CN1896341A - Low-temperature alkaline-solution synthesis of oxygen metal inorganic compound monocrystal nano-material - Google Patents
Low-temperature alkaline-solution synthesis of oxygen metal inorganic compound monocrystal nano-material Download PDFInfo
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- CN1896341A CN1896341A CN 200610044939 CN200610044939A CN1896341A CN 1896341 A CN1896341 A CN 1896341A CN 200610044939 CN200610044939 CN 200610044939 CN 200610044939 A CN200610044939 A CN 200610044939A CN 1896341 A CN1896341 A CN 1896341A
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Abstract
The present invention discloses a hypothermal alkali liquation synthesis process of monocrystalline nanometer materials of oxygenous metal inorganic compounds. The compound oxide monocrystalline nanometer materials are synthesized with the inorganic salt of a metal and the oxide of another metal as main materials, melted mixed alkali as solvent, at atmospheric pressure and relatively low temperature of about 200DEG C. The present invention uses melted alkali as solvent for the first time and can synthesize oxide nanometer materials of different structures, compositions and functions, or monocrystalline nanometer materials of simple oxide and hydroxide. This process utilizes conventional materials and only controls the time and temperature during synthesis in favor of the industrial application. The produced monocrystalline nanometer materials includes ferroelectric and piezoelectric materials, ferromagnetic materials, semiconductive materials, ionic conductive materials, colossal magnetoresistance materials, high dielectric materials superconductors and etc. that can be applied to microelectronics, photoelectronics and communication.
Description
Technical field
The present invention relates to the preparation method of a kind of oxygen metal inorganic compound, particularly oxide compound and oxyhydroxide monocrystal nanostructure, relate in particular to a kind of low-temperature alkaline-solution synthesis of oxygen metal inorganic compound monocrystal nano-material.
Background technology
So-called composite oxides are meant the compound of being made jointly by two or more metal ion and Sauerstoffatom, and its general formula is A
xB
yO
zMany composite oxides, as have uhligite, spinel, an isostructural complex metal oxides of garnet, because have, and be subjected to paying attention to widely as all more important performances such as ferroelectricity, ferromegnetism, semiconducting behavior, luminescent properties, photoelectric properties and catalytic performances.Because the sudden change of the material property that quantum effect and other dimensional effects cause, in recent years, the nanostructure of these materials has been subjected to paying attention to widely.Although some physical method particularly sputter and vapour deposition etc. has successfully prepared the single oxide monocrystal nano-material, as zinc oxide, tindioxide etc., because the composition of composite oxides and the complicacy of structure, these methods are difficult to obtain have the nanostructure of the composite oxides of good form.Therefore, the synthesizing composite oxide monocrystal nano-material, become to limit this class nano material and device research, development and application major obstacle.So far, have only few article to report composite oxide nano-material synthetic of a few species, these nano materials comprise BaTiO
3, SrTiO
3, PbTiO
3, BaMnO
3, La
xBa
1-xMnO
3These methods or related to have the synthetic or reagent that adopted this class costliness of organometallic compound of highly compressed hydro-thermal as presoma, have perhaps adopted porous metal as template or adopted salt to react as the high temperature of solvent more than 800 degree.In a word, these methods are because the condition harshness is difficult to repetition, and perhaps because output is too little, cost is too high, is difficult to drop into industrial production.Nonetheless, because the complicacy of composite oxide material composition and structure, these methods only are suitable for implementing in the laboratory, moreover also just only a few is several for the composite oxide nano-material kind of preparation.
Summary of the invention
At the deficiencies in the prior art, the problem to be solved in the present invention provides a kind of low-temperature alkaline-solution synthesis of simple and feasible oxygen metal inorganic compound monocrystal nano-material.This method as solvent, as reactant, can be synthesized the composite oxide nano-material with monocrystal nanostructure with metal inorganic salt with low cost and oxide compound with the anhydrous mixed base of fused under normal pressure, about 200 ℃ temperature.
The low-temperature alkaline-solution synthesis of the oxygen metal inorganic compound monocrystal nano-material that the present invention relates to, the synthetic method that particularly comprises the complex metal oxides monocrystal nano-material of oxide compound, feelings oxide compound, by batching, heating and melting, isothermal reaction, cooling and washing step are formed (as shown in Figure 1), it is characterized in that, described batching is meant the composite oxides A as synthetic target
xB
yO
zIn A position raw material and B position raw material be that the ratio weighing of A: B=x: y mixes the back and adds and filled in the reaction vessel of mixed base according to atomic ratio; Described heating and melting is that reactor is put into the heating installation that is heated to 160 ℃-220 ℃, carries out preheating and melts, and through 30-90 minute, the solid mixed base of inside reactor is melted fully, and reactant is uniform distribution in the mixed base liquation; Described isothermal reaction is to instigate reaction vessel to continue heating 24-96 hour under the homothermic state, and the A position in the assurance mixed base melt and the compound of B bit element fully react; Described cooling is meant after reaction reaches the time of setting, and reaction vessel is cooled to room temperature (20 ℃-25 ℃); Described washing be with the reaction product that has mixed base of having solidified wash to pH be 7, through the suction filtration oven dry, the product of last gained is the complex metal oxides single crystal nano-powder.
In the low-temperature alkaline-solution synthesis of above-mentioned oxygen metal inorganic compound monocrystal nano-material: A is the metal ion of meta-alkalescence among the described composite oxides AxByOz, and B is the metal ion of both sexes or slant acidity; Two or more A position is arranged in the AxByOz lattice and B position ionic is compound and mix.
Wherein: described A is Ba preferably, Sr, and Ca, one of Pb, described B is Ti preferably, Si, Ce, V, one of Al.
In the low-temperature alkaline-solution synthesis of above-mentioned oxygen metal inorganic compound monocrystal nano-material: described A position raw material is inorganic salt or simple organic salt, and described B position raw material is slant acidity or intermediate oxide; And its valence state is identical with valence state in the composite oxides chemical formula.
Wherein: described A position raw material is muriate preferably, nitrate, vitriol, carbonate, one of acetate;
Described B position raw material is one of titanium oxide, ferric oxide, cobalt oxide, vanadium oxide, aluminum oxide preferably.
In the low-temperature alkaline-solution synthesis of above-mentioned oxygen metal inorganic compound monocrystal nano-material: described mixed base is made up of two or more anhydrous alkali metal hydroxides, its ratio is AOH: BOH: COH=0.1～0.8: 0.1～0.8: 0～0.8.
Above-mentioned alkali blended purpose is to reduce melt temperature, makes building-up reactions carry out under low concentration.The preferable volumetric molar concentration of described reactant in alkaline solution is 0.1-10mmol.
Wherein: described anhydrous alkali metal hydroxides is lithium hydroxide preferably, sodium hydroxide, potassium hydroxide, one of rubidium hydroxide.
In the low-temperature alkaline-solution synthesis of above-mentioned oxygen metal inorganic compound monocrystal nano-material: described heating installation preferably one of retort furnace, resistance furnace, drying machine, baking oven can be to the accurate heating installation of control of temperature; Described reaction vessel preferably one of precious metal vessel, organism container to alkali metal hydroxide inert container.
In the low-temperature alkaline-solution synthesis of above-mentioned oxygen metal inorganic compound monocrystal nano-material: the described type of cooling is that well heater is cooled to room temperature according to setting speed, the stove internal cooling perhaps directly cuts off the power supply, perhaps directly reaction vessel is taken out from well heater, be put in the frozen water after perhaps taking out and cool off.
In the low-temperature alkaline-solution synthesis of above-mentioned oxygen metal inorganic compound monocrystal nano-material: described washing is the product dissolving that has mixed base that will solidify with cold or hot deionized water or diluted acid, adopt whizzer precipitation or pumping and filtering device to filter suspension, filtering product disperses in cold or hot deionized water or diluted acid again, filter once more, reach 7 until filtrate pH value.
The rotating speed of above-mentioned centrifugation is 500-2000 rev/min.
The aperture of above-mentioned pumping and filtering device filter filter membrane is 0.2-0.5 μ m.
Utilization the present invention relates to utilizes molten caustic soda to prepare the method for composite oxide single crystal nano material as solvent, can prepare the monocrystalline oxide nanostructure of various different structure difference in functionalitys, as ferroelectric piezoelectric, ferromagnetic material, giant magnetic resistance, semiconductor material, ionic conductor material etc.These materials can be widely used in having ferromagnetic memory cell, infrared components, magnetic memory cell, magnetic-electric device, semiconductor element, luminescent device, ionization cell and the aspects such as gas and biosensor of nanostructure, thereby promote the development in fields such as microelectronics, photoelectron, communication, environmental protection, chemical industry, biology.
The low-temperature alkaline-solution synthesis of the oxygen metal inorganic compound monocrystal nano-material that the present invention relates to, first with anhydrous molten caustic soda as solvent, inorganic salt and oxide compound with routine are raw material, synthesizing composite oxide monocrystal nano-material under normal pressure, about 200 ℃ lesser temps.This method is suitable for industrialized mass production because low, the atmospheric operation of synthesis temperature is realized the control of building-up process easily; Because adopting inorganic salt and oxide compound nontoxic, routine is raw material, raw material is easy to get and low production cost.Because the viscosity of the viscosity ratio water of molten caustic soda is big, the nano material speed of growth is slower, obtains having the nano crystal of solid shape easily; Owing to do not adopt any tensio-active agent and other organic additive in the preparation process, the nano-material surface cleaning after water cleans can be brought into play the functional of nano material to greatest extent, and not have the influence of second phase.So, to in following new technologies and methods, be applied with this method synthetic ferro-electricity single crystal nanocubes, ferromagnetic nanocubes and cube rod and nano belt, huge magnetic impedance nano belt and semiconductor nano-strip, as, construct ferroelectric random storer (ferroelectric random memory), magnetic memory device, magnetic-electric transducer, all gases transmitter and biosensor etc.
The low-temperature alkaline-solution synthesis of the oxygen metal inorganic compound monocrystal nano-material that the present invention relates to also is applicable to the synthetic of some oxyhydroxide and single oxide monocrystal nano-material, is a kind of pervasive synthetic method of oxygen inorganic metal compound that contains.
Except composite oxides, the present invention also is suitable for the synthetic of some oxide compounds and oxyhydroxide monocrystal nanostructure.
Description of drawings
The low-temperature alkaline-solution synthesis schematic flow sheet of Fig. 1 oxygen metal inorganic compound monocrystal nano-material of the present invention
Fig. 2 adopts the barium titanate and the strontium-barium titanate nanocubes of the inventive method preparation.
Fig. 3 adopts the ferriferrous oxide nano cubes of the inventive method preparation.
Fig. 4 the inventive method synthetic cobalt ferrite nano belt.
Fig. 5 the inventive method synthetic Rosensthiel's green nano belt.
The oval nano belt of Fig. 6 the inventive method synthetic titanium Rosensthiel's green.
Fig. 7 the inventive method synthetic cerium acid barium nanostructure.
Fig. 8 the inventive method is synthesized the lead vanadate nano belt.
Fig. 9 the inventive method synthetic lanthanum hydroxide nano belt.
Embodiment
Embodiment 1:
Barium titanate nano is cubical synthetic
1. prepare burden:
(1) claiming 10 gram KOH and 7 gram NaOH to add volumes is in 25 milliliters the polytetrafluoroethylcontainer container.
(2) claim 1mmol bariumchloride and 1mmol titanium dioxide to add in the alkali in the above polytetrafluoroethylcontainer container.
(3) will gather four not ethene container sealing, to keep the cleaning of reaction process.
2. heating and melting:
With retort furnace or baking oven for heating to 210 ℃, the polytetrafluoroethylcontainer container of sealing is put into heating installation.Make heating installation insulation 1 hour, stir and make liquation and reactant uniform mixing.
3. isothermal reaction:
Reactant in the solution was reacted 48 hours under these conditions, carry out fully until reaction.
4. cooling:
Reaction vessel is taken out from heating installation, put into mixture of ice and water and cool off, reduce to room temperature to reaction vessel.
5. washing:
Fall the alkali fusion that cools off after coagulation with deionized water, solution is filtered by filter (aperture is 0.2 μ m), obtain throw out.Throw out is dispersed in the deionized water again suction filtration.Repeat above-mentioned steps 5 times, reach 7 until pH value of filtrate.
6. oven dry:
The powder that filtration obtains is dried about 50-60 ℃, obtain single crystal nano-powder.
X-ray diffraction is the result show, the powder that obtains is the barium titanate of single-phase perovskite structure.Scanning and transmission electron microscopy are observed and are shown that powder is the barium titanate cubes (Fig. 2) that is of a size of the 30-50 nanometer.Electron diffraction collection of illustrative plates and high resolution have further been supported the result of X-ray diffraction.
Embodiment 2:
Synthesizing of strontium-barium titanate nanocubes
1. prepare burden:
(1) claiming 10 gram KOH and 7 gram NaOH to add volumes is in 25 milliliters the polytetrafluoroethylcontainer container.
(2) claim 0.5mmol bariumchloride and 0.5mmol strontium chloride and 1mmol titanium dioxide to add in the alkali in the above polytetrafluoroethylcontainer container.
(3) will gather four not ethene container sealing, to keep the cleaning of reaction process
2. heating and melting:
With retort furnace or baking oven for heating to 220 ℃, the polytetrafluoroethylcontainer container of sealing is put into heating installation.Make heating installation insulation 1 hour, stir and make liquation and reactant uniform mixing.
3. isothermal reaction:
Reactant in the solution was reacted 60 hours under these conditions, carry out fully until reaction.
4. cooling:
Reaction vessel is taken out from heating installation, put into mixture of ice and water and cool off, reduce to room temperature to reaction vessel.
5. washing:
Fall the alkali fusion that cools off after coagulation with deionized water, solution is filtered by filter (aperture is 0.2 μ m), obtain throw out.Throw out is dispersed in the deionized water again suction filtration.Repeat above-mentioned steps 5 times, reach 7 to pH value of filtrate.The salt acid soak of adding pH=2 5 hours continues to wash to pH=7.
6. oven dry:
The powder that filtration obtains is dried about 60 ℃, obtain single crystal nano-powder.
X-ray diffraction is the result show, the powder that experiment obtains is the strontium-barium titanate of single-phase perovskite structure.Scanning and transmission electron microscopy are observed and are shown that powder is the strontium-barium titanate cubes that is of a size of the 30-50 nanometer.Electron diffraction collection of illustrative plates and high resolution have further been supported the result of X-ray diffraction.
Embodiment 3:
Synthesizing of ferriferrous oxide nano cubes and nano cubic post
1. prepare burden:
(1) claiming 10 gram KOH and 7 gram NaOH to add volumes is in 25 milliliters the polytetrafluoroethylcontainer container.
(2) claim 1mmol iron(ic) chloride and 1mmol ferric oxide to add in the alkali in the above polytetrafluoroethylcontainer container.
(3) will gather four not ethene container sealing, to keep the cleaning of reaction process.
2. heating and melting:
With retort furnace or baking oven for heating to 200 ℃, the polytetrafluoroethylcontainer container of sealing is put into heating installation.Make heating installation insulation 1 hour, stir and make liquation and reactant uniform mixing.
3. isothermal reaction:
Reactant in the solution was reacted 70 hours under these conditions, carry out fully until reaction.
4. cooling:
Reaction vessel is taken out from heating installation, in air, cool off, reduce to room temperature to reaction vessel.
5. washing:
Fall the alkali fusion that cools off after coagulation with deionized water, solution is filtered by filter (aperture is 0.2 μ m), obtain throw out.Throw out is dispersed in the deionized water again suction filtration.Repeat above-mentioned steps 6 times with hot water, reach 7 until pH value of filtrate.
6. oven dry:
The powder that filtration is obtained obtains single crystal nano-powder 70 ℃ of oven dry.
X-ray diffraction is the result show, the powder that experiment obtains is the Z 250 of single-phase spinel structure.Scanning and transmission electron microscopy are observed and are shown that powder is to be of a size of the Z 250 cubes of 250 nanometers or the cube rod (Fig. 3) of 250 * 250 * 300-500 nanometer.The electron diffraction collection of illustrative plates has further been verified the result of X-ray diffraction.
Embodiment 4:
Synthesizing of cobalt ferrite nano belt
1. prepare burden:
(1) claiming 10 gram KOH and 7 gram NaOH to add volumes is in 25 milliliters the polytetrafluoroethylcontainer container.
(2) claim 1mmol Xiao Suangu and 1mmol ferric oxide to add in the alkali in the above polytetrafluoroethylcontainer container.
(3) will gather four not ethene container sealing, to keep the cleaning of reaction process.
2. heating and melting:
Retort furnace is heated to 200 ℃, the polytetrafluoroethylcontainer container of sealing is put into retort furnace.Make retort furnace insulation 1 hour, the concussion container makes solution and reactant uniform mixing.
3. isothermal reaction:
Reactant in the solution was reacted 50 hours under these conditions, carry out fully until reaction.
4. cooling:
Heating installation is reduced to room temperature together with reaction vessel according to 10 ℃ of/minute speed.
5. washing:
With deionized water fall the cooling after coagulation alkali fusion, with solution under 1500 rev/mins rotating speed through 5 minutes, obtain throw out.Throw out is dispersed in the deionized water again, precipitates again according to above-mentioned rotating speed.Repeat above-mentioned steps 5 times, reach 7 until pH value of filtrate.
6. oven dry:
The powder that filtration is obtained obtains single crystal nano-powder 50 ℃ of oven dry.
X-ray diffraction is the result show, the powder that experiment obtains is the cobalt ferrite of single-phase spinel structure.Scanning and transmission electron microscopy are observed and are shown that powder is for being of a size of the 20-40 nanometer thickness.The 150-250 nanometer is wide, and length is greater than 10 microns nano belt (Fig. 4).Electron diffraction collection of illustrative plates and electron energy loss spectroscopy (EELS) have further been verified the result of X-ray diffraction.
Embodiment 5:
Synthesizing of Rosensthiel's green nano belt
1. prepare burden:
(1) claiming 10 gram KOH and 7 gram NaOH to add volumes is in 25 milliliters the polytetrafluoroethylcontainer container.
(2) claim 0.5mmol bariumchloride and 0.5mmol Manganse Dioxide to add in the alkali in the above polytetrafluoroethylcontainer container.
(3) will gather four not ethene container sealing, to keep the cleaning of reaction process.
2. heating and melting:
With retort furnace or baking oven for heating to 180 ℃, the polytetrafluoroethylcontainer container of sealing is put into heating installation.Make heating installation insulation 1 hour, stir and make liquation and reactant uniform mixing.
3. isothermal reaction:
Reactant in the solution was reacted 48 hours under these conditions, carry out fully until reaction.
4. cooling:
Reaction vessel is taken out from heating installation, in air, cool off, reduce to room temperature to reaction vessel.
5. washing:
Fall the alkali fusion that cools off after coagulation with deionized water, solution is filtered by filter (aperture is 0.25 μ m), obtain throw out.Throw out is dispersed in again in the deionized water of 90 degree suction filtration.Repeat above-mentioned steps 5 times, reach 7 until pH value of filtrate.Hydrochloric acid soln with pH=2 soaked 4 hours, washed to pH=7 again.
6. oven dry:
The powder that filtration is obtained obtains single crystal nano-powder 80 ℃ of oven dry.
X-ray diffraction is the result show, the powder that experiment obtains is six side's Rosensthiel's green phases.Transmission electron microscopy is observed and is shown, powder is for being of a size of the nano belt (Fig. 5) of 20-30 * 50-80 * 800-100 nanometer, electron energy loss spectroscopy (EELS) has confirmed the wherein atomic ratio complex chemical compound metering ratio of barium/manganese/titanium, and the electron diffraction collection of illustrative plates has further been verified the result of X-ray diffraction.
Embodiment 6:
Synthesizing of manganese barium titanate nano band
1. prepare burden:
(1) claiming 10 gram KOH and 7 gram NaOH to add volumes is in 25 milliliters the polytetrafluoroethylcontainer container.
(2) claim 0.5mmol bariumchloride and 0.25mol Manganse Dioxide and 0.25mmol titanium dioxide to add in the alkali in the above polytetrafluoroethylcontainer container.
(3) will gather four not ethene container sealing, to keep the cleaning of reaction process.
2. heating and melting:
With retort furnace or baking oven for heating to 190 ℃, the polytetrafluoroethylcontainer container of sealing is put into heating installation.Make heating installation insulation 1 hour, the concussion container makes solution and reactant uniform mixing.
3. isothermal reaction:
Reactant in the solution was reacted 50 hours under these conditions, carry out fully until reaction.
4. cooling:
Reaction vessel is taken out from heating installation, put into mixture of ice and water and cool off, reduce to room temperature to reaction vessel.
5. washing:
Fall the alkali fusion that cools off after coagulation with deionized water, solution is filtered by filter (aperture is 0.2 μ m), obtain throw out.Throw out is dispersed in the deionized water again suction filtration.Repeat above-mentioned steps 5 times, reach 7 until pH value of filtrate.
6. oven dry:
The powder that filtration is obtained obtains single crystal nano-powder 50 ℃ of oven dry.
X-ray diffraction is the result show, the crystalline structure of reaction product and BaMnO
3Crystalline structure is identical, and BaTi is found in transmission electron microscopy observation
0.5Mn
0.5O
3Crystal grain is that width is 40 nanometers, and thickness is 20 nanometers, and length is the oval nano belt (Fig. 6) about 500 nanometers.Electron energy loss spectroscopy (EELS) studies show that the ratio of titanium and manganese is 1: 1 in the reaction product, meets the ratio in the chemical formula.The electron diffraction collection of illustrative plates also confirms the XRD experimental result.
Embodiment 7:
Width is that 30-50nm, length are the synthetic of 50-100nm Rosensthiel's green nano belt
1. prepare burden:
(1) claiming 10 gram KOH and 7 gram NaOH to add volumes is in 25 milliliters the polytetrafluoroethylcontainer container.
(2) claim 0.5mmol bariumchloride and 0.5mmol Manganse Dioxide to add in the alkali in the above polytetrafluoroethylcontainer container.
(3) will gather four not ethene container sealing, to keep the cleaning of reaction process.
2. heating and melting:
With retort furnace or baking oven for heating to 200 ℃, the polytetrafluoroethylcontainer container of sealing is put into heating installation.Make heating installation insulation 1 hour, stir and make liquation and reactant uniform mixing.
3. isothermal reaction:
Reactant in the solution was reacted 24 hours under these conditions, carry out fully until reaction.
4. cooling:
Reaction vessel is taken out from heating installation, in air, cool off, reduce to room temperature to reaction vessel.
5. washing:
Fall the alkali fusion that cools off after coagulation with deionized water, solution is filtered by filter (aperture is 0.25 μ m), obtain throw out.Throw out is dispersed in again in the deionized water of 90 degree suction filtration.Repeat above-mentioned steps 5 times, reach 7 until pH value of filtrate.Hydrochloric acid soln with pH=2 soaked 4 hours, washed to pH=7 again.
6. oven dry:
The powder that filtration is obtained obtains single crystal nano-powder 80 ℃ of oven dry.Electron microscopic study shows that 200 ℃, 24 hours synthetic powder are that width is that 30-50nm, length are the nano belt of 50-100nm.
Embodiment 8:
Width is that 20-30nm, length are the synthetic of 100-200nm Rosensthiel's green nano belt
1. prepare burden:
(1) claiming 10 gram KOH and 7 gram NaOH to add volumes is in 25 milliliters the polytetrafluoroethylcontainer container.
(2) claim 0.5mmol bariumchloride and 0.5mmol Manganse Dioxide to add in the alkali in the above polytetrafluoroethylcontainer container.
(3) will gather four not ethene container sealing, to keep the cleaning of reaction process.
2. heating and melting:
With retort furnace or baking oven for heating to 200 ℃, the polytetrafluoroethylcontainer container of sealing is put into heating installation.Make heating installation insulation 1 hour, stir and make liquation and reactant uniform mixing.
3. isothermal reaction:
Reactant in the solution was reacted 72 hours under these conditions.
4. cooling:
Reaction vessel is taken out from heating installation, in air, cool off, reduce to room temperature to reaction vessel.
5. washing:
Fall the alkali fusion that cools off after coagulation with deionized water, solution is filtered by filter (aperture is 0.25 μ m), obtain throw out.Throw out is dispersed in again in the deionized water of 90 degree suction filtration.Repeat above-mentioned steps 5 times, reach 7 until pH value of filtrate.Hydrochloric acid soln with pH=2 soaked 4 hours, washed to pH=7 again.
6. oven dry:
The powder that filtration is obtained obtains single crystal nano-powder 80 ℃ of oven dry.Electron microscopic study shows that 200 ℃, 72 hours synthetic powder are that width is that 20-30nm, length are the nano belt of 100-200nm.
Embodiment 9:
Width is the synthetic of 30nm, length 300-500nm Rosensthiel's green nano belt
1. prepare burden:
(1) claiming 10 gram KOH and 7 gram NaOH to add volumes is in 25 milliliters the polytetrafluoroethylcontainer container.
(2) claim 0.5mmol bariumchloride and 0.5mmol Manganse Dioxide to add in the alkali in the above polytetrafluoroethylcontainer container.
(3) will gather four not ethene container sealing, to keep the cleaning of reaction process.
2. heating and melting:
With retort furnace or baking oven for heating to 200 ℃, the polytetrafluoroethylcontainer container of sealing is put into heating installation.Make heating installation insulation 1 hour, stir and make liquation and reactant uniform mixing.
3. isothermal reaction:
Reactant in the solution was reacted 120 hours under these conditions.
4. cooling:
Reaction vessel is taken out from heating installation, in air, cool off, reduce to room temperature to reaction vessel.
5. washing:
Fall the alkali fusion that cools off after coagulation with deionized water, solution is filtered by filter (aperture is 0.25 μ m), obtain throw out.Throw out is dispersed in again in the deionized water of 90 degree suction filtration.Repeat above-mentioned steps 5 times, reach 7 until pH value of filtrate.Hydrochloric acid soln with pH=2 soaked 4 hours, washed to pH=7 again.
6. oven dry:
The powder that filtration is obtained obtains single crystal nano-powder 80 ℃ of oven dry.Electron microscopic study shows, 200 ℃, 120 hours synthetic powder are the nano belt of wide 30nm, length 300-500nm.
Embodiment 10:
Width is that 50-70nm, length are the synthetic of 500-1000nm Rosensthiel's green nano belt
1. prepare burden:
(1) claiming 10 gram KOH and 7 gram NaOH to add volumes is in 25 milliliters the polytetrafluoroethylcontainer container.
(2) claim 0.5mmol bariumchloride and 0.5mmol Manganse Dioxide to add in the alkali in the above polytetrafluoroethylcontainer container.
(3) will gather four not ethene container sealing, to keep the cleaning of reaction process.
2. heating and melting:
With retort furnace or baking oven for heating to 200 ℃, the polytetrafluoroethylcontainer container of sealing is put into heating installation.Make heating installation insulation 1 hour, stir and make liquation and reactant uniform mixing.
3. isothermal reaction:
Reactant in the solution was reacted 24 hours under these conditions, carry out fully until reaction.
4. cooling:
Reaction vessel is taken out from heating installation, in air, cool off, reduce to room temperature to reaction vessel.
5. washing:
Fall the alkali fusion that cools off after coagulation with deionized water, solution is filtered by filter (aperture is 0.25 μ m), obtain throw out.Throw out is dispersed in again in the deionized water of 90 degree suction filtration.Repeat above-mentioned steps 5 times, reach 7 until pH value of filtrate.Hydrochloric acid soln with pH=2 soaked 4 hours, washed to pH=7 again.
6. oven dry:
The powder that filtration is obtained obtains single crystal nano-powder 80 ℃ of oven dry.Electron microscopic study shows that 170 ℃, 72 hours synthetic powder are that width is that 50-70nm, length are the nano belt of 500-1000nm
Embodiment 11:
Synthesizing of grass shape cerium acid barium nanostructure
1. prepare burden:
(1) claiming 10 gram KOH and 7 gram NaOH to add volumes is in 25 milliliters the polytetrafluoroethylcontainer container.
(2) claim 0.5mmol bariumchloride and 0.5mmol cerium dioxide to add in the alkali in the above polytetrafluoroethylcontainer container.
(3) will gather four not ethene container sealing, to keep the cleaning of reaction process.
2. heating and melting:
With retort furnace or baking oven for heating to 210 ℃, the polytetrafluoroethylcontainer container of sealing is put into heating installation.Make heating installation insulation 1 hour, stir and make liquation and reactant uniform mixing.
3. isothermal reaction:
Reactant in the solution was reacted 90 hours under these conditions, carry out fully until reaction.
4. cooling:
The retort furnace outage is cooled to room temperature, reaction vessel is taken out from retort furnace.
5. washing:
Fall the alkali fusion that cools off after coagulation with deionized water, solution is filtered by filter (aperture is 0.2 μ m), obtain throw out.Throw out is dispersed in the deionized water again suction filtration.Repeat above-mentioned steps 5 times, reach 7 until pH value of filtrate.
6. oven dry:
The powder that filtration is obtained obtains single crystal nano-powder 100 ℃ of oven dry.
X-ray diffraction is the result show, the powder that experiment obtains is the cerium acid barium of single-phase tetragonal.Scanning and transmission electron microscopy are observed and are shown that powder is the careless shape nanostructure of being made up of nano belt, and the wide position of " blade of grass " is the 150-180 nanometer, and narrow position is 20-30 nanometer (Fig. 7).Electron diffraction collection of illustrative plates and high-resolution electron microscopy result have further verified the result of X-ray diffraction.As shown in Figure 4.
Embodiment 12:
Synthesizing of lead vanadate nano belt
1. prepare burden:
(1) claiming 10 gram KOH and 7 gram NaOH to add volumes is in 25 milliliters the polytetrafluoroethylcontainer container.
(2) claim 0.5mmol lead nitrate and 0.5mmol Vanadium Pentoxide in FLAKES to add in the alkali in the above polytetrafluoroethylcontainer container.
(3) will gather four not ethene container sealing, to keep the cleaning of reaction process.
2. heating and melting:
With retort furnace or baking oven for heating to 180 ℃, the polytetrafluoroethylcontainer container of sealing is put into heating installation.Make heating installation insulation 1 hour, stir and make liquation and reactant uniform mixing.
3. isothermal reaction:
Reactant in the solution was reacted 72 hours under these conditions, carry out fully until reaction.
4. cooling:
Reaction vessel is taken out from heating installation, cool off in the air, reduce to room temperature to reaction vessel.
5. washing:
Fall the alkali fusion that cools off after coagulation with deionized water, solution is filtered by filter (aperture is 0.22 μ m), obtain throw out.Throw out is dispersed in the deionized water that is heated to 90 ℃ again suction filtration.
6. oven dry:
The powder that filtration is obtained obtains single crystal nano-powder 80 ℃ of oven dry.
XRD result shows that reaction product is monocline Pb
2V
2O
7Scanning and transmission electron microscope observation are found, reaction product is a width 50-70 nanometer, thickness is the 25-30 nanometer, length is that several microns nano belt (Fig. 8) electron energy loss spectroscopy (EELS) shows, chemical constitution in the nano belt is the metering ratio in the chemical formula, and electron diffraction and high-resolution electron microscopy studies confirm that XRD result.
Embodiment 13:
Synthesizing of lanthanum hydroxide nano belt
1. prepare burden:
(1) claiming 5 gram KOH and 9 gram NaOH and 5 gram LiOH to add volumes is in 25 milliliters the polytetrafluoroethylcontainer container.
(2) claim the 0.5mmol lanthanum acetate to add in the alkali in the above polytetrafluoroethylcontainer container.
(3) will gather four not ethene container sealing, to keep the cleaning of reaction process.
2. heating and melting:
With retort furnace or baking oven for heating to 200 ℃, the polytetrafluoroethylcontainer container of sealing is put into heating installation.Make heating installation insulation 1 hour, stir and make liquation and reactant uniform mixing.
3. isothermal reaction:
Reactant in the solution was reacted 40 hours under these conditions, carry out fully until reaction.
4. cooling:
Reaction vessel is taken out from heating installation, cool off in the air, reduce to room temperature to reaction vessel.
5. washing:
Fall the alkali fusion that cools off after coagulation with deionized water, solution is filtered by filter (aperture is 0.2 μ m), obtain throw out.Throw out is dispersed in the deionized water that is heated to 90 ℃ again suction filtration.The suction filtration process repeats 6 times, to pH=7.
6. oven dry:
The powder that filtration is obtained obtains single crystal nano-powder 80 ℃ of oven dry.
X-ray diffraction is the result show, the powder that experiment obtains is the lanthanum hydroxide of hexagonal structure.Scanning and transmission electron microscopy are observed and are shown that powder is the nano belt structure, and the width of nano belt is the 150-250 nanometer, and thickness reaches tens microns (Fig. 9) for the 30-50 nanometer length.Electron energy loss spectroscopy (EELS) has shown that the chemical ingredients of nano belt is oxygen and lanthanum (protium can't detect), and the electron diffraction collection of illustrative plates has further been verified the result of X-ray diffraction.
Embodiment 14:
Cr
2O
3Synthesizing of nano belt
1. prepare burden:
(1) claiming 10 gram KOH and 6 gram LiOH to add volumes is in 25 milliliters the polytetrafluoroethylcontainer container.
(2) claim 0.5mmol titanium dioxide lanthanum to add in the alkali in the above polytetrafluoroethylcontainer container.
(3) will gather four not ethene container sealing, to keep the cleaning of reaction process.
2. heating and melting:
With retort furnace or baking oven for heating to 200 ℃, the polytetrafluoroethylcontainer container of sealing is put into heating installation.Make heating installation insulation 1 hour, rock reaction vessel and make liquation and reactant uniform mixing.
3. isothermal reaction:
Reactant in the solution was reacted 48 hours under these conditions, carry out fully until reaction.
4. cooling:
Reaction vessel is taken out from heating installation, cool off in the air, reduce to room temperature to reaction vessel.
5. washing:
Fall the alkali fusion that cools off after coagulation with deionized water, solution is filtered by filter (aperture is 0.2 μ m), obtain throw out.Throw out is dispersed in the deionized water that is heated to 90 ℃ again suction filtration.The suction filtration process repeats 5 times, to pH=7.
6. oven dry:
The powder that filtration is obtained obtains single crystal nano-powder 80 ℃ of oven dry.
X-ray diffraction is the result show, the powder that experiment obtains is the Cr of hexagonal structure
2O
3Scanning and transmission found that reaction product is that width is that 30-50 nanometer, thickness are 20 nanometers, and length is the nano belt of 300-500 nanometer.Electron energy loss spectroscopy (EELS) studies show that the chemical ingredients of nano belt meets Cr
2O
3The atomic ratio of middle Cr and O, the result of electron diffraction supports the analytical results of XRD.
Embodiment 15
Synthesizing of cerium oxide nanoparticles
1. prepare burden:
(1) claiming 8 gram NaOH and 6 gram LiOH to add volumes is in 25 milliliters the polytetrafluoroethylcontainer container.
(2) claim 0.5mmol Ce (NO
3)
3Add in the alkali in the above polytetrafluoroethylcontainer container.
(3) will gather four not ethene container sealing, to keep the cleaning of reaction process.
2. heating and melting:
With retort furnace or baking oven for heating to 190 ℃, the polytetrafluoroethylcontainer container of sealing is put into heating installation.Make heating installation insulation 1 hour, rock reaction vessel and make liquation and reactant uniform mixing.
3. isothermal reaction:
Reactant in the solution was reacted 48 hours under these conditions, carry out fully until reaction.
4. cooling:
Reaction vessel is taken out from heating installation, cool off in the air, reduce to room temperature to reaction vessel.
5. washing:
Fall the alkali fusion that cools off after coagulation with deionized water, solution is filtered by filter (aperture is 0.2 μ m), obtain throw out.Throw out is dispersed in the deionized water that is heated to 90 ℃ again suction filtration.The suction filtration process repeats 5 times, to pH=7.
6. oven dry:
The powder that filtration is obtained obtains single crystal nano-powder 80 ℃ of oven dry.
X-ray diffraction is the result show, the powder that experiment obtains is the CeO of cubic structure
2Scanning and transmission found that reaction product is that width is the nanometer monocrystalline particle of 20-50 nanometer.Electron energy loss spectroscopy (EELS) studies show that the chemical ingredients of nano particle meets CeO
2The atomic ratio of middle Ce and O, the result of electron diffraction supports the analytical results of XRD.High-resolution electron microscopy discovers, this nano particle is that nanometer monocrystalline particle about 5 nanometers is formed by diameter.
All methods and technology of preparing that the present invention discloses and proposes, those skilled in the art can be by using for reference this paper content, links such as appropriate change raw material and technology realize, although method of the present invention and technology of preparing are described with preferred embodiment, person skilled obviously can not change or reconfigure method as herein described and technological line in not break away from content of the present invention, spirit and scope, realizes final film technique.Special needs to be pointed out is that replacement and change that all are similar are real conspicuous for a person skilled in the art, they are regarded as being included in spirit of the present invention, scope and the content.
Claims (10)
1. the low-temperature alkaline-solution synthesis of an oxygen metal inorganic compound monocrystal nano-material, by batching, heating and melting, isothermal reaction, cooling and washing step are formed, it is characterized in that described batching is meant to be that the ratio weighing of A: B=x: y mixes the back and adds and filled in the reaction vessel of mixed base according to atomic ratio as A position raw material and B position raw material among the composite oxides AxByOz of synthetic target; Described heating and melting is that reactor is put into the heating installation that is heated to 160 ℃-220 ℃, carries out preheating and melts, and through 30-90 minute, the solid mixed base of inside reactor is melted fully, and reactant is uniform distribution in mixed ammonium/alkali solutions; Described isothermal reaction is to instigate reaction vessel to continue heating 24-96 hour under the homothermic state, and the A position in the assurance mixed base melt and the compound of B bit element fully react; Described cooling is meant after reaction reaches the time of setting, reaction vessel is cooled to room temperature; Described washing be with the reaction product that has mixed base of having solidified wash to pH be 7, through the suction filtration oven dry, the product of last gained is the complex metal oxides single crystal nano-powder.
2. the low-temperature alkaline-solution synthesis of oxygen metal inorganic compound monocrystal nano-material as claimed in claim 1, it is characterized in that: A is the metal ion of meta-alkalescence among the described composite oxides AxByOz, B is the metal ion of both sexes or slant acidity; Two or more A position is arranged in the AxByOz lattice and B position ionic is compound and mix.
3. the low-temperature alkaline-solution synthesis of oxygen metal inorganic compound monocrystal nano-material as claimed in claim 2, it is characterized in that: described A is Ba, Sr, Ca, one of Pb, described B is Ti, Si, Ce, V, one of Al.
4. the molten caustic soda process for thermosynthesizing of complex metal oxides monocrystal nano-material as claimed in claim 1 or 2 is characterized in that: described A position raw material is inorganic salt or simple organic salt, and described B position raw material is slant acidity or intermediate oxide; And its valence state is identical with valence state in the composite oxides chemical formula.
5. the low-temperature alkaline-solution synthesis of oxygen metal inorganic compound monocrystal nano-material as claimed in claim 4, it is characterized in that: described A position raw material is a muriate, nitrate, vitriol, carbonate, one of acetate; Described B position raw material is one of titanium oxide, ferric oxide, cobalt oxide, vanadium oxide, aluminum oxide.
6. the low-temperature alkaline-solution synthesis of oxygen metal inorganic compound monocrystal nano-material as claimed in claim 1, it is characterized in that: described mixed base is made up of two or more anhydrous alkali metal hydroxides, its ratio is AOH: BOH: COH=0.1～0.8: 0.1～0.8: 0～0.8.
7. the low-temperature alkaline-solution synthesis of oxygen metal inorganic compound monocrystal nano-material as claimed in claim 6, it is characterized in that: described anhydrous alkali metal hydroxides is a lithium hydroxide, sodium hydroxide, potassium hydroxide, one of rubidium hydroxide.
8. the low-temperature alkaline-solution synthesis of oxygen metal inorganic compound monocrystal nano-material as claimed in claim 1 is characterized in that: described heating installation be one of retort furnace, resistance furnace, drying machine, baking oven can be to the accurate heating installation of control of temperature; Described reaction vessel be one of precious metal vessel, organism container to alkali metal hydroxide inert container.
9. the low-temperature alkaline-solution synthesis of oxygen metal inorganic compound monocrystal nano-material as claimed in claim 1, it is characterized in that: the described type of cooling is that well heater is cooled to room temperature according to setting speed, the stove internal cooling perhaps directly cuts off the power supply, perhaps directly reaction vessel is taken out from well heater, be put in the frozen water after perhaps taking out and cool off.
10. the low-temperature alkaline-solution synthesis of oxygen metal inorganic compound monocrystal nano-material as claimed in claim 1, it is characterized in that: described washing is the product dissolving that has mixed base that will solidify with cold or hot deionized water or diluted acid, adopt whizzer precipitation or pumping and filtering device to filter suspension, filtering product disperses in cold or hot deionized water or diluted acid again, filter once more, reach 7 until filtrate pH value.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100497163C (en) * | 2007-06-21 | 2009-06-10 | 重庆大学 | Compound alkali metal hydrate dissolvent synthesis method for metallic sulfide nano crystal material |
| CN100553833C (en) * | 2008-01-14 | 2009-10-28 | 重庆大学 | The method for preparing metallic simple substance nano-crystal material |
| CN102008951A (en) * | 2010-11-10 | 2011-04-13 | 武汉理工大学 | Mo-C-codoped method for preparing one-dimensional titanate nanobelt photocatalyst material |
| CN102219256A (en) * | 2011-03-03 | 2011-10-19 | 刘爱林 | Thermochromic vanadium dioxide powder and preparation method thereof |
| WO2020125483A1 (en) * | 2018-12-17 | 2020-06-25 | 深圳先进技术研究院 | Preparation method for metal oxide or composite material thereof, metal oxide or composite material and application thereof, and battery |
-
2006
- 2006-06-20 CN CNB2006100449393A patent/CN100497757C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100497163C (en) * | 2007-06-21 | 2009-06-10 | 重庆大学 | Compound alkali metal hydrate dissolvent synthesis method for metallic sulfide nano crystal material |
| CN100553833C (en) * | 2008-01-14 | 2009-10-28 | 重庆大学 | The method for preparing metallic simple substance nano-crystal material |
| CN102008951A (en) * | 2010-11-10 | 2011-04-13 | 武汉理工大学 | Mo-C-codoped method for preparing one-dimensional titanate nanobelt photocatalyst material |
| CN102008951B (en) * | 2010-11-10 | 2012-05-30 | 武汉理工大学 | Mo-C-codoped method for preparing one-dimensional titanate nanobelt photocatalyst material |
| CN102219256A (en) * | 2011-03-03 | 2011-10-19 | 刘爱林 | Thermochromic vanadium dioxide powder and preparation method thereof |
| WO2020125483A1 (en) * | 2018-12-17 | 2020-06-25 | 深圳先进技术研究院 | Preparation method for metal oxide or composite material thereof, metal oxide or composite material and application thereof, and battery |
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|---|---|
| CN100497757C (en) | 2009-06-10 |
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