CN101279767B - Preparation of lanthanide series rare-earth doped bismuth titanate nano-tube - Google Patents
Preparation of lanthanide series rare-earth doped bismuth titanate nano-tube Download PDFInfo
- Publication number
- CN101279767B CN101279767B CN2008100643956A CN200810064395A CN101279767B CN 101279767 B CN101279767 B CN 101279767B CN 2008100643956 A CN2008100643956 A CN 2008100643956A CN 200810064395 A CN200810064395 A CN 200810064395A CN 101279767 B CN101279767 B CN 101279767B
- Authority
- CN
- China
- Prior art keywords
- lanthanide series
- earth doped
- preparation
- bismuth titanate
- series rare
- 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Disclosed is a method for the production of a lanthanide rare-earth doping bismuth titanate nano-tube, which relates to a method for the production of a bismuth titanate nano-tube. The method solves the problems of complex technique and equipment, long preparation cycle, high cost, low yield and being unable to control the size of the nanostructure material accurately when preparing the lanthanide rare-earth doping bismuth titanate nanostructure material by the prior art. The method of preparation has steps of: firstly, weighting nitrate and tetrabutyl titanate in bismuth salt and lanthanide rare-earth; secondly, preparing a lanthanide rare-earth doping bismuth titanate sol, thirdly, dripping the lanthanide rare-earth doping bismuth titanate sol on the surface of an aluminum oxide template and drying the template after being soaked; fourthly, repeating the third step and preserving the heat of the dried template at a certain temperature; and fifthly, repeating the third and the fourth steps and taking out the template at a certain temperature and then placing the template in a KOH or NaOH solution, thereby obtaining the lanthanide rare-earth doping bismuth titanate nano-tube. The method of preparation has advantages of simple process and equipment, short preparation cycle, low cost, high yield and being able to control the size of the nano-tube accurately.
Description
Technical field
The present invention relates to the preparation method of bismuth titanate nano-tube.
Background technology
The lanthanide series rare-earth doped bismuth titanate material has excellent polarization reversal characteristic, resistent fatigue characteristic, ageing resistance, low-k, low-dielectric loss, high-curie temperature and does not have advantage such as Lead contamination, has become the focus of current novel ferroelectric functional materials research.The one dimension Nano structure of lanthanide series rare-earth doped bismuth titanate material, for example, nano wire, nanotube can greatly improve the storage density of lanthanide series rare-earth doped bismuth titanate material.
The method that prepare at present the lanthanide series rare-earth doped bismuth titanate nano structural material mainly contains hydrothermal method and electrospinning precursor solution method, and the shortcoming that they all have the nano structural material size accurately to control is unfavorable for synthesizing the nano structural material of diameter and length homogeneous; And the hydrothermal method complicated operating process needs bigger pressure to cause cost higher, and preparation cycle is long and productive rate is low; Electrospinning precursor solution method equipment complexity.Thereby adopt method simple, cheap and that can accurately control nanostructure size to prepare lanthanide series rare-earth doped one dimension bismuth titanates ferroelectric nano material tool to have very important significance.
Summary of the invention
The present invention seeks to for the complex process, the equipment complexity that solve prior art for preparing lanthanide series rare-earth doped bismuth titanate nano structural material, preparation cycle is long, cost is high, productive rate is low and can not accurately control the problem of nano structural material size, and provides a kind of preparation method of lanthanide series rare-earth doped bismuth titanate nano-tube.
The preparation method of lanthanide series rare-earth doped bismuth titanate nano-tube realizes according to the following steps: one, according to chemical formula Bi
4-xR
xTi
3O
12, wherein R is a lanthanide series rare-earth elements, and 0＜x＜0.9 takes by weighing the nitrate and the tetrabutyl titanate of time bismuth salt, lanthanide rare by stoichiometric ratio, takes by weighing and makes its excessive 0.1～10% (quality) bismuth salt, and bismuth salt is bismuth subnitrate or bismuth acetate; Two, nitrate and the bismuth salt with lanthanide rare is dissolved in the acetic acid mixed solution, adds tetrabutyl titanate again, gets lanthanide series rare-earth doped bismuth titanate colloidal sol after the stirring; Wherein the acetic acid mixed solution be acetic acid with ethylene glycol, ethylene glycol monomethyl ether, methyl ethyl diketone in a kind of mixing; Three, lanthanide series rare-earth doped bismuth titanate colloidal sol is dropped in the alumina formwork surface, soak into 5～8min, be put in 60～80 ℃ of oven dry down; Four, the operation of repeating step 3 is 3～10 times, and the template after the oven dry is incubated 45～90min under 300～400 ℃ condition, be incubated 20～60min then under 450～550 ℃ condition; Five, repeating step three and four operation are 2～4 times, take out after being incubated 20～60min under 700～750 ℃ the condition, put into KOH or the NaOH solution that volumetric molar concentration is 6mol/L again and soak 150～200min, promptly obtain lanthanide series rare-earth doped bismuth titanate nano-tube.
The present invention utilizes the method that lanthanide series rare-earth doped bismuth titanate colloidal sol repeatedly soaks into alumina formwork to synthesize lanthanide series rare-earth elements doped bismuth titanate nano-tube complete, smooth, homogeneous, can accurately control the nanotube size according to the size in alumina formwork space, and the nanotube productive rate more; Technology of the present invention is simple, equipment is simple, preparation cycle is short and cost is low.
Description of drawings
Fig. 1 is the sem photograph of 10,000 times of amplifications of the bismuth titanate nano-tube of products therefrom doping lanthanum in the embodiment ten.
Embodiment
Embodiment one: the preparation method of present embodiment lanthanide series rare-earth doped bismuth titanate nano-tube realizes according to the following steps: one, according to chemical formula Bi
4-xR
xTi
3O
12, wherein R is a lanthanide series rare-earth elements, and 0＜x＜0.9 takes by weighing the nitrate and the tetrabutyl titanate of time bismuth salt, lanthanide rare by stoichiometric ratio, takes by weighing and makes its excessive 0.1～10% (quality) bismuth salt, and bismuth salt is bismuth subnitrate or bismuth acetate; Two, nitrate and the bismuth salt with lanthanide rare is dissolved in the acetic acid mixed solution, adds tetrabutyl titanate again, gets lanthanide series rare-earth doped bismuth titanate colloidal sol after the stirring; Wherein the acetic acid mixed solution be acetic acid with ethylene glycol, ethylene glycol monomethyl ether, methyl ethyl diketone in a kind of mixing; Three, lanthanide series rare-earth doped bismuth titanate colloidal sol is dropped in the alumina formwork surface, soak into 5～8min, be put in 60～80 ℃ of oven dry down; Four, the operation of repeating step 3 is 3～10 times, and the template after the oven dry is incubated 45～90min under 300～400 ℃ condition, be incubated 20～60min then under 450～550 ℃ condition; Five, repeating step three and four operation are 2～4 times, take out after being incubated 20～60min under 700～750 ℃ the condition, put into KOH or the NaOH solution that volumetric molar concentration is 6mol/L again and soak 1～200min, promptly obtain lanthanide series rare-earth doped bismuth titanate nano-tube.
Can control the size of nanotube in the present embodiment according to the size in alumina formwork space.
Embodiment two: what present embodiment and embodiment one were different is that lanthanide series rare-earth elements is La, Sm, Nd, Eu, Yb, Dy, Tb, Ho or Lu in the step 1.Other step and parameter are identical with embodiment one.
Embodiment three: that present embodiment and embodiment one are different is chemical formula Bi in the step 1
4-xR
xTi
3O
12Middle x's preferably is 0.1＜x＜0.9.Other step and parameter are identical with embodiment one.
Embodiment four: what present embodiment and embodiment one were different is that the nitrate of used bismuth salt, lanthanide rare in the step 1 and the purity of tetrabutyl titanate are analytical pure.Other step and parameter are identical with embodiment one.
Embodiment five: what present embodiment and embodiment one were different is to take by weighing in the step 1 to make its excessive 5% (quality) bismuth salt.Other step and parameter are identical with embodiment one.
Taking by weighing excessive purpose in the present embodiment is the volatilization that remedies bismuth ion in the calcination process.
Embodiment six: what present embodiment and embodiment one were different is that the acetic acid mixed solution is that purity is that analytically pure acetic acid is that a kind of 1: 0.5 by volume～1.5 in analytically pure ethylene glycol, ethylene glycol monomethyl ether, the methyl ethyl diketone mixes with purity in the step 2.Other step and parameter are identical with embodiment one.
Embodiment seven: what present embodiment and embodiment one were different is to soak into 6min in the step 3, is put in 75 ℃ of oven dry down.Other step and parameter are identical with embodiment one.
Embodiment eight: present embodiment and embodiment one are different is the operation 5 times of repeating step three in the step 4, and the template after the oven dry is protected 60min under 350 ℃ condition, be incubated 30min then under 500 ℃ condition.Other step and parameter are identical with embodiment one.
Embodiment nine: present embodiment and embodiment one are different is repeating step three and four operation 3 times in the step 5, taking out behind the insulation 30min under 700 ℃ the condition, put into KOH or the NaOH solution that volumetric molar concentration is 6mol/L again and soak 150min.Other step and parameter are identical with embodiment one.
Embodiment ten: the preparation method of present embodiment lanthanide series rare-earth doped bismuth titanate nano-tube realizes according to the following steps: one, according to chemical formula Bi
3.25La
0.75Ti
3O
12, take by weighing bismuth subnitrate, lanthanum nitrate and tetrabutyl titanate by stoichiometric ratio, take by weighing and make its excessive 5% (quality) bismuth subnitrate; Two, lanthanum nitrate and bismuth subnitrate are dissolved in the mixed solution of acetic acid and methyl ethyl diketone, add tetrabutyl titanate again, the bismuth titanates colloidal sol of the lanthanum that must mix after the stirring; Three, the bismuth titanates colloidal sol with the doping lanthanum drops in the alumina formwork surface, soaks into 6min, is put in 75 ℃ of oven dry down; Four, the operation of repeating step 3 is 5 times, and the template after the oven dry is incubated 60min under 350 ℃ condition, be incubated 30min then under 500 ℃ condition; Five, repeating step three and four operation are 3 times, are taking out behind the insulation 30min under 700 ℃ the condition, and the KOH solution of putting into volumetric molar concentration again and be 6mol/L soaks 150min, promptly obtains lanthanide series rare-earth doped bismuth titanate nano-tube.
The bismuth titanate nano-tube that present embodiment prepares gained doping lanthanum is complete, smooth, the homogeneous of nanotube as seen from Figure 1.
Claims (8)
1. the preparation method of lanthanide series rare-earth doped bismuth titanate nano-tube is characterized in that the preparation method of lanthanide series rare-earth doped bismuth titanate nano-tube realizes according to the following steps: one, according to chemical formula Bi
4-xR
xTi
3O
12, wherein R is a lanthanide series rare-earth elements, and 0＜x＜0.9 takes by weighing the nitrate and the tetrabutyl titanate of time bismuth salt, lanthanide rare by stoichiometric ratio, takes by weighing and makes its excessive 0.1～10% (quality) bismuth salt, and bismuth salt is bismuth subnitrate or bismuth acetate; Two, nitrate and the bismuth salt with lanthanide rare is dissolved in the acetic acid mixed solution, adds tetrabutyl titanate again, gets lanthanide series rare-earth doped bismuth titanate colloidal sol after the stirring; Wherein the acetic acid mixed solution be acetic acid with ethylene glycol, ethylene glycol monomethyl ether, methyl ethyl diketone in a kind of mixing; Three, lanthanide series rare-earth doped bismuth titanate colloidal sol is dropped in the alumina formwork surface, soak into 5～8min, be put in 60～80 ℃ of oven dry down; Four, the operation of repeating step 3 is 3～10 times, and the template after the oven dry is incubated 45～90min under 300～400 ℃ condition, be incubated 20～60min then under 450～550 ℃ condition; Five, repeating step three and four operation are 2～4 times, take out after being incubated 20～60min under 700～750 ℃ the condition, put into KOH or the NaOH solution that volumetric molar concentration is 6mol/L again and soak 150～200min, promptly obtain lanthanide series rare-earth doped bismuth titanate nano-tube.
2. the preparation method of lanthanide series rare-earth doped bismuth titanate nano-tube according to claim 1 is characterized in that lanthanide series rare-earth elements is La, Sm, Nd, Eu, Yb, Dy, Tb, Ho or Lu in the step 1.
3. the preparation method of lanthanide series rare-earth doped bismuth titanate nano-tube according to claim 1 is characterized in that the nitrate of used bismuth salt, lanthanide rare in the step 1 and the purity of tetrabutyl titanate are analytical pure.
4. the preparation method of lanthanide series rare-earth doped bismuth titanate nano-tube according to claim 1 is characterized in that taking by weighing in the step 1 and makes its excessive 5% (quality) bismuth salt.
5. the preparation method of lanthanide series rare-earth doped bismuth titanate nano-tube according to claim 1 is characterized in that the acetic acid mixed solution is that purity is that analytically pure acetic acid is that a kind of 1: 0.5 by volume～1.5 in analytically pure ethylene glycol, ethylene glycol monomethyl ether, the methyl ethyl diketone mixes with purity in the step 2.
6. the preparation method of lanthanide series rare-earth doped bismuth titanate nano-tube according to claim 1 is characterized in that soaking into 6min in the step 3, is put in 75 ℃ of oven dry down.
7. the preparation method of lanthanide series rare-earth doped bismuth titanate nano-tube according to claim 1 is characterized in that the operation 5 times of repeating step three in the step 4, and the template after the oven dry is protected 60min under 350 ℃ condition, be incubated 30min then under 500 ℃ condition.
8. the preparation method of lanthanide series rare-earth doped bismuth titanate nano-tube according to claim 1, it is characterized in that repeating step three in the step 5 and four operation 3 times, taking out behind the insulation 30min under 700 ℃ the condition, put into KOH or the NaOH solution that volumetric molar concentration is 6mol/L again and soak 150min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100643956A CN101279767B (en) | 2008-04-28 | 2008-04-28 | Preparation of lanthanide series rare-earth doped bismuth titanate nano-tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100643956A CN101279767B (en) | 2008-04-28 | 2008-04-28 | Preparation of lanthanide series rare-earth doped bismuth titanate nano-tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101279767A CN101279767A (en) | 2008-10-08 |
| CN101279767B true CN101279767B (en) | 2010-06-16 |
Family
ID=40012472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008100643956A Expired - Fee Related CN101279767B (en) | 2008-04-28 | 2008-04-28 | Preparation of lanthanide series rare-earth doped bismuth titanate nano-tube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101279767B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8709304B2 (en) * | 2009-12-14 | 2014-04-29 | Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada, Reno | Hydrothermal synthesis of nanocubes of sillenite type compounds for photovoltaic applications and solar energy conversion of carbon dioxide to fuels |
| CN104096576B (en) * | 2014-06-26 | 2016-04-06 | 杭州电子科技大学 | A kind of preparation method of environmental photocatlytsis nano material |
| CN104096577B (en) * | 2014-06-26 | 2016-04-06 | 杭州电子科技大学 | A kind of preparation method of water treatment nano material |
| CN104098129B (en) * | 2014-06-26 | 2015-10-07 | 杭州电子科技大学 | A kind of preparation method of multi-element doping metatitanic acid nanometer short tube |
| CN104098128B (en) * | 2014-06-26 | 2015-11-04 | 杭州电子科技大学 | A kind of preparation method of inorganic composite nano material |
| CN104529436B (en) * | 2015-01-22 | 2016-05-18 | 哈尔滨工业大学 | A kind of high-compactness Bi4-xNdxTi3O12The preparation method of ferroelectric ceramics |
| CN106391010B (en) * | 2016-09-26 | 2018-10-16 | 常州大学 | A kind of Ag/BaTiO3Heterogeneous photocatalyst structure of nano-tube array and preparation method thereof |
| CN106390982B (en) * | 2016-09-26 | 2018-10-16 | 常州大学 | A kind of rear-earth-doped BaTiO3Nano-tube array photochemical catalyst and preparation method thereof |
| CN112342020A (en) * | 2019-08-08 | 2021-02-09 | 广西大学 | Holmium-ytterbium co-doped bismuth titanate composite phosphor powder and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424257A (en) * | 2003-01-10 | 2003-06-18 | 清华大学 | Rare earth hydroxide nano tubes and synthesis of serial rare earth compounds nano tubes |
| CN1850722A (en) * | 2006-05-23 | 2006-10-25 | 湖北大学 | Optimized-oriented-growth preparing method for BndT ferro-electric film |
| CN1872696A (en) * | 2006-06-08 | 2006-12-06 | 南昌大学 | Method for preparing Nano tube of lanthanum hydroxide, and Nano tube of lanthanum oxide |
-
2008
- 2008-04-28 CN CN2008100643956A patent/CN101279767B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1424257A (en) * | 2003-01-10 | 2003-06-18 | 清华大学 | Rare earth hydroxide nano tubes and synthesis of serial rare earth compounds nano tubes |
| CN1850722A (en) * | 2006-05-23 | 2006-10-25 | 湖北大学 | Optimized-oriented-growth preparing method for BndT ferro-electric film |
| CN1872696A (en) * | 2006-06-08 | 2006-12-06 | 南昌大学 | Method for preparing Nano tube of lanthanum hydroxide, and Nano tube of lanthanum oxide |
Non-Patent Citations (4)
| Title |
|---|
| 李佳等.镧掺杂钛酸铋铁电薄膜的研究进展.中国陶瓷43 8.2007,43(8),9-13. |
| 李佳等.镧掺杂钛酸铋铁电薄膜的研究进展.中国陶瓷43 8.2007,43(8),9-13. * |
| 马骏等.钕掺杂钛酸铋自组装纳米颗粒的制备和微结构分析.四川大学学报42 增刊2.2005,42(增刊2),207-212. |
| 马骏等.钕掺杂钛酸铋自组装纳米颗粒的制备和微结构分析.四川大学学报42 增刊2.2005,42(增刊2),207-212. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101279767A (en) | 2008-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101279767B (en) | Preparation of lanthanide series rare-earth doped bismuth titanate nano-tube | |
| CN104086172B (en) | A kind of ultra-wide temperature high stable lead-free capacitor ceramics dielectric material and preparation method thereof | |
| CN106340627B (en) | A kind of preparation method of sodium-ion battery positive material | |
| Petrykin et al. | Chemistry and applications of polymeric gel precursors | |
| CN102617958B (en) | Polyvinylidene difluoride-trifluoroethylene/ nickel doped titanium dioxide composite film | |
| CN102195042A (en) | High performance lithium ion battery anode material lithium manganate and preparation method thereof | |
| CN102044700B (en) | Lithium lanthanum bismuthate-based solid electrolyte material and preparation method thereof | |
| CN103700841A (en) | High-property lithium manganate gradient anode material and preparation method thereof | |
| US20150115201A1 (en) | Metal nanoparticle-coating titanate fluorescent material and preparation method therefor | |
| CN104030676B (en) | The preparation method of barium strontium titanate nano powder | |
| CN103553589A (en) | Method for preparing CaCu3Ti4O12 ceramic material | |
| CN104478235A (en) | Multiferroic Bi(0.98-x)Sr0.02RExFe0.97Mn0.03O3-CuFe2O4 composite film and preparation method thereof | |
| CN104529436B (en) | A kind of high-compactness Bi4-xNdxTi3O12The preparation method of ferroelectric ceramics | |
| CN102557634B (en) | Method for preparing multi-component trace codoping zirconium barium strontium titanate-based micro powder | |
| CN101544492B (en) | Method for preparing composite inorganic metal oxide | |
| CN102320826B (en) | Multi-case-layer structure X8R capacitor dielectric ceramic and preparation method thereof | |
| CN104446445A (en) | Preparation method of monodisperse nano-powdery barium titanate | |
| Liu et al. | Highly enhanced f–f transitions of Eu3+ in La2O3 phosphor via citric acid and poly (ethylene glycol) precursor route | |
| CN103833353B (en) | Preparation process for praseodymium- iron- co-doped strontium titanate multiferroic film | |
| CN100467421C (en) | Preparation method of calcium, copper, titanium lanthanum oxygen dielectric ceramic powder | |
| CN105567232A (en) | Preparation method of titanate fluorescent powder for LED | |
| CN104945645B (en) | The preparation method of composite polyethylene material | |
| CN107275475A (en) | A kind of TiO2Composite dielectric material of@PZT nano-wire arrays/polymer and preparation method thereof | |
| CN104673308B (en) | Material for realizing near-infrared luminescence under ultraviolet excitation and preparation method thereof | |
| CN105218076B (en) | One kind prepares SrMnO using sol-gal process3The method of ceramic powder |
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: 20100616 Termination date: 20110428 |