CN1778684A - Base metal stannate nanometer tube and its production thereof - Google Patents
Base metal stannate nanometer tube and its production thereof Download PDFInfo
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- CN1778684A CN1778684A CN 200510019638 CN200510019638A CN1778684A CN 1778684 A CN1778684 A CN 1778684A CN 200510019638 CN200510019638 CN 200510019638 CN 200510019638 A CN200510019638 A CN 200510019638A CN 1778684 A CN1778684 A CN 1778684A
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- nanometer tube
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Abstract
An alkaline earth metal stannate salt nanometer tube and its production are disclosed. The process is carried out by taking soluble tin salt as raw materials, forming complex anion in alkali solution, hydrothermal treating or oxidation-reduction reacting to obtain precursor under the reaction of surface active agent directly, which is high-content polymer with C-O long chain, and alkaline earth metal ion exchanging by precursor to obtain alkaline earth metal stannate salt nanometer tube. It has simple operation, easy size control with external diameter 100nm-280nm and internal diameter 20nm-170nm, low cost and high output. It can be used for dielectric ceramic, sensor and luminous materials.
Description
Technical field
The present invention relates to a kind of " soft template " effect, utilize hydrothermal method and ion exchange technique to combine and synthesize the method for base metal stannate nanometer tube, belong to the inorganic material preparation process technical field by tensio-active agent.
Background technology
Iijima had found carbon nanotube by the observation of high-resolution electron microscope in 1991, promoted the research of whole quasi-one-dimensional nanometer material, other various one dimension tubular nanometer materials are because its unique microtexture, and by and performance such as the distinguished electricity, optics, magnetics and the electrochemistry that produce and receiving much concern, wherein metal (as Pd, B), metal oxide are (as V
2O
5, TiO
2), metallic sulfide is (as WS
2, MoS
2), metal nitride (as BN, BCN), halogenide be (as NiCl
2), sulfide is (as InS, NbS
2, NbS
2, TaS
2) wait nanotube to come out one after another, but still not satisfying the demand of a plurality of researchs and Application Areas, the nanotube of more kinds of materials and type remains exploitation, especially ternary compound nanotube, because rare up to now research.
The perovskite typed base metal stannate causes people's very big concern in recent years; it can be widely used in electrode materials of dielectric ceramic, transmitter, luminescent material matrix and battery etc.; three kinds of methods of the general employing of the preparation of such material: high temperature solid-state reactions method (being higher than 1250 ℃), sol-gel method and common hydrothermal method; the pattern of the product that these three kinds of methods obtain is the small-particle or the square bodily form, is applied in above-mentioned field already.But development along with microelectronics, the trend toward miniaturization of electron device is irresistible, " microtubule " of base metal stannate changed also extremely urgent thereupon, it can play a significant role at the manufacture view of mesoscopic physics and nanoscale devices, and the preparation of therefore exploring base metal stannate nanometer tube has crucial meaning undoubtedly.
Summary of the invention
The object of the present invention is to provide a kind of uniform diameter, base metal stannate nanometer tube that length-to-diameter ratio is big, and the method for preparing base metal stannate nanometer tube in conjunction with common hydrothermal method and ion exchange technique.
The base metal stannate nanometer tube that the present invention proposes is that a kind of monocrystalline opening nanotube, external diameter of pipe are 100nm～280nm, and internal diameter is 20nm～170nm, and pipe range reaches more than 1.5 microns, uniform diameter.
The preparation method of base metal stannate nanometer tube of the present invention comprises the steps:
1st, with the solubility tin-salt solution with after the tensio-active agent that contains the C-O long-chain mixes mutually with 1: 0.16～1.5 mol ratios, the NaOH solution of 3～5 mol is slowly joined in the above-mentioned solution, placing power then is 80W, frequency is in the ultrasonic generator of 40kHz, carries out the sonochemistry reaction; Used solubility pink salt is any in oxymuriate, nitrate or the acetate;
In the stainless steel cauldron of the mixing solutions immigration polytetrafluoroethylsubstrate substrate of the reaction of sonochemistry that 2nd, step 1 is obtained, carry out hydro-thermal reaction to fully under boosting in reaction, get white cured shape product, hydrothermal temperature is 120 ℃～220 ℃;
3rd, behind the white cured shape product and solution separating that step 2 is obtained, dissolve in the alkaline including earth metal ionic pure water, make it to dissolve and with the same ultrasound condition of step 1 under carry out ion-exchange, 0.5 stop after～1 hour, through leave standstill, after ageing and the centrifugation, promptly get the base metal stannate nanometer tube that contains crystal water, wherein said alkaline-earth metal ions is any in calcium, magnesium, strontium and the barium;
4th, the base metal stannate nanometer tube that contains crystal water that step 3 is obtained is in 400 ℃～600 ℃ heating, and the water that decrystallizes promptly obtains base metal stannate nanometer tube.
Above-mentioned steps 1 described tensio-active agent is the tensio-active agent that contains the C-O long-chain, i.e. high-molecular weight polyoxyethylene glycol (PEG), primary amine C
nH
2n+1NH
2N=12 wherein, 14 or 16, quaternary cationics C
16TMABr (hexadecyl trimethyl ammonium bromide, TMA=trimethylammonium), long-chain vitriol C
nH
2n+1OSO
3Na is n=12 wherein, and 14 or 16, long-chain phosphoric acid salt C
nH
2n+1OPO
3H
2N=12 wherein, 14,16, AOT (the AOT=[2-ethylhexyl] sulfo group amber ripple acid sodium and AEO-9 (a kind of in the AEO-9=polyester fat polyoxyethylenated alcohol, or two kinds mixture.
The 2 described hydro-thermal reaction times of above-mentioned steps are 4～9 hours.
Characteristics of the present invention are the common hydrothermal method preparation base metal stannate nanometer tube that combines with ion exchange technique, uniform diameter, controllable size, this product has wide application prospects in the fields such as electrode materials of dielectric ceramic, transmitter, luminescent material and battery.The entire synthesis process energy consumption is low, equipment is simple, is a kind of high yield, has a preparation method of industrial applications prospect cheaply.
Method of the present invention can be used for preparing the stannate nano pipe of transition metal ion cadmium.
Embodiment
Below in conjunction with example the present invention is described in further detail
Embodiment 1:CaSnO
3The preparation of nanotube.
1, under the room temperature with 1mmolSnCl
4.5H
2O and 3g molecular weight are after 20000 polyoxyethylene glycol is dissolved in the 50ml deionized water, your concentration of rubbing is that the NaOH solution of 4M slowly joins in the above-mentioned solution with 20mL, placing power then is 80W, and frequency is in the ultrasonic generator of 40kHz, carries out the sonochemistry reaction;
The mixing solutions of the reaction of sonochemistry that 2, step 1 is obtained moves in the stainless steel cauldron of polytetrafluoroethylsubstrate substrate, carries out hydro-thermal reaction to fully under boosting in reaction, obtains containing the solution of white cured shape product;
3, behind the white cured shape product and solution separating that step 2 is obtained, dissolve in alkaline including earth metal Ca
2+Pure water in dissolve, and with the same ultrasound condition of step 1 under carry out ion-exchange, stop after 0.5 hour, through leave standstill, ageing and centrifugal after, must contain the base metal stannate nanometer tube of crystal water;
4, the base metal stannate nanometer tube that contains crystal water that step 3 is obtained adds the heat abstraction crystal water in 400 ℃, promptly gets CaSnO
3Nanotube, external diameter of pipe are 220nm～280nm, and internal diameter is 130nm～170nm, and pipe range reaches 5 microns.
Embodiment 2:BaSnO
3The preparation of nanotube.
1, under the room temperature with 1mmolSnCl
4.5H
2After O and 3g polyester fat polyoxyethylenated alcohol were dissolved in the 50ml deionized water, your concentration of rubbing was that the NaOH solution of 4M slowly joins in the above-mentioned solution with 20mL, and placing power then is 80W, and frequency is in the 40kHz ultrasonic generator, carries out the sonochemistry reaction;
2, step 2 is identical with embodiment 1 step 2, obtains containing the solution of white cured shape product;
3, behind the white cured shape product and solution separating that step 2 is obtained, dissolve in alkaline including earth metal Ba
2+Solution in dissolve, and under the ultrasound condition identical, carry out ion-exchange with step 1, stop after 1 hour, through leave standstill, ageing and centrifugal after, must contain the base metal stannate nanometer tube of crystal water;
4, the base metal stannate nanometer tube that contains crystal water that step 3 is obtained adds the heat abstraction crystal water in 450 ℃, promptly gets BaSnO
3Nanotube, external diameter of pipe are 150nm～180nm, and internal diameter is 70nm～80nm, and pipe range reaches 2.5 microns.
The preparation of embodiment 3:CaSnO3 nanotube.
1, under the room temperature with 1.0gSnCl
4.5H
2O and 1.0g hexadecyl amine bromide are dissolved in the 60ml deionized water, are slow the adding in the above-mentioned solution of NaOH solution of 4M with 30ml concentration, and placing power then is 80W, and frequency is in the 40kHz ultrasonic generator, carries out the sonochemistry reaction.
2, step 2 is identical with embodiment 1 step 2, obtains containing the solution of white cured shape product;
3, behind the white cured shape product and solution separating that step 2 is obtained, add and contain Ca
2+Solution in dissolve, and under the ultrasound condition identical, carry out ion-exchange with step 1, stop behind the 30min, put through essence, ageing and centrifugal after, must contain the base metal stannate nanometer tube of crystal water;
4, the base metal stannate nanometer tube that contains crystal water that step 3 is obtained adds the heat abstraction crystal water in 500 ℃, promptly gets CaSnO
3Nanotube, external diameter of pipe are 110nm～130nm, and internal diameter is 20nm～50nm, and pipe range reaches 2 microns.
The preparation of embodiment 4:MgSnO3 nanotube.
1, under the room temperature with 1.0gSnCl
4.5H
2O and 0.5g primary amine C
nH
2n+1NH
2(n=12,14 or 16) are dissolved in the 60ml deionized water, are slow the adding in the above-mentioned solution of NaOH solution of 4M with 30ml concentration, and placing power then is 80W, and frequency is in the 40kHz ultrasonic generator, carries out the sonochemistry reaction;
2, step 2 is identical with embodiment 1 step 2, obtains containing the solution of white cured shape product;
3, behind the white cured shape product and solution separating that step 2 is obtained, add and contain Mg
2+Solution in dissolve, and under the ultrasound condition identical, carry out ion-exchange with step 1, stop behind the 30min, put through essence, ageing and centrifugal after, must contain the base metal stannate nanometer tube of crystal water;
4, the base metal stannate nanometer tube that contains crystal water that step 3 is obtained adds the heat abstraction crystal water in 600 ℃, promptly gets MgSnO
3Nanotube, external diameter of pipe are 100nm～140nm, and internal diameter is 60nm～80nm, and pipe range reaches 1.5 microns.
Embodiment 5:CaSnO
3The preparation of nanotube.
1, under the room temperature with 1.0gSnCl
4.5H
2O and 0.5g long-chain vitriol C
nH
2n+1OSO
3Na is dissolved in the 60ml deionized water, is slow the adding in the above-mentioned solution of NaOH solution of 5M with 30ml concentration, and placing power then is 80W, and frequency is in the 40kHz ultrasonic generator, carries out the sonochemistry reaction;
2, step 2 is identical with embodiment 1 step 2, obtains containing the solution of white cured shape product;
3, behind the white cured shape product and solution separating that step 2 is obtained, add and contain Ca
2+Solution in dissolve, and under ultrasound condition, carry out ion-exchange, stop behind the 45min, put through essence, ageing and centrifugal after, promptly get the base metal stannate nanometer tube that contains crystal water;
4, the nanotube that contains crystal water that step 3 is obtained adds the heat abstraction crystal water in 500 ℃ and promptly gets CaSnO
3Nanotube, external diameter of pipe are 110nm～140m, and internal diameter is 60nm～80m, and pipe range reaches 1.5 microns.
Embodiment 6:BaSnO
3The preparation of nanotube.
1, under the room temperature with 1.0gSnCl
4.5H
2O and 0.5g long-chain phosphoric acid salt C
nH
2n+1OPO
3Na is dissolved in the 60ml deionized water, is slow the adding in the above-mentioned solution of NaOH solution of 5M with 30ml concentration, and placing power then is 80W, and frequency is in the 40kHz ultrasonic generator, carries out the sonochemistry reaction;
2, step 2 is identical with embodiment 1 step 2, obtains containing the solution of white cured shape product;
3, behind the white cured shape product and solution separating that step 2 is obtained, add and contain Ba
2+Solution in dissolve, and under the ultrasound condition identical, carry out ion-exchange with step 1, stop behind the 30min, put through essence, ageing and centrifugal after, promptly get the base metal stannate nanometer tube that contains crystal water;
4, the base metal stannate nanometer tube that contains crystal water that step 3 obtains promptly gets BaSnO in 450 ℃ of heating
3Nanotube, external diameter of pipe are 120nm～150nm, and internal diameter is 70nm～90nm, and pipe range reaches 1.8 microns.
The preparation of embodiment 7:MgSnO3 nanotube.
1, under the room temperature with 1.0gSnCl
4.5H
2O and 0.5g AOT[2-ethylhexyl] sodium sulfosuccinate], being dissolved in the 60ml deionized water, is slow the adding in the above-mentioned solution of NaOH solution of 4M with 30ml concentration, and placing power then is 80W, frequency is in the 40kHz ultrasonic generator, carries out the sonochemistry reaction;
2, step 2 is identical with embodiment 1 step 2, obtains containing the solution of white cured shape product;
3, behind the white cured shape product and solution separating that step 2 is obtained, add and contain Mg
2+Solution in dissolve, and under the ultrasound condition identical, carry out ion-exchange with step 1, stop behind the 30min, put through essence, ageing and centrifugal after, promptly get the base metal stannate nanometer tube that contains crystal water;
4, the base metal stannate nanometer tube that contains crystal water that step 3 is obtained promptly gets MgSnO in 500 ℃ of heating
3Nanotube, external diameter of pipe are 120nm～150nm, and internal diameter is 70nm～90nm, and pipe range reaches 2 microns.
Claims (5)
1, a kind of base metal stannate nanometer tube is characterized in that it is a monocrystalline opening nanotube, and external diameter of pipe is 100nm～280nm, and internal diameter is 20nm～170nm, and pipe range reaches more than 1.5 microns.
2, a kind of method for preparing claim 1 described base metal stannate nanometer tube is characterized in that this method comprises the steps:
1st, with the solubility tin-salt solution with after the tensio-active agent that contains the C-O long-chain mixes mutually with 1: 0.16～1.5 mol ratios, the NaOH solution of 3～5 mol is slowly joined in the above-mentioned solution, the ultrasonic generator that places then carries out the sonochemistry reaction; Used solubility pink salt is any in oxymuriate, nitrate or the acetate of tin;
In the stainless steel cauldron of the mixing solutions immigration polytetrafluoroethylsubstrate substrate of the reaction of sonochemistry that 2nd, step 1 is obtained, carry out hydro-thermal reaction to fully under boosting in reaction, get white cured shape product, hydrothermal temperature is 120 ℃～220 ℃;
3rd, behind the white cured shape product and solution separating that step 2 is obtained, dissolve in the alkaline including earth metal ionic pure water, make it to dissolve and with the same ultrasound condition of step 1 under carry out ion-exchange, 0.5 stop after～1 hour, through leave standstill, after ageing and the centrifugation, promptly get the base metal stannate nanometer tube that contains crystal water, wherein said alkaline-earth metal ions is any in calcium, magnesium, strontium and the barium;
4th, the base metal stannate nanometer tube that contains crystal water that step 3 is obtained in 400 ℃～600 ℃ heating water that decrystallizes, promptly obtains base metal stannate nanometer tube.
3, as claim 2 described preparation methods, it is characterized in that: described tensio-active agent is the high-molecular weight polyoxyethylene glycol, primary amine C
nH
2n+1NH
2Its n=12,14 or 16, quaternary cationics hexadecyl trimethyl ammonium bromide, long-chain vitriol C
nH
2n+1OSO
3Its n=12 of Na, 14 or 16, long-chain phosphoric acid salt C
nH
2n+1OPO
3H
2Its n=12,14 or 16, a kind of in [2-ethylhexyl] sulfo group amber ripple acid sodium and the polyester fat polyoxyethylenated alcohol, or two kinds mixture.
4, preparation method as claimed in claim 2 is characterized in that described ultrasonic generator power is 80W, and frequency is 40kHz.
5, preparation method as claimed in claim 2 is characterized in that the described hydro-thermal reaction time is 4～9 hours.
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|---|---|---|---|
| CNB2005100196380A CN1299999C (en) | 2005-10-20 | 2005-10-20 | Base metal stannate nanometer tube and its production thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531044A (en) * | 2011-12-15 | 2012-07-04 | 中国科学院化学研究所 | Lithium ion battery anode material and preparation method and application thereof |
| CN103572410A (en) * | 2013-09-12 | 2014-02-12 | 上海大学 | CaSnO3 nano-fiber prepared by using electrostatic spinning process |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164618C (en) * | 2002-03-14 | 2004-09-01 | 四川大学 | Preparation method of polymer/carbon nano pipe composite material and its in situ mass polymerization |
| CN1204042C (en) * | 2003-06-10 | 2005-06-01 | 东北师范大学 | Method for preparing nano tube of some metalloid oxides and metals with size and shape being controllable |
| CN1214984C (en) * | 2003-10-20 | 2005-08-17 | 武汉大学 | Method for preparing titanium dioxide nano tube |
| CN1256282C (en) * | 2004-05-27 | 2006-05-17 | 上海交通大学 | Preparing method for polymer grafting and modifying titanium dioxide nanometer tube |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531044A (en) * | 2011-12-15 | 2012-07-04 | 中国科学院化学研究所 | Lithium ion battery anode material and preparation method and application thereof |
| CN103572410A (en) * | 2013-09-12 | 2014-02-12 | 上海大学 | CaSnO3 nano-fiber prepared by using electrostatic spinning process |
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Granted publication date: 20070214 Termination date: 20111020 |