower-shaped Indium sesquioxide;
Fig. 5 be adopt method of the present invention institute synthetic hollow ball Indium sesquioxide as the catalytic luminescence sensitive material respectively to the response of the hydrogen sulfide of 2 ppm and 4 ppm.
Embodiment
Has the hollow spheres Indium sesquioxide of secondary structure and the simple method for preparing and the application thereof of flower-shaped Indium sesquioxide is described further below by embodiment to of the present invention.Present embodiment is being to implement under the prerequisite with the present invention program, has provided detailed embodiment and concrete operating process.
Embodiment 1:
A) earlier 2 mmol indium chlorides, 4g SDS are added in the 50mL beaker that the 40mL deionized water is housed, mixed stir about then 20 minutes.Again 4 mL DMF are added in the middle of the above-mentioned solution, continued stir about 10 minutes.This solution is changed in the 60mL teflon-lined autoclave, place 160 ℃ to keep 10 hours down autoclave after the sealing.After 10 hours autoclave is taken out, to be cooledly to room temperature, open autoclave, product is transferred in the beaker;
B) above-mentioned product is cleaned repeatedly with deionized water and dehydrated alcohol.Last white precipitate is placed 60 ℃ of oven dry down.White precipitate is precursor.And prepared white precursor carried out XRD, the sign of SEM;
C) precursor after will drying is transferred in the crucible, with crucible put into retort furnace 400 ℃ keep 5 hours down after, take out, be cooled to room temperature.The yellow final product that obtains has at last been carried out XRD, SEM, the sign of TEM.
Embodiment 2:
A) earlier 2 mmol indium chlorides, 6g SDS are added in the 50mL beaker that the 40mL deionized water is housed, mixed stir about then 20 minutes.Again 4 mL DMF are added in the middle of the above-mentioned solution, continued stir about 10 minutes.This solution is changed in the 60mL teflon-lined autoclave, place 160 ℃ to keep 10 hours down autoclave after the sealing.After 10 hours autoclave is taken out, to be cooledly to room temperature, open autoclave, product is transferred in the beaker;
B) above-mentioned product is cleaned repeatedly with deionized water and dehydrated alcohol.Last white precipitate is placed 60 ℃ of oven dry down.White precipitate is precursor.And prepared white precursor carried out XRD, the sign of SEM;
C) precursor after will drying is transferred in the crucible, with crucible put into retort furnace 600 ℃ keep 5 hours down after, take out, be cooled to room temperature.The yellow final product that obtains has at last been carried out XRD, SEM, the sign of TEM.
Embodiment 3:
A) earlier 2 mmol indium chlorides, 1g SDS are added in the 50mL beaker that the 40mL deionized water is housed, mixed stir about then 20 minutes.Again 4 mL DMF are added in the middle of the above-mentioned solution, continued stir about 10 minutes.This solution is changed in the 60mL teflon-lined autoclave, place 160 ℃ to keep 10 hours down autoclave after the sealing.After 10 hours autoclave is taken out, to be cooledly to room temperature, open autoclave, product is transferred in the beaker;
B) above-mentioned product is cleaned repeatedly with deionized water and dehydrated alcohol.Last white precipitate is placed 60 ℃ of oven dry down.White precipitate is precursor.And prepared white precursor carried out XRD, the sign of SEM;
C) precursor after will drying is transferred in the crucible, with crucible put into retort furnace 400 ℃ keep 5 hours down after, take out, be cooled to room temperature.
Embodiment 4:
Present embodiment is mainly in order to investigate in the above-mentioned Indium sesquioxide process of preparation experiment condition such as the concentration of SDS and hydro-thermal reaction time to the influence of Indium sesquioxide pattern.Concrete preparation method's method is with implementing 1, and different is amount, hydrothermal temperature and the reaction times that changes SDS in the reaction process respectively.The concrete quadrature form (table 1) of pressing is implemented.The SDS amount is many more as can be known by experimental result, and the time, long more then product tended to generate flower-shaped Indium sesquioxide; Long more then product tends to generate the hollow microsphere Indium sesquioxide with secondary structure between SDS measures more after a little while.And the secondary structure of hollow ball also can be along with the variation of the amount of SDS and reaction times length and is changed.
The hydro-thermal reaction experiment condition of the above-mentioned Indium sesquioxide of table 1 preparation
Embodiment 5:
Present embodiment is used for the catalytic luminescence gas sensor test experiment that the gas sensor sensitive material carries out for adopting the prepared Indium sesquioxide of the present invention.Concrete steps are as follows:
A) with the synthetic hollow microsphere Indium sesquioxide dip-coating about 0.05g on the ceramic heat rod.To have Indium sesquioxide after the oven dry
The ceramic heat rod is put into a silica tube good seal, and connects temperature regulator, inlet mouth, gives vent to anger, and puts into the illuminated chamber of catalytic luminescence detector;
B) with air as carrier gas, speed is 600 mL min
– 1, Heating temperature is 400 C.About the blowing air 10min of elder generation
Get rid of the interference of other foreign gases, treat that baseline stability begins the hydrogen sulfide of sample introduction 12ppm later, after signal is got back to baseline, continue the hydrogen sulfide of sample introduction 12ppm, sample introduction 3 times, the record experimental data, the result is as shown in Figure 5.
Experimental result shows that the hollow spheres Indium sesquioxide with secondary structure of the present invention can be used as the gas sensor sensitive material.
Claims (7)
1. novel hollow spheres and flower-shaped Indium sesquioxide with secondary structure is characterized in that its pattern of described hollow spheres is the sphere of comparison rule, outside diameter 1.5～3 μ m, inner hollow, surperficial secondary structure be the length of side 100～500nm cube; Described flower-shaped it is characterized in that clustering round by the lamella between multi-layered thickness 100～300nm form diameter 8～20 μ m.
2. the spherical and flower-shaped Indium sesquioxide of the described sky of claim 1 is as the application of gas sensor sensitive material.
3. novel have the hollow spheres of secondary structure and a preparation method of flower-shaped Indium sesquioxide, it is characterized in that processing step is as follows successively:
(a) earlier a certain amount of indium salt and anion surfactant are added in the corresponding beaker that deionized water is housed, mix to dissolving then, again with a certain amount of N, dinethylformamide (DMF) adds in the middle of the above-mentioned solution, continue to stir and make its dissolving, changing the respective volume liner then over to is in the stainless steel autoclave of tetrafluoroethylene, and sealing back control autoclave temperature was 140～180 ℃ of hydro-thermal reactions 1～10 hour;
(b) after reaction finished, collecting reaction product obtained white precipitate, cleans the precursor of dry washed product Indium sesquioxide then repeatedly through deionized water, dehydrated alcohol;
(c) change precursor over to crucible and place retort furnace, under the certain temperature condition, calcine and promptly obtained Indium sesquioxide in 2～6 hours.
4. described novel the have hollow spheres of secondary structure and the preparation method of flower-shaped Indium sesquioxide of claim 3 is characterized in that indium salt is a kind of in the inorganic salt of indiums such as indium chloride, indium sulfate and indium nitrate; Anion surfactant is sodium laurylsulfonate (SDS) or Sodium dodecylbenzene sulfonate (SDBS).
5. claim 3 is described novelly has the hollow spheres of secondary structure and the preparation method of flower-shaped Indium sesquioxide, thereby it is characterized in that regularly can obtaining by the amount control of control anion surfactant when these experiment conditions one of consumption, temperature of reaction and the hydro-thermal reaction time of indium salt the pattern of Indium sesquioxide.
6. claim 3 is described novelly has the hollow spheres of secondary structure and the preparation method of flower-shaped Indium sesquioxide, thereby it is characterized in that regularly can obtaining by the control of control hydro-thermal reaction time when these experiment conditions one of consumption, temperature of reaction and anion surfactant consumption of indium salt the pattern of Indium sesquioxide.
7. described novel the have hollow spheres of secondary structure and the preparation method of flower-shaped Indium sesquioxide of claim 3 is characterized in that step (3) hollow spheres Indium sesquioxide is being not less than that calcining obtains under 600 ℃ the condition being not less than 400 ℃, flower-shaped Indium sesquioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110039341 CN102134092B (en) | 2011-02-17 | 2011-02-17 | Simple preparation method of hollow-spherical and flower-shaped indium oxide with secondary structure and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110039341 CN102134092B (en) | 2011-02-17 | 2011-02-17 | Simple preparation method of hollow-spherical and flower-shaped indium oxide with secondary structure and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102134092A true CN102134092A (en) | 2011-07-27 |
| CN102134092B CN102134092B (en) | 2013-03-27 |
Family
ID=44294049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110039341 Expired - Fee Related CN102134092B (en) | 2011-02-17 | 2011-02-17 | Simple preparation method of hollow-spherical and flower-shaped indium oxide with secondary structure and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102134092B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503834A (en) * | 2011-09-29 | 2012-06-20 | 苏州大学 | Preparation method for porous sulfo-indium salt |
| CN102557114A (en) * | 2011-12-29 | 2012-07-11 | 中国科学院上海光学精密机械研究所 | Preparation method of indium oxide-based gas-sensitive material with three-dimensional hollow multi-stage structure and application thereof |
| CN103334179A (en) * | 2013-04-27 | 2013-10-02 | 青岛大学 | Hollow structure indium oxide nanometer fiber preparation method |
| CN103781723A (en) * | 2012-07-13 | 2014-05-07 | 首尔大学校产学协力团 | Three-dimensional nanoparticle assembly structure and gas sensor using same |
| CN104229871A (en) * | 2014-06-24 | 2014-12-24 | 济南大学 | Preparation method of flower type indium oxide gas-sensitive material with hierarchical structure |
| CN106006719A (en) * | 2016-07-20 | 2016-10-12 | 济南大学 | Method for preparing indium oxide micro-spheres which comprise nanometer particles and are of classification structures |
| CN107140682A (en) * | 2017-06-12 | 2017-09-08 | 吉林大学 | The indium oxide powder and its low-temperature hydro-thermal synthesis of a kind of morphology controllable |
| CN110642287A (en) * | 2019-10-08 | 2020-01-03 | 济南大学 | Cubic phase In2O3Method for synthesizing micro/nano sphere structure |
| CN112811461A (en) * | 2021-03-12 | 2021-05-18 | 济南大学 | Chain bead-shaped particle self-assembled In2O3Synthetic method of hollow cage and obtained product |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508462A (en) * | 2009-03-11 | 2009-08-19 | 长沙理工大学 | Process for producing flower shaped indium hydroxide powder having high specific surface area |
| CN101857263A (en) * | 2010-06-23 | 2010-10-13 | 东华大学 | Method for preparing nano indium oxide with controllable appearance by hydrothermal method |
-
2011
- 2011-02-17 CN CN 201110039341 patent/CN102134092B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508462A (en) * | 2009-03-11 | 2009-08-19 | 长沙理工大学 | Process for producing flower shaped indium hydroxide powder having high specific surface area |
| CN101857263A (en) * | 2010-06-23 | 2010-10-13 | 东华大学 | Method for preparing nano indium oxide with controllable appearance by hydrothermal method |
Non-Patent Citations (2)
| Title |
|---|
| 《 J. Phys. Chem. C》 20080906 Hui Zhu et al. Self-Assembled 3D Microflowery In(OH)3 Architecture and Its Conversion to In2O3 15285-15292 1-7 第112卷, 第39期 * |
| 《Eur. J. Inorg. Chem》 20080131 Li-Yong Chen et al. Tunable Synthesis of Various Hierarchical Structures of In(OH)3 and In2O3 Assembled by Nanocubes 1445-1451 1-2 , * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102503834A (en) * | 2011-09-29 | 2012-06-20 | 苏州大学 | Preparation method for porous sulfo-indium salt |
| CN102503834B (en) * | 2011-09-29 | 2013-11-13 | 苏州大学 | Preparation method for porous sulfo-indium salt |
| CN102557114B (en) * | 2011-12-29 | 2014-06-25 | 中国科学院上海光学精密机械研究所 | Preparation method of indium oxide-based gas-sensitive material with three-dimensional hollow multi-stage structure and application thereof |
| CN102557114A (en) * | 2011-12-29 | 2012-07-11 | 中国科学院上海光学精密机械研究所 | Preparation method of indium oxide-based gas-sensitive material with three-dimensional hollow multi-stage structure and application thereof |
| CN103781723B (en) * | 2012-07-13 | 2015-12-02 | 首尔大学校产学协力团 | 3D nanoparticle collecting structure body and use its gas sensor |
| CN103781723A (en) * | 2012-07-13 | 2014-05-07 | 首尔大学校产学协力团 | Three-dimensional nanoparticle assembly structure and gas sensor using same |
| CN103334179B (en) * | 2013-04-27 | 2015-07-22 | 青岛大学 | Hollow structure indium oxide nanometer fiber preparation method |
| CN103334179A (en) * | 2013-04-27 | 2013-10-02 | 青岛大学 | Hollow structure indium oxide nanometer fiber preparation method |
| CN104229871A (en) * | 2014-06-24 | 2014-12-24 | 济南大学 | Preparation method of flower type indium oxide gas-sensitive material with hierarchical structure |
| CN106006719A (en) * | 2016-07-20 | 2016-10-12 | 济南大学 | Method for preparing indium oxide micro-spheres which comprise nanometer particles and are of classification structures |
| CN107140682A (en) * | 2017-06-12 | 2017-09-08 | 吉林大学 | The indium oxide powder and its low-temperature hydro-thermal synthesis of a kind of morphology controllable |
| CN107140682B (en) * | 2017-06-12 | 2019-03-01 | 吉林大学 | A kind of the indium oxide powder and its low-temperature hydro-thermal synthesis of morphology controllable |
| CN110642287A (en) * | 2019-10-08 | 2020-01-03 | 济南大学 | Cubic phase In2O3Method for synthesizing micro/nano sphere structure |
| CN110642287B (en) * | 2019-10-08 | 2022-01-07 | 济南大学 | Cubic phase In2O3Method for synthesizing micro/nano sphere structure |
| CN112811461A (en) * | 2021-03-12 | 2021-05-18 | 济南大学 | Chain bead-shaped particle self-assembled In2O3Synthetic method of hollow cage and obtained product |
| CN112811461B (en) * | 2021-03-12 | 2022-07-12 | 济南大学 | Chain bead-shaped particle self-assembled In2O3Synthetic method of hollow cage and obtained product |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102134092B (en) | 2013-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102134092B (en) | Simple preparation method of hollow-spherical and flower-shaped indium oxide with secondary structure and application | |
| CN107866234B (en) | High-activity ZnIn2S4/TiO2Preparation method of Z-system catalyst material | |
| CN106179318B (en) | A kind of preparation method of vanadic acid bismuth nano-wire-graphene photo-catalyst | |
| CN107340367A (en) | A kind of preparation method of three-dimensional rGO/In2O3 composite room temperature gas sensitive | |
| CN103055903B (en) | Preparation method of visible light catalytic material with adjustable BiOI-AgI spherical solid solution | |
| CN106111161B (en) | A kind of ZnO/ZnS/CdS composite material and preparation method of porous core-shell structure | |
| CN101920977A (en) | Preparation method of flaky nano-sized magnesium oxide | |
| Niu et al. | Facile synthesis of γ-Fe2O3/BiOI microflowers with enhanced visible light photocatalytic activity | |
| CN103359773B (en) | A kind of preparation method of zinc oxide nano rod | |
| CN104001494B (en) | The synthetic method of the graphite modified nano-zinc stannate of one kind | |
| CN112007632B (en) | Flower-shaped SnO 2 /g-C 3 N 4 Preparation method of heterojunction photocatalyst | |
| Li et al. | Improvement of photocatalytic activity of BiOBr and BiOBr/ZnO under visible-light irradiation by short-time low temperature plasma treatment | |
| CN105271405A (en) | Material based on bismuth oxycarbonate or bismuth oxide nano tube and preparation method thereof | |
| CN103754837A (en) | Method for preparation of bismuth-containing nano-hollow ball by using porous bismuth oxide as template | |
| CN105238349A (en) | Fe3O4-ZnO nano composite material and preparation method thereof | |
| CN105836807A (en) | Tungsten oxide with two-dimensional slice self-assembly multilevel structure and preparation method thereof and application | |
| CN101880054A (en) | Method for preparing hollow zinc oxide microspheres | |
| CN103303980A (en) | Method for preparing nano iron oxide by lignosulfonate template process | |
| CN104192908A (en) | Nanosphere encapsulated MoS2 micron hollow sphere structure semiconductor material and preparation method thereof | |
| CN114160164B (en) | CeO 2-x S x Preparation method and application of/CdZnS/ZnO nano material | |
| CN103611550A (en) | Preparation method of molybdenum disulfide-silver metavanadate composite nano photocatalyst | |
| CN103482682B (en) | Preparation method of HEPES (hydroxyethylpiperazine ethane sulfonic acid) molecule guided porous zinc oxide microspheres | |
| CN103508494B (en) | A kind of preparation method of the alpha-type ferric oxide micro Nano material of morphology controllable | |
| Hu et al. | Novel synthesis of CuO nanofiber balls and films and their UV–visible light filteration property | |
| CN105198004B (en) | A kind of Fe3O4‑SnO2Nano composite material 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130327 Termination date: 20160217 |