CN100586865C - Method for preparing bismuth oxyhalide with even layer thickness - Google Patents
Method for preparing bismuth oxyhalide with even layer thickness Download PDFInfo
- Publication number
- CN100586865C CN100586865C CN200710178744A CN200710178744A CN100586865C CN 100586865 C CN100586865 C CN 100586865C CN 200710178744 A CN200710178744 A CN 200710178744A CN 200710178744 A CN200710178744 A CN 200710178744A CN 100586865 C CN100586865 C CN 100586865C
- Authority
- CN
- China
- Prior art keywords
- biox
- product
- room temperature
- ionic liquid
- layer thickness
- 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
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a method for the preparation of bismuth oxyhalide with homogenous layer thickness. Bismuth oxyhalide prepared by the method has a flake structure. Strong acid such as hydrochloric acid is not used in the preparation process, but the halogen source is provided. And the PH value of reaction solution is not regulated by strong acid and strong alkali. Ionic liquid of room temperature used in the invention can not only provide the halogen source but also help to exactly control the PH value of the reaction solution at 1 to 2, which provides the needed conditions for reaction. The flake bismuth oxyhalide can be produced from hydrolyze nitrate bismuth in halogen anionic solution of room temperature while regulating added amount, reaction time and reaction temperature.
Description
Technical field
The present invention relates to a kind of method for preparing layer thickness homogenized BiOX.
Background technology
BiOX is a kind of very important chemical product.Wherein studying maximum is pearl white, main as pearl pigment, make olivet, pearly-lustre button, pearly-lustre decorative plastic product, pearl white is with its unique pearlescent effect and smooth effect, be used to prepare the cosmetics of super quality of safety non-toxic, useful as catalysts also, the oxidisability coupling of catalytic methane etc.Bismuthyl bromide also is a kind of pigment and photocatalyst that has prospect.When using, its particulate size there is certain requirement as pigment.The mixture of one or several of above-mentioned oxyhalogenide when its size of control is in enough little scope, then has good photocatalytic activity.
Ionic liquid at room temperature is as the novel dissolvent system that develops in recent years, non-volatile or " zero " vapour pressure because of it, low melting point (90 ℃), wide liquid journey (200 ℃); Strong electrostatic field; Wide electrochemical window (even can greater than 5V); Good ionic conduction (25mS/cm) and thermal conductivity, high heat capacity and thermal energy storage density; High thermal stability (decomposition temperature can be higher than 400 ℃); Selective dissolution power; Performances such as designability and receiving much concern especially are that medium can be prepared the nano structural material that conventional solvent is difficult to obtain with the ionic liquid at room temperature.
Summary of the invention
The objective of the invention is to propose a kind of method for preparing layer thickness homogenized BiOX, it relates to the method for preparing BiOX under the non-pH value control condition, prepare by hydrolysis Bismuth trinitrate in halide anion type ionic liquid at room temperature, adjusting add-on, reaction times, temperature of reaction can make the sheet BiOX.
The present invention is a kind of method for preparing layer thickness homogenized BiOX, and this method includes the following step:
The first step: Bismuth trinitrate, halogen-containing anionic ionic liquid at room temperature and water-bearing media are put into the reaction solution that reaction vessel makes pH=1～2, and reaction solution stirs 1～15h after-filtration and obtains thick BiOX product under 18 ℃～100 ℃ conditions of temperature;
Add the Bismuth trinitrate of 0.05～2.00mol in the described water-bearing media of consumption: 1L, add the halogen-containing anionic ionic liquid at room temperature of 0.05～10.0mol;
Described halogen-containing anionic ionic liquid at room temperature is the ionic liquid at room temperature that organic cation and halide anion are formed; Described organic cation is alkyl imidazole positively charged ion, alkyl pyridine positively charged ion, carboxyl pyridine positively charged ion or amino acid positively charged ion; Described halide anion is Cl
-Or Br
-
Described water-bearing media is a deionized water;
Described water-bearing media is deionized water and pure mixed solution, and the alcohol in the mixed solution is 5 alcohol within the carbon;
Second step: the thick BiOX product that the first step makes is put into deionized water, under 18 ℃～25 ℃ conditions of temperature, wash 3～7 after-filtration and get the BiOX product;
The 3rd step: the BiOX product that second step was made is making the sheet BiOX behind dry 20～90min under 50 ℃～80 ℃ conditions of temperature.
In preparation process of the present invention, contain the sosoloid of pure BiOCl or pure BiOBr or pure BiOCl and pure BiOBr in the thick BiOX product.
The present invention compared with prior art has the following advantages and the high-lighting effect:
1. to adopt novel green solvent system one ionic liquid at room temperature and common commercially available analytical pure Bismuth trinitrate be raw material in the present invention, utilizes the simple method that stirs chemical precipitation, prepared the BiOX powder of a large amount of cheapnesss.
2. do not use strong acid in the reaction, example hydrochloric acid provides halogen source; Do not use strong acid (as nitric acid) and highly basic (as sodium hydroxide) to wait the pH value of reaction medium, the ionic liquid at room temperature that uses among the present invention can provide pH value that halogen source can accurately control reaction medium again yet, provide reaction required condition 1～2.
3. along with the difference of reaction conditions, the crystallization phases of products therefrom, pattern and lamella size have certain variation, can wait the crystallization degree and the lamella size of regulating product by control precursor add-on, reaction times, temperature of reaction.
4. this method raw material is cheap and easy to get, uniform product appearance and good dispersity, and technology is simple, produces to be easy to enlarge.
These BiOXs all are the uniform layered crystal structures of thickness, and the product yardstick has good photocatalytic activity when nano level.Prepared constant product quality, controllability is good, thereby has broad application prospects.
Description of drawings
Fig. 1 is the sem photograph of the BiOCl of embodiment 1 preparation.
Fig. 2 is the X-ray diffractogram of the BiOCl of embodiment 1 preparation.
Fig. 3 is the X-ray diffractogram of the BiOBr of embodiment 4 preparations.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
The present invention is a kind of method for preparing layer thickness homogenized BiOX, and this method includes the following step:
The first step: Bismuth trinitrate, halogen-containing anionic ionic liquid at room temperature and water-bearing media are put into the reaction solution that reaction vessel makes pH=1～2, and reaction solution stirs 1～15h after-filtration and obtains thick BiOX product under 18 ℃～100 ℃ conditions of temperature;
Add the Bismuth trinitrate of 0.05～2.00mol in the described water-bearing media of consumption: 1L, add the halogen-containing anionic ionic liquid at room temperature of 0.05～10.0mol;
Described halogen-containing anionic ionic liquid at room temperature is the ionic liquid at room temperature that organic cation and halide anion are formed; Described organic cation is alkyl imidazole positively charged ion, alkyl pyridine positively charged ion, carboxyl pyridine positively charged ion or amino acid positively charged ion; Described halide anion is Cl
-Or Br
-
Described water-bearing media is a deionized water;
Described water-bearing media is deionized water and pure mixed solution, and the alcohol in the mixed solution is 5 alcohol within the carbon;
In the present invention, BiOX solid productive rate is more than 95% in the thick BiOX product that makes of the first step.
Second step: the thick BiOX product that the first step makes is put into deionized water, under 18 ℃～25 ℃ conditions of temperature, wash 3～7 after-filtration and get the BiOX product;
The 3rd step: the BiOX product that second step was made is making the sheet BiOX behind dry 20～90min under 50 ℃～80 ℃ conditions of temperature.
In preparation process of the present invention, contain pure BiOCl or pure BiOBr or pure BiOCl and pure BiOBr sosoloid in the thick BiOX product.
Embodiment 1:
The first step: Bismuth trinitrate, 1-allyl group-3-Methylimidazole chlorine ionic liquid at room temperature and deionized water are put into the reaction solution that reaction vessel makes pH=2, reaction solution stirs the 2h after-filtration and obtains the BiOCl solid and the reaction solution of complete reaction not under 25 ℃ of conditions of temperature; BiOCl solid productive rate is 98%;
Add the Bismuth trinitrate of 0.5mol in the described water-bearing media of consumption: lL, add 1-allyl group-3-Methylimidazole chlorine ionic liquid at room temperature of 0.5mol;
Second step: the BiOCl solid that the first step is made and not the reaction solution of complete reaction put into deionized water, under 25 ℃ of conditions of temperature, wash 3 after-filtration and get the BiOCl product;
The 3rd step: the BiOCl product that second step was made is making sheet BiOCl behind the dry 60min under 50 ℃ of conditions of temperature.Sheet BiOCl carries out electron-microscope scanning, and its structure is referring to shown in Figure 1, and its structure is the uniform sheet structure of thickness.
Sheet BiOCl is carried out XRD analysis, and referring to shown in Figure 2, the sheet BiOCl that makes is consistent by force with peak position, peak that the standard picture library is numbered the standard spectrogram of PCPDF NO.85-861.
The above-mentioned sheet BiOCl that makes is carried out the ultraviolet light photocatalysis performance test:
The photochemical catalysis test set comprises 250W high voltage mercury lamp (predominant wavelength 365nm), circulating cooling system, 722S type spectrophotometer and 800 type whizzers.Estimate the photocatalytic activity of BiOCl with the methyl orange aqueous solution of 10mg/L, concentration with 2g/K in above-mentioned methyl orange solution adds the BiOCl photocatalyst, earlier suspension liquid is in the dark stirred 45min to reach adsorption equilibrium, the Continuous irradiation of turning on light then 40min (logical water coolant takes place to prevent pyrolysis), lamp is 20cm apart from the liquid level distance, therebetween once, every 4min sampling with behind the whizzer high speed centrifugation 10min with the absorbancy of spectrophotometer measurement supernatant liquid.Show that sheet BiOCl can 95.8% pair of tropeolin-D degrade.
Embodiment 2:
The first step: Bismuth trinitrate, 1-normal-butyl-3-Methylimidazole chlorine ionic liquid at room temperature and water-bearing media are put into the reaction solution that reaction vessel makes pH=1, reaction solution stirs the 6h after-filtration and obtains the BiOCl solid and the reaction solution of complete reaction not under 40 ℃ of conditions of temperature; BiOCl solid productive rate is 99.1%;
Add the Bismuth trinitrate of 1.00mol in the described water-bearing media of consumption: 1L, add the halogen-containing anionic ionic liquid at room temperature of 3.0mol;
Described water-bearing media is deionized water and pure mixed solution, and the alcohol in the mixed solution is the alcohol of 2 carbon;
Second step: the BiOCl solid that the first step is made and not the reaction solution of complete reaction put into deionized water, under 18 ℃ of conditions of temperature, wash 5 after-filtration and get the BiOCl product;
The 3rd step: the BiOCl product that second step was made is making sheet BiOCl behind the dry 20min under 80 ℃ of conditions of temperature.
Adopt the mode identical with embodiment 1 to carry out the ultraviolet light photocatalysis performance test sheet BiOCl that makes, this sheet BiOCl can 97.5% pair of tropeolin-D degrade.
Embodiment 3:
The first step: Bismuth trinitrate, tribromide 1-butyl-3-Methylimidazole ionic liquid at room temperature and deionized water are put into the reaction solution that reaction vessel makes pH=2, reaction solution stirs the 4h after-filtration and obtains the BiOBr solid and the reaction solution of complete reaction not under 50 ℃ of conditions of temperature; BiOBr solid productive rate is 95%;
Add the Bismuth trinitrate of 2.00mol in the described water-bearing media of consumption: 1L, add the halogen-containing anionic ionic liquid at room temperature of 10.0mol;
Second step: the BiOBr solid that the first step is made and not the reaction solution of complete reaction put into deionized water, under 25 ℃ of conditions of temperature, wash after-filtration BiOBr product 5 times;
The 3rd step: the BiOX product that second step was made is making sheet BiOBr behind the dry 40min under 80 ℃ of conditions of temperature.
Adopt the mode identical with embodiment 1 to carry out the ultraviolet light photocatalysis performance test sheet BiOBr that makes, this sheet BiOBr can 99.8% pair of tropeolin-D degrade.
Embodiment 4:
The first step: Bismuth trinitrate, 1-allyl group-3-Methylimidazole bromine ionic liquid at room temperature and water-bearing media are put into the reaction solution that reaction vessel makes pH=1, reaction solution stirs the 10h after-filtration and obtains the BiOBr solid and the reaction solution of complete reaction not under 18 ℃ of conditions of temperature; BiOBr solid productive rate is 98.7%;
Add the Bismuth trinitrate of 1.00mol in the described water-bearing media of consumption: 1L, add the halogen-containing anionic ionic liquid at room temperature of 2.0mol;
Described water-bearing media is deionized water and pure mixed solution, and the alcohol in the mixed solution is the alcohol of 5 carbon;
Second step: the BiOBr solid that the first step is made and not the reaction solution of complete reaction put into deionized water, under 18 ℃ of conditions of temperature, wash 7 after-filtration and get the BiOBr product;
The 3rd step: the BiOX product that second step was made is making sheet BiOBr behind the dry 60min under 50 ℃ of conditions of temperature.
Sheet BiOBr is carried out XRD analysis, and referring to shown in Figure 3, the sheet BiOBr that makes is consistent by force with peak position, peak that the standard picture library is numbered the standard spectrogram of PCPDF NO.85-862.
Adopt the mode identical with embodiment 1 to carry out the ultraviolet light photocatalysis performance test sheet BiOBr that makes, this sheet BiOBr can 100% pair of tropeolin-D degrade.
Embodiment 5:
The first step: Bismuth trinitrate, 1-allyl group-3-Methylimidazole chlorine ionic liquid at room temperature, 1-allyl group-3-Methylimidazole bromine ionic liquid at room temperature and deionized water are put into the reaction solution that reaction vessel makes pH=1, reaction solution stirs the 4h after-filtration and obtains the 0.5BiOCl-0.5BiOBr solid and the reaction solution of complete reaction not under 40 ℃ of conditions of temperature; 0.5BiOCl-0.5BiOBr the solid productive rate is 98.3%;
Add the Bismuth trinitrate of 0.5mol in the described water-bearing media of consumption: 1L, add 1-allyl group-3-Methylimidazole chlorine ionic liquid at room temperature of 0.25mol, add 1-allyl group-3-Methylimidazole bromine ionic liquid at room temperature of 0.25mol;
Second step: the 0.5BiOCl-0.5BiOBr solid that the first step is made and not the reaction solution of complete reaction put into deionized water, under 25 ℃ of conditions of temperature, wash 5 after-filtration and get the 0.5BiOCl-0.5BiOBr product;
The 3rd step: the BiOX product that second step was made is making sheet 0.5BiOCl-0.5BiOBr behind the dry 60min under 50 ℃ of conditions of temperature.
Adopt the mode identical with embodiment 1 to carry out the ultraviolet light photocatalysis performance test sheet 0.5BiOCl-0.5BiOBr that makes, this sheet 0.5BiOCl-0.5BiOBr can 99.2% pair of tropeolin-D degrade.
Claims (5)
1, a kind of method for preparing layer thickness homogenized BiOX is characterized in that following preparation steps is arranged:
The first step: Bismuth trinitrate, halogen-containing anionic ionic liquid at room temperature and water-bearing media are put into the reaction solution that reaction vessel makes pH=1～2, and reaction solution stirs 1～15h after-filtration and obtains thick BiOX product under 18 ℃～100 ℃ conditions of temperature;
Add the Bismuth trinitrate of 0.05～2.00mol in the described water-bearing media of consumption: 1L, add the halogen-containing anionic ionic liquid at room temperature of 0.05～10.0mol;
Described halogen-containing anionic ionic liquid at room temperature is the ionic liquid at room temperature that organic cation and halide anion are formed; Described organic cation is alkyl imidazole positively charged ion, alkyl pyridine positively charged ion, carboxyl pyridine positively charged ion or amino acid positively charged ion; Described halide anion is Cl
-Or Br
-
Second step: the thick BiOX product that the first step makes is put into deionized water, under 18 ℃～25 ℃ conditions of temperature, wash 3～7 after-filtration and get the BiOX product;
The 3rd step: the BiOX product that second step was made is making the sheet BiOX behind dry 20～90min under 50 ℃～80 ℃ conditions of temperature.
2, the method for the layer thickness homogenized BiOX of preparation according to claim 1 is characterized in that: water-bearing media described in the first step is a deionized water and the mixed solution of alcohol, and the alcohol in the mixed solution is 5 alcohol within the carbon.
3, the method for the layer thickness homogenized BiOX of preparation according to claim 1, it is characterized in that: the described water-bearing media in the first step is a deionized water.
4, the method for the layer thickness homogenized BiOX of preparation according to claim 1 is characterized in that: contain pure BiOCl or pure BiOBr or pure BiOCl and pure BiOBr sosoloid in the thick BiOX product that the first step makes.
5, the method for the layer thickness homogenized BiOX of preparation according to claim 1, it is characterized in that: BiOX solid productive rate is more than 95% in the thick BiOX product that the first step makes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710178744A CN100586865C (en) | 2007-12-05 | 2007-12-05 | Method for preparing bismuth oxyhalide with even layer thickness |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710178744A CN100586865C (en) | 2007-12-05 | 2007-12-05 | Method for preparing bismuth oxyhalide with even layer thickness |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101186336A CN101186336A (en) | 2008-05-28 |
| CN100586865C true CN100586865C (en) | 2010-02-03 |
Family
ID=39479001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710178744A Expired - Fee Related CN100586865C (en) | 2007-12-05 | 2007-12-05 | Method for preparing bismuth oxyhalide with even layer thickness |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100586865C (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786660B (en) * | 2010-01-29 | 2013-02-27 | 上海第二工业大学 | Preparation method of three-dimensional hierarchical structure halogenated bismuth oxide microspheres with adjustable bandwidth |
| CN101786006B (en) * | 2010-04-08 | 2012-08-08 | 中国科学院水利部成都山地灾害与环境研究所 | Preparation method of bismuth oxybromide photocatalyst |
| CN101844808B (en) * | 2010-06-03 | 2012-04-25 | 安徽大学 | Method for preparing bismuthyl chloride nano-flower |
| CN101850263A (en) * | 2010-06-17 | 2010-10-06 | 江西理工大学 | Ag doped BiOBr catalytic material and preparation method and application thereof |
| CN102373507A (en) * | 2010-08-27 | 2012-03-14 | 中国科学院过程工程研究所 | Method for hydrothermally synthesizing Bi2WO6 material under assistance of imidazole ionic liquids |
| US9943833B2 (en) | 2010-11-16 | 2018-04-17 | Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. | Bismuth oxyhalide compounds useful as photocatalysts |
| CN102010003B (en) * | 2010-12-14 | 2012-07-04 | 中国科学院新疆理化技术研究所 | Method for preparing bismuth oxychloride by solid-phase reaction at room temperature |
| CN102225341B (en) * | 2011-04-26 | 2013-04-03 | 山东大学 | Method for preparing hierarchical structure bismuth oxybromide hollow microsphere photocatalysis material |
| CN102626644A (en) * | 2012-03-26 | 2012-08-08 | 哈尔滨工业大学 | Preparation method of lamellar porous bismuthyl iodide nano photocatalyst |
| CN103316701B (en) * | 2013-07-02 | 2015-04-15 | 辽宁石油化工大学 | Method for preparing Bi2S3/BiOCl heterojunction photocatalyst |
| CN103787413B (en) * | 2014-03-04 | 2015-08-12 | 南京信息工程大学 | Hexagon hollow tubulose Bi 2o (OH) 2sO 4the preparation method of photochemical catalyst and application |
| CN104190445B (en) * | 2014-08-19 | 2016-04-20 | 河北科技大学 | BiOBr base heterojunction of a kind of visible light catalysis activity and preparation method thereof |
| CN104310471B (en) * | 2014-11-14 | 2016-01-13 | 山东大学 | A kind of method of synthesizing bismuth oxychloride pearlescent pigment |
| CN104689838A (en) * | 2015-02-13 | 2015-06-10 | 湘潭大学 | Preparation method for BiOCl photocatalyst with controllable morphology and crystal face |
| CN105214694B (en) * | 2015-09-30 | 2017-10-10 | 南京大学 | A kind of method that soft template method prepares BiOCl hollow shells |
| CN105833895A (en) * | 2016-05-05 | 2016-08-10 | 陈建峰 | Preparation method of modified BiOBr visible light catalyst |
| CN107497457B (en) * | 2017-06-12 | 2018-06-08 | 南阳师范学院 | A kind of Bi3O4Cl0.5Br0.5Mischcrystal photocatalyst and its preparation and application |
| CN107686130B (en) * | 2017-09-14 | 2019-03-29 | 济南大学 | A kind of synthesis of bismuth iodine hybrid material and it is used to prepare BiOI nanometer sheet |
| CN108479815B (en) * | 2018-03-09 | 2019-11-15 | 绍兴文理学院 | A kind of BiOCl photochemical catalyst octahedronlike and the preparation method and application thereof |
| CN114225950A (en) * | 2021-12-21 | 2022-03-25 | 南京环保产业创新中心有限公司 | Bismuth oxybromide photocatalyst filler and preparation method and application thereof |
-
2007
- 2007-12-05 CN CN200710178744A patent/CN100586865C/en not_active Expired - Fee Related
Non-Patent Citations (6)
| Title |
|---|
| 均匀分散氯化氧铋胶体粒子制备. 韩恩山等.物理化学学报，第9卷第1期. 1993 |
| 均匀分散氯化氧铋胶体粒子制备. 韩恩山等.物理化学学报，第9卷第1期. 1993 * |
| 层状BiOCl-云母珠光颜料的研制. 张高科等.金属矿山，第3期. 2002 |
| 层状BiOCl-云母珠光颜料的研制. 张高科等.金属矿山，第3期. 2002 * |
| 硝酸铋转化水解法制备片状BiOCl粉末的研究. 王云燕等.湖南冶金，第31卷第3期. 2003 |
| 硝酸铋转化水解法制备片状BiOCl粉末的研究. 王云燕等.湖南冶金，第31卷第3期. 2003 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101186336A (en) | 2008-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100586865C (en) | Method for preparing bismuth oxyhalide with even layer thickness | |
| Yada et al. | Yttrium-based porous materials templated by anionic surfactant assemblies | |
| CN104226339A (en) | Visible-light-induced photocatalyst Bi4O5Br2 and preparation method thereof | |
| CN102910654B (en) | Preparation method of fibrous boehmite with large specific surface area and large pore area | |
| CN106268734A (en) | A kind of preparation method of water dispersible ternary mixed crystal nano titanium dioxide photocatalyst | |
| Xue et al. | La/Ce-codoped Bi2O3 composite photocatalysts with high photocatalytic performance in removal of high concentration dye | |
| CN102082270A (en) | Manganese spinel nano material as well as preparation method and application of manganese spinel nano material | |
| CN103949274B (en) | A kind of Co0.85Se catalyst material and preparation method | |
| CN103708424A (en) | Preparation method of {001} crystal surface-exposed BioBr square nanosheet | |
| CN101407339A (en) | Method for synthesizing quadrangle tungsten oxide nano-powder | |
| CN103055903B (en) | Preparation method of visible light catalytic material with adjustable BiOI-AgI spherical solid solution | |
| Wang et al. | Preparation and characterization of nanometer-scale powders ceria by electrochemical deposition method | |
| CN104418382B (en) | A kind of hydrothermal method prepares the method for zinc metastannate | |
| CN105800686A (en) | Method for preparing Bi5O7I | |
| CN103736505A (en) | Visible-light-driven photocatalyst Bi5O7Br and preparation method thereof | |
| CN105460983B (en) | A kind of ultracapacitor preparation method of cobalt acid nickel nano material | |
| NaderiNasrabadi et al. | Biomass-depolarized electrolysis | |
| CN107638886A (en) | The method that ion-exchange prepares bismoclite/bismuth oxyiodide composite ultra-thin nanometer sheet | |
| CN102553620B (en) | Visible light photocatalyst Bi12O17Cl2 and preparation method thereof | |
| CN109794271B (en) | Ultra-thin PbBiO with oxygen-enriched defect2Preparation method and application of Br nanosheet | |
| CN103588476A (en) | Preparation method of spherical lithium metatitanate solid tritium fertile material | |
| CN102408132B (en) | Method for preparing nanometer lanthanum ferrite powder by using microwave process | |
| CN103933990B (en) | A kind of preparation method of 26 body structure CaCu 3 Ti 4 Os | |
| CN108017083B (en) | A kind of CeO constructed by hollow bead2Porous nano cluster and preparation method thereof | |
| CN106582726A (en) | Bi4o5Br2 hollow sphere and preparation method using micro-emulsion as template |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100203 Termination date: 20101205 |