CN1789140A - Method for preparing hollow nano-material of stannic oxide - Google Patents
Method for preparing hollow nano-material of stannic oxide Download PDFInfo
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- CN1789140A CN1789140A CN 200510129960 CN200510129960A CN1789140A CN 1789140 A CN1789140 A CN 1789140A CN 200510129960 CN200510129960 CN 200510129960 CN 200510129960 A CN200510129960 A CN 200510129960A CN 1789140 A CN1789140 A CN 1789140A
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Abstract
A method for preparing stannic oxide hollow nano material, relating to the nano material prepartion, especially relating to a method for preparing stannic oxide hollow nano material by taking zinc oxide as mould, and providing a general method for preparing stannic oxide hollow nano material in various shape. The steps comprises: preparing zinc oxide nano material, preparing SnH4 predecessor material, the produced SnH4 is carried into an air-pocket by nitrogen for emergency, producing SnO2 housing, that is to produce ZnO/SnO2 composite material with kernel-housing structure on the silicon substrate, removing ZnO inner core and getting the SnO2 hollow nano material keeping the ZnO original shape. The ZnO nano material is characterized by the rich shapes, good crystallinity of outer housing and controllable width of the SnO2 hollow material outer wall.
Description
Technical field
The present invention relates to a kind of preparation of nano material, especially relating to a kind of is to sacrifice the method that template prepares hollow nano-material of stannic oxide with zinc oxide.
Technical background
Since Iijima in 1991 found carbon nanotube, hollow nano-materials such as nanotube and nanometer ball were because it has caused people's research interest gradually at the special performance that aspects such as optics, electricity and air-sensitive show.Compare with solid materials such as nano wire, nanometer rod and nano particles, hollow nano-material has the characteristics of low density high-specific surface area, and the application in fields such as gas sensors has huge advantage.In addition, the cavity of hollow nano-material can be used as small container and holds some functional materials or drug molecule, and its outer wall can play the effect of protection, therefore at aspects such as biomarker and medicament slow releases good prospects for application is arranged also.
Stannic oxide (SnO
2) be a kind of n type metal oxide semiconductor material of broad-band gap, its energy gap is 3.6eV during 300K, obtain widespread use in fields such as gas sensor, transparency conductive electrode, transistor and solar cells, be considered to one of functional materials of tool application prospect.In the more than ten years in past, about SnO
2The work of nano material mainly concentrates on the research aspect of the synthetic and physicochemical property of solid materials such as nano thin-film, nano particle and nano wire, to SnO
2The research of hollow structure compares less.At present, reported SnO
2The preparation method of hollow structure mainly is a template.For example Lee is imitated jade etc. (CN200410039474.3) to utilize emulsion particle is nuclear, does husk as raw material with the inorganic tin of mixing antimony, forms organic/inorganic core shell structure particle by ion exchange reaction, and organic core is removed in calcining then, obtains hollow stannic oxide powder particle; (Chen Yanhui etc., the Prepared by Sol Gel Method of tin dioxide nanometer tube array and structural characterization, science communication, 2004,49 (23): 2422-2425) in the template of anodised aluminium, prepared SnO such as Chen Yanhui with sol-gel method
2Nanotube, Electronic Speculum characterization result show that its tube wall is a polycrystalline cassiterite structure; (J.Phys.Chem.B 2004, serve as to sacrifice template with α-MoO3 nanometer rod 108:5867-5874), prepared the uniform SnO that takes measurements greatly by the auxiliary hydro-thermal reaction method of salt for Liu Bin etc.
2Nanotube, but its tube wall is polycrystalline equally.Because above these SnO
2The preparation of hollow structure all realizes in solution environmental, so the SnO that obtains
2The outer wall degree of crystallinity of hollow material is poor, all is polycrystalline; And the form of hollow material is single, can only synthesize tubulose or globular hollow structure, synthesize the SnO of other form
2Hollow structure just is difficult to realize.Therefore developing a kind of method that operation is simple prepares the SnO that crystalline state is good, form is various in a large number
2Hollow nano-material is very important for satisfying its application aspect following nano-device.
Summary of the invention
The objective of the invention is at existing SnO
2Above shortcomings among the hollow nano-material preparation method provide a kind of SnO for preparing various forms
2The universal method of hollow nano-material.The technical solution used in the present invention is to utilize ZnO and SnO
2Difference on acid resistance serves as to sacrifice template with the abundant ZnO nano material of form, the SnO of the ZnO form that is maintained through coating with after removing the nuclear step
2Hollow nano-material.
Processing step of the present invention is as follows:
1) preparation of ZnO template: prepare the ZnO nano material by ordinary methods such as chemical vapour deposition, ionic liquid or laser splashs;
2) SnH
4The preparation of presoma: with SnCl
45H
2The O aqueous solution is added drop-wise to KOH and KBH
4In the mixed aqueous solution, the gas SnH of generation
4Pass through N
2Carry enter in the air bag standby;
3) SnO
2The growth of shell: the ZnO nano material for preparing is dispersed in cuts out on the good silicon chip substrate, be placed on then in the reaction chamber of chemical vapor deposition unit as SnO
2The substrate of growth after the question response chamber vacuumizes, is heated to 600～800 ℃ with silicon chip substrate, feeds the SnH for preparing
4/ N
2Gas mixture, deposition back stop supplies SnH
4/ N
2Gas mixture and the power supply of closing heating controller are lowered the temperature silicon chip naturally, close vacuum system at last, and promptly growth obtains having the ZnO/SnO of nucleocapsid structure on silicon chip substrate
2Matrix material;
4) removing of ZnO kernel: deposition SnO
2The product of back gained is immersed in together with silicon chip substrate in the culture dish that fills dilute acid soln, cleans to pH with clear water to be neutral after drying, the SnO of the ZnO original shape that promptly is maintained again
2Hollow nano-material.
In step 1), described ZnO nano material is four jiaos of forked ZnO, aircraft shape ZnO, array-like ZnO, hexa-prism ZnO, pyramid shape ZnO or banded ZnO etc.
In step 2) in, be the SnCl of 0.10～0.30g/ml with concentration
45H
2The O aqueous solution is added drop-wise to KOH and the KBH that concentration is 0.025～0.075g/ml
4Mixed aqueous solution; The mass ratio of each reactant is SnCl
45H
2O: KOH: KBH
4=1: (0.3～0.8): (0.3～0.8) is preferably SnCl
45H
2O: KOH: KBH
4=1: 0.5: 0.5, the gas SnH of generation
4By flow velocity is the N of 100～300sccm
2Carry enter in the air bag standby.
In step 3), feed the SnH for preparing
4/ N
2The flow velocity of gas mixture is 10～80sccm, and depositing time is 1～10min.
In step 4), deposition SnO
2The soak time that the product of back gained is immersed in the culture dish that fills dilute acid soln together with silicon chip substrate is preferably 1～4h; Described diluted acid is selected from dilute hydrochloric acid, rare nitric acid, dilute sulphuric acid or dilute phosphoric acid etc., and described dilute acid concentration is chosen as 0.05～1M.
With prepare SnO in the existing solution
2The method of hollow material is compared, and the present invention has following outstanding advantage: the SnO that 1) obtains
2The form of hollow material is abundant.Owing to have extremely abundant form as the ZnO nano material of sacrificing template, process coats and removes after the nuclear step, SnO
2Fully the profile of ZnO is duplicated and remain, therefore utilize the present invention to prepare to comprise the SnO of variforms such as four jiaos of forked, aircraft shapes, array-like, hexa-prism, pyramid shape and band shape
2Hollow nano-material.2) SnO that obtains
2The degree of crystallinity of hollow material outer wall is good.Because SnO
2The step of clading ZnO template is an epitaxially grown step, whole SnO
2Shell is well-crystallized's a monocrystalline.3) SnO that obtains
2The controllable thickness of hollow material outer wall.Because be SnO
2The step of clading ZnO template is the step of a vapour deposition, to SnO
2The control of shell growth thickness can be passed through SnH
4/ N
2The accurate control of the concentration of gas mixture, flow velocity and depositing time realizes.
Description of drawings
Fig. 1 is raw material for (a) with the Zn powder, the transmission electron microscope photo of four jiaos of forked ZnO that prepare by chemical Vapor deposition process; (b) be with SnH
4Be Xi Yuan, at four jiaos of forked ZnO template surface deposition SnO
2After four jiaos of forked ZnO/SnO of obtaining with nucleocapsid structure
2The transmission electron microscope photo; (c) four jiaos of forked SnO for after peracid treatment, obtaining
2The transmission electron microscope photo of hollow nano-material.
Fig. 2 (a) is for being raw material with the Zn powder, by chemical Vapor deposition process prepare the transmission electron microscope photo of aircraft shape ZnO; (b) be with SnH
4Be Xi Yuan, at aircraft shape ZnO template surface deposition SnO
2After the aircraft shape ZnO/SnO that obtains with nucleocapsid structure
2Electron scanning micrograph; (c) the aircraft shape SnO for after peracid treatment, obtaining
2The electron scanning micrograph of hollow nano-material.
Fig. 3 (a) is for being raw material with the Zn grain, the electron scanning micrograph of the array ZnO nano wire for preparing by chemical Vapor deposition process; (b) be with SnH
4Be Xi Yuan, at array-like ZnO template surface deposition SnO
2After the array-like ZnO/SnO that obtains with nucleocapsid structure
2The electron scanning micrograph of composite nano-line; (c) the array-like SnO for after peracid treatment, obtaining
2The electron scanning micrograph of hollow nano-material.
Fig. 4 (a) is for being raw material with the Zn grain, the electron scanning micrograph of the hexa-prism ZnO for preparing by the laser splash method; (b) be with SnH
4Be Xi Yuan, at hexa-prism ZnO template surface deposition SnO
2After the hexa-prism ZnO/SnO that obtains with nucleocapsid structure
2The electron scanning micrograph of composite Nano rod; (c) the hexa-prism SnO for after peracid treatment, obtaining
2The electron scanning micrograph of hollow nano-material.
Fig. 5 (a) decomposes the electron scanning micrograph of the pyramid shape ZnO that obtains for being raw material with the zinc acetate in ionic liquid; (b) be with SnH
4Be Xi Yuan, at pyramid shape ZnO template surface deposition SnO
2After the pyramid shape ZnO/SnO that obtains with nucleocapsid structure
2Electron scanning micrograph; (c) the pyramid shape SnO for after peracid treatment, obtaining
2The electron scanning micrograph of hollow nano-material.
Embodiment
The present invention is further illustrated in conjunction with the accompanying drawings below by embodiment.Used in the present embodiment chemical vapor deposition unit adopts the chemical vapor deposition unit (referring to CN1546723A and CN2655310Y patent) that integrates the silicon chip heating deposition, silicon chip both as heating source also as deposition substrate, its basic functional principle is for to be heated to different temperature through the size of current of silicon chip with silicon chip by controlling flow, but to be equally applicable to the tube furnace be the conventional gas-phase deposition apparatus of heating source to this preparation method.
The chemical vapor deposition unit that integrates the silicon chip heating deposition is provided with 1) boost-up circuit, the external silicon chip (load) that is heated of boost-up circuit output terminal, be used for when silicon chip is in cold state, voltage of supply is boosted with the startup silicon chip, and reduce voltage in real time along with silicon chip heats up.2) pulse-width modulation circuit, its pulse-width signal output termination boost-up circuit control signal input terminus, for boost-up circuit provides pulse-width signal, the current signal output end of over-current signal input termination boost-up circuit is for boost-up circuit provides overcurrent protection.3) overpressure protection circuit, its superpressure is judged the external silicon chip that is heated of signal input part, its superpressure shutdown signal is exported the modulation signal input terminus of termination pulse-width modulation circuit, is used for monitoring in real time the output voltage of boost-up circuit.4) constant-current circuit, the external silicon chip that is heated of its input terminus is used to control the silicon chip electric current, to realize the purpose of control silicon temperature.5) boost or switching circuit is judged in the step-down constant current automatically, connect boost-up circuit and constant-current circuit respectively, the work that is used for boost-up circuit and constant-current circuit is switched.6) interface circuit, its current sample port connects constant-current circuit, is heated the external silicon chip that is heated of silicon chip both end voltage sample port, is computer or micro-chip control temperature interface, and monitors silicon chip both end voltage, current sample port.7) power supply connects boost-up circuit, pulse-width modulation circuit, overpressure protection circuit, constant-current circuit respectively, boosts or switching circuit and interface circuit etc. are judged in the step-down constant current automatically.
Embodiment 1
1) preparation of four jiaos of forked ZnO kernels: take by weighing the 0.1gZn powder, place on the silicon chip substrate of the chemical vapor deposition unit that integrates the silicon chip heating deposition, start the heating controller power supply, setting electric current is that 5A is that temperature is 800 ℃, heating Zn powder, four jiaos of forked ZnO that evaporation obtains were collected at the 1cm place directly over the silicon slice placed of tailoring with other a slice placed the Zn powder simultaneously;
2) SnH
4The preparation of presoma: take by weighing KBH respectively
4With each 15g of KOH, be mixed with in the three-necked flask of packing into behind the 200ml aqueous solution; Take by weighing 30g SnCl
45H
2O is mixed with the 100ml aqueous solution, in the constant pressure funnel of packing into.Three-necked flask intermediary eck is connected with constant pressure funnel, and all the other two ecks are N
2The import of (carrier gas/carrier gas) and outlet.With the SnCl in the constant pressure funnel
45H
2The O aqueous solution dropwise adds KOH and KBH in the three-necked flask
4Mixed aqueous solution, the SnH of generation
4Gas is the N of 300sccm by flow velocity
2Carrier gas carries that to enter an airbag standby;
3) SnO
2The growth of shell: the silicon chip that will deposit four jiaos of forked ZnO is fixed on two electrodes of reaction unit, after treating that the silica tube reaction chamber vacuumizes, start silicon chip microcell heating controller power supply, setting electric current is that 5A is that temperature is 800 ℃, feeds the SnH for preparing with the flow velocity of 60sccm
4/ N
2Gas mixture is closed silicon chip microcell heating controller power supply through behind the 5min, closes vacuum system.
4) removing of ZnO kernel: will be immersed in together with silicon chip substrate through the product of twice deposition gained and fill in the watch-glass of dilute hydrochloric acid solution that 20ml concentration is 0.05～0.1M, and behind the 1h product be taken out; Again product is immersed in the clear water, changes clear water one time, be neutral until pH value of solution every 30min.Dry then with the product that centrifugation method is collected after cleaning, promptly obtain four jiaos of forked SnO
2Hollow nano-material.
The sedimentation products that each step obtains is all passed through transmission electron microscope and is characterized.The product that is obtained by chemical Vapor deposition process mainly is four jiaos of forked ZnO, and the diameter of every nanometer rod is that (Fig. 1 a) for 30～100nm; Through SnO
2After the coating, the size of four jiaos of forks increases to some extent, and the diameter of every nanometer rod is 40～130nm (Fig. 1 b); Four jiaos of forks that corroded through diluted acid are hollow shape, and profile keeps better, and the thickness of tube wall is 10～30nm.
Preparation process is similar to embodiment 1, just step 2) middle KBH
4Respectively take by weighing 5g and SnCl with KOH
45H
2O takes by weighing 10g, carrier gas N
2Flow velocity be 100sccm; Flow velocity with 80sccm in the step 3) feeds the SnH for preparing
4/ N
2Gas mixture, depositing time are 10min; Employed diluted acid is a dilute hydrochloric acid in the step 4), and concentration is 0.1～0.5M, and soak time is 2h.
The sedimentation products that each step obtains is all passed through scanning electronic microscope and is characterized.The product that is obtained by chemical Vapor deposition process also contains the ZnO of a spot of aircraft shape except four jiaos of forked ZnO of high yield, (Fig. 2 a) for smooth surface; Through SnO
2After the coating, the size of this aircraft shape structure increases to some extent, and the surface becomes coarse (Fig. 2 b); The SnO that the process hcl corrosion is crossed
2Material is hollow aircraft shape, and profile keeps better, and the thickness of tube wall is 20～50nm (Fig. 2 c).
Embodiment 3
1) be raw material with the Zn grain, obtain array-like ZnO nano wire by chemical Vapor deposition process deposition on the good silicon chip substrate of sanction, its diameter is 100～200nm, and length is 1～20 μ m;
2) step 3), 4) substantially the same manner as Example 1, be step 2) middle KBH
4Respectively take by weighing 10g and SnCl with KOH
45H
2O takes by weighing 20g, carrier gas N
2Flow velocity be 200sccm; The ZnO nano wire that will deposit array-like in the step 3) is as SnO
2Sedimentary substrate, the current settings by silicon chip is that 4A is that temperature is 750 ℃, feeds the SnH for preparing with the flow velocity of 40sccm
4/ N
2Gas mixture, depositing time are 8min; Employed diluted acid is a dilute hydrochloric acid in the step 4), and concentration is 0.5～1M, and soak time is 3h.
The sedimentation products that each step obtains is all passed through scanning electronic microscope and is characterized.The ZnO that is prepared by chemical Vapor deposition process is that (Fig. 3 a) for the nano wire of array-like; Through SnO
2After the coating, the size of array-like structure increases to some extent, and the surface becomes coarse (Fig. 3 b); Through obtaining SnO after the diluted acid corrosion
2Open tube (Fig. 3 c) still perpendicular to silicon chip substrate, is keeping array-like, and thickness of pipe is 50～100nm.
Embodiment 4
1) be raw material with the Zn grain, deposition obtains the ZnO nanometer rod to the method by laser splash on the good silicon chip substrate cutting out, and its diameter is 250～500nm, and length is 1.5～3 μ m;
2) step 3), 4) substantially the same manner as Example 1, just will deposit the ZnO nanometer rod as SnO in the step 3)
2Sedimentary substrate, the current settings by silicon chip is that 2.5A is that temperature is set at 600 ℃; Employed diluted acid is rare nitric acid in the step 4), and concentration is 0.5～0.8M, and soak time is 2h.
The product that each step obtains all passes through scanning electronic microscope and characterizes.The ZnO that obtains by the laser splash method is the nanometer rod of hexa-prism, and its diameter is that (Fig. 4 a) for 200～500nm; Through SnO
2After the coating, the size of hexa-prism structure increases to some extent, and the surface becomes coarse (Fig. 4 b); Through the SnO that obtains after the diluted acid corrosion
2It is 100～200nm that hollow nano-material (Fig. 4 c) is still keeping hexa-prism, thickness of pipe.
Embodiment 5
1) being raw material with the zinc acetate, is solvent with the ionic liquid, prepares pyramid shape ZnO by thermolysis.The pyramid shape ZnO powder for preparing is dispersed in the dehydrated alcohol, gets a little ZnO suspension liquid with dropper and dropwise drop on the good silicon chip substrate of sanction, under infrared lamp, dry;
2) step 3), 4) substantially the same manner as Example 1, just will deposit the silicon chip of pyramid shape ZnO as SnO in the step 3)
2Sedimentary substrate, the current settings by silicon chip is that 3.5A is that temperature is 700 ℃ of SnH
4/ N
2The flow rate control of gas mixture is at 10～40sccm, and the time is controlled at 1～3min.Employed diluted acid is a dilute sulphuric acid in the step 4), and concentration is 0.05～0.15M, and soak time is 3h.
The product that each step obtains all passes through scanning electronic microscope and characterizes.The ZnO that obtains by the ionic liquid method is the hecaprismo of pyramid shape, and its bottom surface diameter is that (Fig. 5 a) for 1～1.5 μ m; Through SnO
2After the coating, the size of pyramid shape structure increases to some extent, and the surface becomes coarse (Fig. 5 b); Through the SnO that obtains after the diluted acid corrosion
2It is 50～250nm that hollow nano-material (Fig. 5 c) is keeping pyramid shape, thickness of pipe.
Embodiment 6
1) with the zinc powder be raw material, deposition obtains the ZnO nano belt to the method by chemical vapour deposition on the good silicon chip substrate cutting out, and its width is 50～300nm, and thickness is 10～50nm, and length is 10～200 μ m;
2) step 3), 4) substantially the same manner as Example 1, just will deposit the silicon chip of banded ZnO as SnO in the step 3)
2Sedimentary substrate; Employed diluted acid is a dilute phosphoric acid in the step 4), and concentration is 0.1～0.3M, and soak time is 4h.
When preparation ZnO nano material, can adopt ordinary methods such as chemical vapour deposition, ionic liquid or laser splash in the foregoing description;
When adopting chemical Vapor deposition process, the Zn powder can be placed on the reaction chamber central authorities of chemical vapor deposition unit, place silicon chip as the sedimentary substrate of ZnO at its downstream direction, after the question response chamber vacuumizes, reaction chamber is heated to 600～800 ℃, close the power supply of heating controller after the deposition and lower the temperature naturally, close vacuum system at last, promptly growth obtains the ZnO nano material on silicon chip substrate.
When adopting the ionic liquid method, the oxysalt of zinc can be joined in the ionic liquid that constitutes by quadrol (or trioctylamine or 30% aqueous methylamine solution) and oleic acid, then at 270-400 ℃ of following constant temperature 20min-240min, cooling at room temperature at last, take off the faint yellow precipitation of layer and clean up repeatedly, promptly obtain the ZnO nano material with normal hexane and ethanol.
When adopting the laser splash method, the Zn grain can be placed on the reaction chamber bottom of an end closure, place silicon chip as the sedimentary substrate of ZnO at its downstream direction, after the question response chamber vacuumizes, silicon chip is heated to 600～800 ℃ also makes its evaporation with laser radiation Zn grain, close the power supply of laser and heating controller after the deposition and lower the temperature naturally, close vacuum system at last, promptly growth obtains the ZnO nano material on silicon chip substrate.
Claims (10)
1, the preparation method of hollow nano-material of stannic oxide is characterized in that its step is as follows:
1) preparation of ZnO template: prepare the ZnO nano material by chemical vapour deposition, ionic liquid or laser splash method;
2) SnH
4The preparation of presoma: with SnCl
45H
2The O aqueous solution is added drop-wise to KOH and KBH
4In the mixed aqueous solution, the gas SnH of generation
4Pass through N
2Carry enter in the air bag standby;
3) SnO
2The growth of shell: the ZnO nano material for preparing is dispersed in cuts out on the good silicon chip substrate, be placed on then in the reaction chamber of chemical vapor deposition unit as SnO
2The substrate of growth after the question response chamber vacuumizes, is heated to 600～800 ℃ with silicon chip substrate, feeds the SnH for preparing
4/ N
2Gas mixture, deposition back stop supplies SnH
4/ N
2Gas mixture and the power supply of closing heating controller are lowered the temperature silicon chip naturally, close vacuum system at last, and promptly growth obtains having the ZnO/SnO of nucleocapsid structure on silicon chip substrate
2Matrix material;
4) removing of ZnO kernel: deposition SnO
2The product of back gained is immersed in together with silicon chip substrate in the culture dish that fills dilute acid soln, cleans to pH with clear water to be neutral after drying, the SnO of the ZnO original shape that promptly is maintained again
2Hollow nano-material.
2, the preparation method of hollow nano-material of stannic oxide as claimed in claim 1 is characterized in that in step 1), and described ZnO nano material is four jiaos of forked ZnO, aircraft shape ZnO, array-like ZnO, hexa-prism ZnO, pyramid shape ZnO or banded ZnO.
3, the preparation method of hollow nano-material of stannic oxide as claimed in claim 1 is characterized in that in step 2) in, be the SnCl of 0.10～0.30g/ml with concentration
45H
2The O aqueous solution is added drop-wise to KOH and the KBH that concentration is 0.025～0.075g/ml
4Mixed aqueous solution.
4, the preparation method of hollow nano-material of stannic oxide as claimed in claim 1 is characterized in that in step 2) in, mass ratio SnCl pressed
45H
2The O aqueous solution, KOH and KBH
4The content of mixed aqueous solution is SnCl
45H
2O: KOH: KBH
4=1: 0.3～0.8: 0.3～0.8.
5, the preparation method of hollow nano-material of stannic oxide as claimed in claim 4 is characterized in that in step 2) in, SnCl
45H
2O: KOH: KBH
4=1: 0.5: 0.5.
6, the preparation method of hollow nano-material of stannic oxide as claimed in claim 1 is characterized in that in step 2) in, the gas SnH of generation
4By flow velocity is the N of 100～300sccm
2Carry enter in the air bag standby.
7, the preparation method of hollow nano-material of stannic oxide as claimed in claim 1 is characterized in that in step 3), feeds the SnH for preparing
4/ N
2The flow velocity of gas mixture is 10～80sccm.
8, the preparation method of hollow nano-material of stannic oxide as claimed in claim 1 is characterized in that in step 3), and depositing time is 1～10min.
9, the preparation method of hollow nano-material of stannic oxide as claimed in claim 1 is characterized in that in step 4), deposition SnO
2The soak time that the product of back gained is immersed in together with silicon chip substrate in the culture dish that fills dilute acid soln is 1～4h.
As the preparation method of claim 1 or 9 described hollow nano-material of stannic oxide, it is characterized in that in step 4) that 10, described diluted acid is selected from the dilute hydrochloric acid that concentration is 0.05～1M, rare nitric acid, dilute sulphuric acid or dilute phosphoric acid.
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| CN100463860C (en) * | 2007-02-01 | 2009-02-25 | 郑州大学 | Method for preparing stannic oxide hollow sphere |
| CN101428847B (en) * | 2008-12-15 | 2010-06-02 | 吉林大学 | Process for producing nanostructured tin dioxide lithium ion battery negative pole material |
| CN101638247B (en) * | 2009-08-26 | 2011-11-09 | 福州大学 | Method for preparing tin dioxide nano hollow sphere comprising nano rods and application in lithium battery |
| CN105481004A (en) * | 2014-09-17 | 2016-04-13 | 中国科学院上海硅酸盐研究所 | Stannic oxide nanotubes with high electrical properties and preparation method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1260133C (en) * | 2003-03-14 | 2006-06-21 | 中国科学院上海硅酸盐研究所 | Method for preparing nano tin-oxide powder |
| CN1201860C (en) * | 2003-05-26 | 2005-05-18 | 中国科学院广州地球化学研究所 | Preparation method of nano Zno-SnO2 composite oxide photo-catalyst |
| CN100480166C (en) * | 2003-09-28 | 2009-04-22 | 中国科学院化学研究所 | Nano composite inorganic semiconductor hollow ball and preparation method thereof |
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2005
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100463860C (en) * | 2007-02-01 | 2009-02-25 | 郑州大学 | Method for preparing stannic oxide hollow sphere |
| CN101428847B (en) * | 2008-12-15 | 2010-06-02 | 吉林大学 | Process for producing nanostructured tin dioxide lithium ion battery negative pole material |
| CN101638247B (en) * | 2009-08-26 | 2011-11-09 | 福州大学 | Method for preparing tin dioxide nano hollow sphere comprising nano rods and application in lithium battery |
| CN105481004A (en) * | 2014-09-17 | 2016-04-13 | 中国科学院上海硅酸盐研究所 | Stannic oxide nanotubes with high electrical properties and preparation method therefor |
| CN105481004B (en) * | 2014-09-17 | 2017-07-14 | 中国科学院上海硅酸盐研究所 | A kind of high electric property tin dioxide nanometer tube and preparation method thereof |
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