CN101519191B - Method for preparing oxide nano-materials by melted hydrated salt - Google Patents

Method for preparing oxide nano-materials by melted hydrated salt Download PDF

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CN101519191B
CN101519191B CN2009101132755A CN200910113275A CN101519191B CN 101519191 B CN101519191 B CN 101519191B CN 2009101132755 A CN2009101132755 A CN 2009101132755A CN 200910113275 A CN200910113275 A CN 200910113275A CN 101519191 B CN101519191 B CN 101519191B
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insoluble product
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nano particle
deionized water
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CN101519191A (en
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潘世烈
田雪林
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention relates to a method for preparing oxide nano-materials by hydrated salt. The method is as follows: melted hydrated salt or compound melted hydrated salt is taken as solvent and reacts with metal oxides, metal halides, metal hydroxides or metal oxyacid salts under the closed reaction condition; and the oxide nano-materials are obtained by washing, separation and drying. By adopting the melted hydrated salt, the method is suitable for preparing simple binary oxides, and is more suitable for preparing complex ternary, quaternary and multi-component oxides. The method has the advantages of large-scale preparation, environment protection, synthesis at low temperature, and the like, and is particularly suitable for the industrially large-scale and environmental-friendly preparationof the oxide nano-materials.

Description

A kind of method of preparing oxide nano-materials by melted hydrated salt
Technical field
The invention belongs to the functional oxide field of nanometer material technology, relate to a kind of new can be in a large number, the method for environmental friendliness preparing oxide nano-materials by melted hydrated salt.
Background technology
Oxide-based nanomaterial is the basis of functional materialss such as development of new light, electricity, magnetic, catalysis and sensing, has broad application prospects in fields such as information technology, the energy, environment, medicine and national defense safeties.The method of synthesis oxide nano material commonly used has vapour deposition, solvent thermal, sol-gel and metallo-organic decomposition process etc.Yet, utilize aforesaid method often to involve organometallic precursor or organic solvent, and the amount that synthesizes product is often in the milligram magnitude, be difficult to realize a large amount of synthetic of nano material, be not suitable for industrialization promotion.And want to realize the commercial application of nano material, realize material a large amount of and eco-friendly synthetic be an important prerequisite.
Molten-salt growth method is a kind of method of nano materials in a large number.This method use high-temperature fusion salt such as NaCl, KCl, KNO 3Deng, or composite molten salt such as LiCl-KCl, LiNO 3-KNO 3Deng as solvent, be used to the mineral compound of synthetic various block phases all the time, be used for the synthetic of nano material in nearly ten years by investigator's exploration both at home and abroad.Diffusion length therein is short because characteristics such as the high polarity of fused-salt medium, high viscosity make reaction monomers, comes a large amount of synthesis of nano yardstick products thereby can introduce the high density pre-reaction material.And melting salt also has high thermal conduction, high heat capacity, use temperature scope and extensively reaches characteristics such as dissolving power is strong, makes it be very beneficial for the synthetic of material.But molten-salt growth method also has the weak point of oneself, and with respect to other liquid-phase synthesis process, its temperature of reaction is too high.Because need to use high-temperature fusion salt, its temperature of reaction is generally more than 800 ℃; Even utilize composite molten salt as medium, its temperature of reaction is also often more than 400 ℃.High temperature of reaction not only consumes energy greatly, and can propose harsher requirement to conversion unit, thereby makes the material preparation cost increase greatly.
At the too high problem of molten-salt growth method temperature of reaction, the present invention uses salt hydrate to reduce temperature of reaction as reaction solvent.Salt hydrate is as LiNO 33H 2O, MnCl 24H 2O, CaCl 26H 2O, MgCl 26H 2O, SrCl 26H 2O, Ba (OH) 28H 2O, Sr (OH) 28H 2O etc. are the crystalline compounds of a class uniqueness, and its fusing point generally from tens to more than 100 degrees centigrade, is often used as phase-changing energy storage material.Use high-temperature molten salt as solvent in view of molten-salt growth method, use low-melting salt hydrate to come the synthesis oxide nano material, can reduce temperature of reaction greatly, and simplify conversion unit as solvent.But there is a problem in melted hydrated salt, and it can decompose and the son that dries out gradually in the system of opening wide, and causes its fusing point constantly to raise.Be subjected to the inspiration of solvent-thermal method, utilize the confined reaction system to avoid this problem.Therefore, the present invention uses melted hydrated salt to carry out the synthetic of nano material as solvent in confined conditions.Have not yet to see the relevant patent and the bibliographical information that utilize melted hydrated salt solvent nano materials.
Summary of the invention
The object of the invention is to provide a kind of method of preparing oxide nano-materials by melted hydrated salt, this method is under the confined reaction condition, use melted hydrated salt or composite molten salt hydrate as solvent, react with metal oxide, metal halide, metal hydroxides or metal oxygen-containing hydrochlorate, wash then, separate, drying, thereby make oxide-based nanomaterial.Adopt the melted hydrated salt method both can prepare the simple binary oxide compound, be more suitable in preparation complicated ternary, quaternary and other multivariant oxide.This method has advantages such as a large amount of preparations, environmental friendliness and low temperature is synthetic, is particularly suitable for industrial mass-producing, greenization prepares oxide-based nanomaterial.
The method of a kind of preparing oxide nano-materials by melted hydrated salt of the present invention follows these steps to carry out
A, melted hydrated salt or composite molten salt hydrate are placed closed reaction vessel, heating fusing in 30 minutes-1 hour under 60-140 ℃ of condition;
B, open encloses container, add metal oxide, metal halide, metal hydroxides or metal oxygen-containing hydrochlorate rapidly, stir, reseal container then, put into thermostat container, temperature 110-180 ℃ of reaction 1-30 hour with teflon rod;
After c, the cooling, take out the gained solid product, with deionized water or 50-70 ℃ of hot water or 0.05-0.2M formic acid or acetic acid dilute solution dissolving washing, the gained mixed solution utilizes high speed centrifugation to separate or vacuum filtration is isolated insoluble product;
D, the isolating insoluble product of step c is alternately washed 3-4 time with 95% ethanol and deionized water, seasoning or temperature 60-100 ℃ constant pressure and dry or vacuum-drying promptly get oxide-based nanomaterial.
Step a encloses container is autoclave or airtight pressure vessel.
Step a melted hydrated salt is the compound L iNO that contains crystal water 33H 2O or MnCl 24H 2O, CaCl 26H 2O or MgCl 26H 2O or SrCl 26H 2O or Ba (OH) 28H 2O or Sr (OH) 28H 2O, its fusing point is from 28-150 degree centigrade.
Step a composite molten salt hydrate is LiNO 33H 2O and MnCl 24H 2O or Ba (OH) 28H 2O and Sr (OH) 28H 2O.
Step b metal oxide is TiO 2Or rutile TiO 2Or MnO 2Or Nb 2O 5Metal halide is MnCl 2Or MoCl 6Metal hydroxides is Ti (OH) 2Or Mn (OH) 2Or NaOH; The metal oxygen-containing hydrochlorate is Zn (CH 3COO) 2Or Mg (CH 3COO) 2Or Li 2CO 3
The isolated insoluble product of step c is the spheroidal particle greater than 200nm, also separates with vacuum filtration.
Step c isolates the liquid that is left behind the insoluble product, obtains salt hydrate by recrystallization and reuses.
The method of a kind of preparing oxide nano-materials by melted hydrated salt of the present invention, this method adopt the melted hydrated salt method to have the plurality of advantages of molten-salt growth method and solvent-thermal method concurrently.At first, characteristics such as the high viscosity of melted hydrated salt, high polarity make it can strengthen nanoparticle nucleated process in the reaction process, thereby can introduce the pre-reaction material of high density, in addition the synthetic yield height, therefore be beneficial to a large amount of preparations that realize nano material, this point is similar with molten-salt growth method.Secondly, with respect to molten-salt growth method, the melted hydrated salt method uses salt hydrate as solvent, and temperature of reaction reduces greatly, will cut down the consumption of energy significantly, and avoid harsh requirement to conversion unit; Furthermore this method not with an organic solvent or pre-reaction material such as organometallics can avoid the pollution to environment, so the melted hydrated salt method is not a kind of eco-friendly synthetic method.In addition, the melted hydrated salt method is reacted in confined conditions, and the reaction under high pressure system that this air tight condition causes helps realizing the low temperature crystallized preparation of nano material.In a word, advantages such as that the melted hydrated salt method has is a large amount of synthetic, environmental friendliness, low-temp reaction, and be easy to realize that industry amplifies, the mass-producing, greenization, the cost degradation preparation that are expected to for oxide-based nanomaterial provide a general approach.
The melted hydrated salt method mainly comprises two parts: the synthetic and product separation purification of material:
Material is synthetic
At first in encloses container salt hydrate (or two kinds of salt hydrate mixtures) being heated to the certain temperature fusing (spends to more than 100 degree from tens, get final product a little more than the salt hydrate fusing point), open container and add other reactant rapidly, after stirring fast, place closed reactor again, react the suitable time in certain temperature, guarantee fully carrying out of reaction.Be noted that if the salt hydrate that uses is alkalescence, then entire reaction course need be used tetrafluoroethylene or other inertia material container and stirring rod etc.
Product separates purifies
Separating purification mainly is to isolate product from the salt hydrate solvent.Because salt hydrate is easily molten mostly or be slightly soluble in water, and prepared oxide-based nanomaterial is mostly water insoluble, therefore can make water or hot water wash dissolving salt hydrate composition, thereby isolates product.For the salt hydrate of alkalescence, also can consider to use the weak acid dilute solution to wash dissolving salt hydrate composition, separation means can be used centrifugation technique; The big product of particle diameter also can use the vacuum filtration device.
Description of drawings
Fig. 1 is the BaTiO of the present invention's preparation 3X-ray powdery diffractometry (XRD) the test result figure of hollow nano particle.
Fig. 2 is the BaTiO of the present invention's preparation 3The transmission electron microscope of hollow nano particle (TEM) photo figure.
Fig. 3 is the BaTiO of the present invention's preparation 3The TEM photo figure of nano particle.
Embodiment
The embodiment agents useful for same is the analytical pure commercial reagents.
Embodiment 1: the melted hydrated salt legal system is equipped with BaTiO 3The hollow nano particle
With 12g Ba (OH) 28H 2O places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 1 hour under 90 ℃ of conditions;
Open encloses container then, add 0.8g TiO rapidly 2Powder stirred with teflon rod, reseals container then, puts into thermostat container, in 180 ℃ of reactions of temperature 3 hours;
After the cooling, take out the gained solid product, with 50 ℃ of hot water dissolving's washings, the gained mixed solution utilizes the supercentrifuge centrifugation to go out insoluble product;
Insoluble product is alternately washed 3 times with 95% ethanol and deionized water, and 60 ℃ of constant pressure and dries of temperature 1 hour promptly get single BaTiO of dispersion 3The hollow nano particle, weighing is no less than 2.2g, isolates the liquid that is left behind the insoluble product, and obtaining salt hydrate by recrystallization can reuse.
By accompanying drawing 1XRD test shows product is the BaTiO of high purity uhligite phase 3, do not contain BaCO 3Deng the impurity that is prone to.The TEM observed result shows that product particle monodispersity is good in the accompanying drawing 2, and yardstick is about the 90-110 nanometer.
Embodiment 2: the melted hydrated salt legal system is equipped with BaTiO 3Nano particle
With 8g Ba (OH) 28H 2O places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 40 minutes under 110 ℃ of conditions;
Open encloses container then, add 0.6g self-control rutile TiO rapidly 2Powder (this rutile TiO 2Utilization is to containing 0.15M TiCl 3The NaCl saturated aqueous solution carry out hydrothermal treatment consists and obtained in 3 hours), stir with teflon rod, reseal container then, put into thermostat container, in 160 ℃ of reactions of temperature 1 hour;
After the cooling, take out the gained solid product, with 0.1M acetic acid dilute solution dissolving washing, the gained mixed solution utilizes high speed centrifugation to isolate insoluble product;
Insoluble product is alternately washed 4 times with 95% ethanol and deionized water, and seasoning promptly gets BaTiO 3Nano particle, weighing is no less than 1.7g, isolates the liquid that is left behind the insoluble product, and obtaining salt hydrate by recrystallization can reuse.
TEM test result (accompanying drawing 3) shows that the gained grain diameter is in the 250-500 nanometer range.
Embodiment 3: the melted hydrated salt legal system is equipped with SrTiO 3Nano particle
With 12g SrCl 26H 2O places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 1 hour under 130 ℃ of conditions of temperature;
Open encloses container then, add 1g TiO rapidly 2, stir with teflon rod, reseal container then, put into thermostat container, in 170 ℃ of reactions of temperature 16 hours;
After the cooling, take out the gained solid product, with the deionized water dissolving washing, the gained mixed solution is isolated insoluble product (greater than the 200nm particle) with the vacuum pumping rate;
Insoluble product is alternately washed 3 times with 95% ethanol and deionized water, and vacuum-drying promptly gets SrTiO 3Nano particle, weighing is no less than 2.1g, and yardstick is isolated the liquid that is left behind the insoluble product about the 150-300 nanometer, obtain salt hydrate by recrystallization and reuse.
Embodiment 4: the melted hydrated salt legal system is equipped with LiMn 2O 4Nano particle
With 12g LiNO 33H 2O places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 30 minutes under 60 ℃ of conditions of temperature;
Open encloses container then, add 0.8g Mn (OH) rapidly 2, stir with teflon rod, reseal container then, put into thermostat container, in 180 ℃ of reactions of temperature 24 hours;
After the cooling, take out the gained solid product, with 0.05M formic acid dilute solution dissolving washing, the gained mixed solution is isolated insoluble product with high speed centrifugation;
Insoluble product is alternately washed 4 times with 95% ethanol and deionized water, and seasoning promptly gets LiMn 2O 4Nano material, yardstick are isolated the liquid that is left behind the insoluble product in the 250-500 nanometer range, obtain salt hydrate by recrystallization and reuse.
Embodiment 5: the melted hydrated salt legal system is equipped with the ZnO nano particle
With 10g LiNO 33H 2O places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 40 minutes under 70 ℃ of conditions;
Open encloses container then, add 0.6g Zn (CH rapidly 3COO) 2, stir with teflon rod, reseal container then, put into thermostat container, in 140 ℃ of reactions of temperature 8 hours;
After the cooling, take out the gained solid product, with the deionized water dissolving washing, the gained mixed solution is isolated insoluble product with supercentrifuge;
Insoluble product is alternately washed 4 times with 95% ethanol and deionized water, in 100 ℃ of constant pressure and dries of temperature 18 hours, promptly get the ZnO nano particle, yardstick is in the 400-600 nanometer, isolates remaining liquid behind the insoluble product, obtains salt hydrate by recrystallization and reuses.
Embodiment 6: the melted hydrated salt legal system is equipped with CaTiO 3Nano particle
With 12g CaCl 26H 2O places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 55 minutes under 60 ℃ of conditions of temperature;
Open encloses container then, add 1g Ti (OH) rapidly 4, stir with teflon rod, reseal container then, put into thermostat container, in 120 ℃ of reactions of temperature 12 hours;
After the cooling, take out the gained solid product, with 0.2M acetic acid dilute solution dissolving washing, the gained mixed solution is isolated insoluble product (greater than the 200nm particle) with the vacuum pumping rate;
Insoluble product is alternately washed 4 times with 95% ethanol and deionized water, and vacuum-drying promptly gets CaTiO 3Nano particle, yardstick are isolated the liquid that is left behind the insoluble product about the 100-200 nanometer, obtain salt hydrate by recrystallization and reuse.
Embodiment 7: the melted hydrated salt legal system is equipped with MgNb 2O 6Nano particle
With 10g MgCl 26H 2O places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 45 minutes under 140 ℃ of conditions;
Open encloses container then, add 0.6g Nb rapidly 2O 5, stir with teflon rod, reseal container then, put into thermostat container, in 180 ℃ of reactions of temperature 10 hours;
After the cooling, take out the gained solid product, with the deionized water dissolving washing, the gained mixed solution is isolated insoluble product with supercentrifuge;
Insoluble product is alternately washed 3 times with 95% ethanol and deionized water, in 80 ℃ of constant pressure and dries of temperature 12 hours, promptly get MgNb again 2O 6Nano particle, yardstick are isolated the liquid that is left behind the insoluble product in the 200-400 nanometer, obtain salt hydrate by recrystallization and reuse.
Embodiment 8: the melted hydrated salt legal system is equipped with LiMn 2O 4Nano particle
With 8g MnCl 24H 2O places the airtight polytetrafluoroethylcontainer container of 50mL, heating fusing in 1 hour under 80 ℃ of conditions;
Open encloses container then, add 1.0g Li rapidly 2CO 3, stir with teflon rod, reseal container then, put into thermostat container, in 170 ℃ of reactions of temperature 6 hours;
After the cooling, take out the gained solid product, with the deionized water dissolving washing, the gained mixed solution is isolated insoluble product with supercentrifuge;
Insoluble product is alternately washed 3 times with 95% ethanol and deionized water, and seasoning promptly gets LiMn 2O 4Nano material, yardstick are isolated the liquid that is left behind the insoluble product in the 200-400 nanometer range, obtain salt hydrate by recrystallization and reuse.
Embodiment 9: the melted hydrated salt legal system is equipped with BaMoO 4Nano particle
With 10g Ba (OH) 28H 2O places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 50 minutes under 70 ℃ of conditions;
Open encloses container then, add 1.2g MoCl rapidly 6Powder stirred with teflon rod, reseals container then, puts into thermostat container, in 180 ℃ of reactions of temperature 8 hours;
After the cooling, take out the gained solid product, with 70 ℃ of hot water dissolving's washings, the gained mixed solution utilizes the supercentrifuge centrifugation to go out insoluble product;
Insoluble product is alternately washed 4 times with 95% ethanol and deionized water, and 65 ℃ of constant pressure and dries 1 hour promptly get BaMoO 4Nano material, yardstick are isolated the liquid that is left behind the insoluble product in the 250-400 nanometer range, obtain salt hydrate by recrystallization and reuse.
Embodiment 10: the melted hydrated salt legal system is equipped with LiMn 2O 4Nano particle
With 4.917g LiNO 33H 2O and 7.914g MnCl 24H 2O (Li: the Mn mol ratio is 1: 2) places the airtight polytetrafluoroethylcontainer container of 50mL, heating fusing in 1 hour under 80 ℃ of conditions;
Open encloses container then, add 0.6g NaOH rapidly, stir, reseal container then, put into thermostat container, in 160 ℃ of reactions of temperature 15 hours with teflon rod;
After the cooling, take out the gained solid product, with the deionized water dissolving washing, the gained mixed solution utilizes the supercentrifuge centrifugation to go out insoluble product;
Insoluble product is alternately washed 4 times with 95% ethanol and deionized water, and 85 ℃ of constant pressure and dries of temperature are 1 hour again, promptly get LiMn 2O 4Nano particle, particle diameter 200-300 nanometer is isolated the liquid that is left behind the insoluble product, obtains salt hydrate by recrystallization and reuses.
Embodiment 11: the melted hydrated salt legal system is equipped with Ba xSr 1-xTiO 3(x=0.5) nano particle
With 6.513g Ba (OH) 28H 2O and 5.487g Sr (OH) 28H 2O (Ba: the Sr mol ratio is 1: 1) places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 55 minutes under 100 ℃ of conditions of temperature;
Open encloses container then, add 0.8g TiO rapidly 2, stir with teflon rod, reseal container then, put into thermostat container, in 110 ℃ of reactions of temperature 30 hours;
After the cooling, take out the gained solid product, with 65 ℃ of hot water dissolving's washings, the gained mixed solution utilizes the supercentrifuge centrifugation to go out insoluble product;
Insoluble product is alternately washed 3 times with 95% ethanol and deionized water, and 95 ℃ of constant pressure and dries of temperature are 2 hours again, promptly get single Ba of dispersion 0.5Sr 0.5TiO 3Nano particle, weighing is no less than 1.9g, and grain diameter 200-350 nanometer is isolated the liquid that is left behind the insoluble product, obtains salt hydrate by recrystallization and reuses.
Melted hydrated salt compound of the present invention or composite molten salt hydrate compound are not limited to the compound described in the embodiment.
Metal oxide of the present invention, metal chloride, metal hydroxides and metal oxygen-containing hydrochlorate are not limited to the compound described in the embodiment.
Oxide-based nanomaterial by method preparation of the present invention is simple binary oxide compound ZnO, TiO 2, WO 3, Fe 2O 3, Fe 3O 4Deng insoluble compound nano material and complicated pluralism oxide compound BaTiO 3, SrTiO 3, LiMn 2O 4, Ba xSr 1-xTiO 3, Ca 1-xSr xTiO 3, PbTi xZr 1-xO 3Deng the insoluble compound nano material.

Claims (11)

1. preparing oxide nano-materials by melted hydrated salt BaTiO 3The method of hollow nano particle is characterized in that following these steps to carrying out:
A, with 12g Ba (OH) 28H 2O places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 1 hour under 90 ℃ of conditions;
B, open encloses container then, add 0.8g TiO rapidly 2Powder stirred with teflon rod, reseals container then, puts into thermostat container, in 180 ℃ of reactions of temperature 3 hours;
After c, the cooling, take out the gained solid product, with 50 ℃ of hot water dissolving's washings, the gained mixed solution utilizes the supercentrifuge centrifugation to go out insoluble product;
D, insoluble product is alternately washed 3 times with 95% ethanol and deionized water, 60 ℃ of constant pressure and dries of temperature 1 hour promptly get single BaTiO of dispersion 3The hollow nano particle, weighing is no less than 2.2g, isolates the liquid that is left behind the insoluble product, obtains salt hydrate by recrystallization and reuses.
2. preparing oxide nano-materials by melted hydrated salt BaTiO 3The method of nano particle is characterized in that following these steps to carrying out:
A, with 8g Ba (OH) 28H 2O places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 40 minutes under 110 ℃ of conditions;
B, open encloses container then, add 0.6g self-control rutile TiO rapidly 2Powder, this rutile TiO 2Utilization is to containing 0.15M TiCl 3The NaCl saturated aqueous solution carry out hydrothermal treatment consists and obtained in 3 hours, stir with teflon rod, reseal container then, put into thermostat container, in 160 ℃ of reactions of temperature 1 hour;
After c, the cooling, take out the gained solid product, with 0.1M acetic acid dilute solution dissolving washing, the gained mixed solution utilizes high speed centrifugation to isolate insoluble product;
D, insoluble product is alternately washed 4 times with 95% ethanol and deionized water, seasoning promptly gets BaTiO 3Nano particle, weighing is no less than 1.7g, isolates the liquid that is left behind the insoluble product, obtains salt hydrate by recrystallization and reuses.
3. preparing oxide nano-materials by melted hydrated salt SrTiO 3The method of nano particle is characterized in that following these steps to carrying out:
A, with 12g SrCl 26H 2O places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 1 hour under 130 ℃ of conditions of temperature;
B, open encloses container then, add 1g TiO rapidly 2, stir with teflon rod, reseal container then, put into thermostat container, in 170 ℃ of reactions of temperature 16 hours;
After c, the cooling, take out the gained solid product, with the deionized water dissolving washing, the gained mixed solution is isolated insoluble product greater than the 200nm particle with the vacuum pumping rate;
D, insoluble product is alternately washed 3 times with 95% ethanol and deionized water, vacuum-drying promptly gets SrTiO 3Nano particle, weighing is no less than 2.1g, and yardstick is isolated the liquid that is left behind the insoluble product in the 150-300 nanometer, obtains salt hydrate by recrystallization and reuses.
4. preparing oxide nano-materials by melted hydrated salt LiMn 2O 4The method of nano particle is characterized in that following these steps to carrying out:
A, with 12g LiNO 33H 2O places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 30 minutes under 60 ℃ of conditions of temperature;
B, open encloses container then, add 0.8g Mn (OH) rapidly 2, stir with teflon rod, reseal container then, put into thermostat container, in 180 ℃ of reactions of temperature 24 hours;
After c, the cooling, take out the gained solid product, with 0.05M formic acid dilute solution dissolving washing, the gained mixed solution is isolated insoluble product with high speed centrifugation;
D, insoluble product is alternately washed 4 times with 95% ethanol and deionized water, seasoning promptly gets LiMn 2O 4Nano material, yardstick are isolated the liquid that is left behind the insoluble product in the 250-500 nanometer range, obtain salt hydrate by recrystallization and reuse.
5. the method for a preparing oxide nano-materials by melted hydrated salt ZnO nano particle is characterized in that following these steps to carrying out:
A, with 10g LiNO 33H 2O places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 40 minutes under 70 ℃ of conditions;
B, open encloses container then, add 0.6g Zn (CH rapidly 3COO) 2, stir with teflon rod, reseal container then, put into thermostat container, in 140 ℃ of reactions of temperature 8 hours;
After c, the cooling, take out the gained solid product, with the deionized water dissolving washing, the gained mixed solution is isolated insoluble product with supercentrifuge;
D, insoluble product is alternately washed 4 times with 95% ethanol and deionized water, in 100 ℃ of constant pressure and dries of temperature 18 hours, promptly get the ZnO nano particle, yardstick is in the 400-600 nanometer, isolate the liquid that is left behind the insoluble product, obtain salt hydrate by recrystallization and reuse.
6. preparing oxide nano-materials by melted hydrated salt CaTiO 3The method of nano particle is characterized in that following these steps to carrying out:
A, with 12g CaCl 26H 2O places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 55 minutes under 60 ℃ of conditions of temperature;
B, open encloses container then, add 1g Ti (OH) rapidly 4, stir with teflon rod, reseal container then, put into thermostat container, in 120 ℃ of reactions of temperature 12 hours;
After c, the cooling, take out the gained solid product, with 0.2M acetic acid dilute solution dissolving washing, the gained mixed solution is isolated insoluble product greater than the 200nm particle with the vacuum pumping rate;
D, insoluble product is alternately washed 4 times with 95% ethanol and deionized water, vacuum-drying promptly gets CaTiO 3Nano particle, yardstick are isolated the liquid that is left behind the insoluble product in the 100-200 nanometer, obtain salt hydrate by recrystallization and reuse.
7. preparing oxide nano-materials by melted hydrated salt MgNb 2O 6The method of nano particle is characterized in that following these steps to carrying out:
A, with 10g MgCl 26H 2O places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 45 minutes under 140 ℃ of conditions;
B, open encloses container then, add 0.6g Nb rapidly 2O 5, stir with teflon rod, reseal container then, put into thermostat container, in 180 ℃ of reactions of temperature 10 hours;
After c, the cooling, take out the gained solid product, with the deionized water dissolving washing, the gained mixed solution is isolated insoluble product with supercentrifuge;
D, insoluble product is alternately washed 3 times with 95% ethanol and deionized water, in 80 ℃ of constant pressure and dries of temperature 12 hours, promptly get MgNb again 2O 6Nano particle, yardstick are isolated the liquid that is left behind the insoluble product in the 200-400 nanometer, obtain salt hydrate by recrystallization and reuse.
8. preparing oxide nano-materials by melted hydrated salt LiMn 2O 4The method of nano particle is characterized in that following these steps to carrying out:
A, with 8g MnCl 24H 2O places the airtight polytetrafluoroethylcontainer container of 50mL, heating fusing in 1 hour under 80 ℃ of conditions;
B, open encloses container then, add 1.0g Li rapidly 2CO 3, stir with teflon rod, reseal container then, put into thermostat container, in 170 ℃ of reactions of temperature 6 hours;
After c, the cooling, take out the gained solid product, with the deionized water dissolving washing, the gained mixed solution is isolated insoluble product with supercentrifuge;
D, insoluble product is alternately washed 3 times with 95% ethanol and deionized water, seasoning promptly gets LiMn 2O 4Nano material, yardstick are isolated the liquid that is left behind the insoluble product in the 200-400 nanometer range, obtain salt hydrate by recrystallization and reuse.
9. preparing oxide nano-materials by melted hydrated salt BaMoO 4The method of nano particle is characterized in that following these steps to carrying out:
A, with 10g Ba (OH) 28H 2O places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 50 minutes under 70 ℃ of conditions;
B, open encloses container then, add 1.2g MoCl rapidly 6Powder stirred with teflon rod, reseals container then, puts into thermostat container, in 180 ℃ of reactions of temperature 8 hours;
After c, the cooling, take out the gained solid product, with 70 ℃ of hot water dissolving's washings, the gained mixed solution utilizes the supercentrifuge centrifugation to go out insoluble product;
D, insoluble product is alternately washed 4 times with 95% ethanol and deionized water, 65 ℃ of constant pressure and dries 1 hour promptly get BaMoO 4Nano material, yardstick are isolated the liquid that is left behind the insoluble product in the 250-400 nanometer range, obtain salt hydrate by recrystallization and reuse.
10. preparing oxide nano-materials by melted hydrated salt LiMn 2O 4The method of nano particle is characterized in that following these steps to carrying out:
A, with 4.917g LiNO 33H 2O and 7.914g MnCl 24H 2O, Li: the Mn mol ratio is 1: 2, places the airtight polytetrafluoroethylcontainer container of 50mL, heating fusing in 1 hour under 80 ℃ of conditions;
B, open encloses container then, add 0.6g NaOH rapidly, stir, reseal container then, put into thermostat container, in 160 ℃ of reactions of temperature 15 hours with teflon rod;
After the c cooling, take out the gained solid product, with the deionized water dissolving washing, the gained mixed solution utilizes the supercentrifuge centrifugation to go out insoluble product;
D, insoluble product is alternately washed 4 times with 95% ethanol and deionized water, 85 ℃ of constant pressure and dries of temperature are 1 hour again, promptly get LiMn 2O 4Nano particle, particle diameter 200-300 nanometer is isolated the liquid that is left behind the insoluble product, obtains salt hydrate by recrystallization and reuses.
11. preparing oxide nano-materials by melted hydrated salt Ba xSr 1-xTiO 3The method of nano particle is characterized in that following these steps to carrying out:
A, with 6.513g Ba (OH) 28H 2O and 5.487g Sr (OH) 28H 2O, Ba: the Sr mol ratio is 1: 1, places the airtight polytetrafluoroethylcontainer container of 23mL, heating fusing in 55 minutes under 100 ℃ of conditions of temperature;
B, open encloses container then, add 0.8g TiO rapidly 2, stir with teflon rod, reseal container then, put into thermostat container, in 110 ℃ of reactions of temperature 30 hours;
After c, the cooling, take out the gained solid product, with 65 ℃ of hot water dissolving's washings, the gained mixed solution utilizes the supercentrifuge centrifugation to go out insoluble product;
D, insoluble product is alternately washed 3 times with 95% ethanol and deionized water, 95 ℃ of constant pressure and dries of temperature are 2 hours again, promptly get single Ba of dispersion 0.5Sr 0.5TiO 3Nano particle, weighing is no less than 1.9g, and grain diameter 200-350 nanometer is isolated the liquid that is left behind the insoluble product, obtains salt hydrate by recrystallization and reuses.
CN2009101132755A 2009-03-31 2009-03-31 Method for preparing oxide nano-materials by melted hydrated salt Expired - Fee Related CN101519191B (en)

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