CN101279754A - Preparation for nano-boehmite with diverse morphologies - Google Patents
Preparation for nano-boehmite with diverse morphologies Download PDFInfo
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- CN101279754A CN101279754A CNA2008100377318A CN200810037731A CN101279754A CN 101279754 A CN101279754 A CN 101279754A CN A2008100377318 A CNA2008100377318 A CN A2008100377318A CN 200810037731 A CN200810037731 A CN 200810037731A CN 101279754 A CN101279754 A CN 101279754A
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- boehmite
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Abstract
The invention relates to a method for the production of a nanometer boehmite with a plurality of patterns, in particular relates to a method for the production of nanometer boehmite materials such as nano-fibers, core shell inner balls, solid balls and hollow balls, and belongs to the technique field of inorganic nano-material preparation process. The method of the invention is characterized in that: a given amount of soluble aluminum salt is dissolved in water then an organic auxiliary solvent is added thereto, a given amount of pattern control agent is added as well under agitation, then the mixed liquid is put into a hydrothermal kettle for reaction at the temperature of between 160 and 250 DEG C for two to sixty hours, the reaction product is separated and the prepared deposition is washed with deionized water and ethanol, finally, the boehmite materials with specific patterns are obtained by being dried at the temperature of between 60 and 80 DEG C. The pattern control agent is one of citrate, tartrate, oxalate and disodium ethylenediamine tetraacetic acid, and the quantity added thereto is ranging from 0 to 20mmol.
Description
Technical field
The present invention relates to the preparation method of one kind of multiple pattern nm boehmite, specifically, relate to nm boehmite preparation methods such as nanofiber, nucleocapsid ball endosphere, solid sphere, hollow ball, belong to the inorganic nano material preparation process technology field.
Background technology
Sapphire whisker has the intensity height, modulus is big, thermal conductivity is little, thermal expansivity is low, advantages such as heat-resisting resistance to elevated temperatures is good, and the surfactivity height can form the matrix material of superior performance with resin, metal, pottery, is widely used in high-tech areas such as space flight, military project.
The hollow parts of alumina core shell structure and hollow ball can hold a large amount of guest molecules or large size object, thereby produce some unusual character based on microcosmic " encapsulation ", " parcel " effect, the hollow structure of these nanoscales or meso-scale compare with its block materials have low density, characteristic such as high-specific surface area, good stability, good surface seepage ability and special optical property and receive very big concern, and hollow shell can be constructed by the various materials that using value arranged according to people's interest and forms.Since more than many characteristics of possessing; make it a lot of important use all be arranged, for example filter, transmission, electricity device and the Accoustical sound proofing material etc. of the protection of coating, pigment, artificial cell, catalyzer, photoactive substance, makeup, ink, fuel, parting material, coating, sustained release capsule, medicine in fields such as chemistry, biology and Materials science.
More than owing to have special pattern thereby have the nano aluminium oxide of special applications all can obtain through high-temperature calcination by aluminium hydroxide or boehmite.
At present, in the preparation method of numerous boehmites and alumina material, vapor phase process, sol-gel method, microemulsion method, precipitation hydrolysis method etc. is occupied than consequence.For example: " advanced material " (Advanced Materials, 2007,19,102) utilize atomic deposition to prepare hollow ball; (Ind.Eng.Chem.Res.2007,46,8004) such as East China science and engineering Li utilize the method for high-velocity flame spray to prepare the hollow ball of the thick about 30nm of shell; (Ceramics International, 2007,33,305) such as the Pan of Shanghai Silicate Inst., Chinese Academy of Sciences utilize aluminium foil and sulfuric acid reaction to prepare the Al/AlOOH core-shell nano; (Nano letter, 2007,7,3489) such as Claus Feldmann utilize microemulsion method to prepare the AlOOH hollow ball of the about 30nm of diameter; But these methods are not to need high temperature, costliness and complex apparatus, will use many organic solvents exactly, and operational condition is generally relatively harsher.Thereby develop a kind of raw material and be easy to get, with low cost, simple to operate, it is convenient to handle, the reaction conditions gentleness, and it is significant to be easy to industrialized nm boehmite synthetic method.
Summary of the invention
The object of the present invention is to provide the preparation method of one kind of multiple pattern nm boehmite, to overcome the existing in prior technology defective.
The aluminum oxide that the present invention makes, aluminium hydroxide and hydrate thereof, its similar is in natural mineral boehmite (boehmite), so be called boehmite material.
The preparation method of one kind of multiple pattern nm boehmite of the present invention is characterized in that having following process and step:
A. a certain amount of aluminum soluble salt is dissolved in a certain amount of water, forming concentration is the solution of 0.01～0.2mol/L;
B. under agitation, add organic secondary solvent of 0～30ml, and mix;
C. under stirring at room, a certain amount of morphology control agent is joined in the above-mentioned solution, continue to stir to form uniform solution;
D. above-mentioned mixed solution is transferred in the water heating kettle, screws kettle cover, place baking oven, under 160～250 ℃ of temperature, react 2～60h, after reaction finishes, centrifugation, throw out is used deionized water and absolute ethanol washing for several times;
E. the clean throw out with above-mentioned gained descended dry 12 hours at 60～80 ℃, promptly got the boehmite of specific morphology;
Described aluminum soluble salt is any in aluminum nitrate, aluminum chloride, the Tai-Ace S 150;
Described organic assisted solution is any in methyl alcohol, ethanol, acetone, tetracol phenixin, the ethylene glycol;
Described morphology control agent is any in Citrate trianion, tartrate, oxalate, disodium ethylene diamine tetraacetate, the sodium alginate; The add-on of morphology control agent is 0～2mmol.
It is as described below to adopt the morphology control agent to form the mechanism of multiple pattern nm boehmite among the preparation method of the present invention:
Citrate, tartrate anion, disodium ethylene diamine tetraacetate (EDTA-2Na) etc. are to a lot of metal ions such as Ca
2+, Zn
2+, Al
3+Deng being good coordination agent, can form compound ion, it also can be used as the stablizer of morphology control agent simultaneously, forms complicated microstructure.Self-assembly is considered to form compound Ultrastructural effective means.Self-assembly generally is to promote the nanoparticle self-assembly by Van der Waals force and hydrogen bond.
With the citrate is example: under the situation that is added with trisodium citrate: under high temperature and high pressure, and Al (NO
3)
39H
2Reaction generates boehmite mutually to O with deionized water.At the commitment of reaction, Al (NO
3)
39H
2The slow hydrolysis of O generates the boehmite nanoparticle, and citrate ion selective adsorption boehmite nanoparticle surface allows the boehmite nanoparticle form nanometer rod along a direction growth then.Octahedral structure AlO in hydroxyl in the citrate ion and the boehmite
6In hydroxyl form hydrogen bond, the intensive by hydrogen bond interacts, self-assembly is the nano rod bundle structure of ordered arrangement.As for the formation of nucleocapsid structure even hollow ball be since at high temperature along with the reaction times prolong, due to the nuclear of ball dissolves.
Citrate all is good coordination agent to a lot of metal ions, can form compound ion, and it also can be used as morphology control agent and stablizer simultaneously.Citrate and Al
3+Form coordination ion, its structure forms and is exemplified below:
Reaction equation is:
Al
3++citrate
3-→Al(citrate)
Al
3++H
++citrate
3-→AlH(citrate)
+ (1)
Al
3+3H
2O→Al(OH)
3(amorphous)+3H
+ (2)
Al(OH)
3→r-AlOOH+H
2O (3)
Citrate in the following formula
3-The expression citrate ion.
The characteristics of the inventive method
The inventive method has following characteristics:
(1) the selected system of the inventive method can synthesize the boehmite of different-shape structure, thereby greatly reduce production cost by regulating amount, temperature of reaction and the time of morphology control agent in same system, has improved the production efficiency of nano material.
(2) the inventive method adopts hydrothermal method, and product has numerous circulation ratio good shapes, for good basis is established in the research and development of functional materials.
(3) used water and the organic solvent of the inventive method can recycling, therefore has easy and simple to handlely, and processing unit is simple, free of contamination advantage.
Description of drawings
Fig. 1 is the shape appearance figure that the transmission electron microscope (TEM) of embodiments of the invention one product obtains.
Fig. 2 is the structure iron that the X-ray powder diffraction (XRD) of embodiments of the invention one product obtains.
Fig. 3 is the shape appearance figure that the transmission electron microscope (TEM) of embodiments of the invention two products obtains.
Fig. 4 is the shape appearance figure that the transmission electron microscope (TEM) of embodiments of the invention three products obtains.
Fig. 5 is the shape appearance figure that the transmission electron microscope (TEM) of embodiments of the invention four products obtains.
Fig. 6 is the shape appearance figure that the transmission electron microscope (TEM) of embodiments of the invention five products obtains.
Fig. 7 is the shape appearance figure that the transmission electron microscope (TEM) of embodiments of the invention six products obtains.
Fig. 8 is the shape appearance figure that the transmission electron microscope (TEM) of embodiments of the invention seven products obtains.
Embodiment
Below the experiment and the result of the boehmite nanofiber for preparing for employing the inventive method, solid sphere, nucleocapsid structure, hollow ball illustrate.
Embodiment one: concrete steps are as follows:
A. the 3mmol aluminum nitrate is dissolved in the 20ml deionized water, forms the solution that mixes;
B. stir down, add the 20ml dehydrated alcohol and mix;
C. under the stirring at room, the Trisodium Citrate of 1mmol is joined in the above-mentioned solution, continue to stir the solution that 50min mixes with formation;
D. the above-mentioned solution that mixes is transferred in the water heating kettle, screws kettle cover, place 220 ℃ of reactions of baking oven 48h.After reaction finishes, centrifugal, with deionized water and absolute ethanol washing several.
E. with the sample of steps d gained at 80 ℃ of dry 12h, promptly getting nucleocapsid structure is the boehmite of spherical structure in the ball.
With this example products therefrom, characterize with the pattern of transmission electron microscope (TEM) to product.As can be seen from Fig. 1, products therefrom is by the about 1.7 μ m of outer spherical diameter, and interior spherical diameter is 1 μ m nucleocapsid structure, and outer shell is piled up by bundles of nanofibers and formed.As can be seen from Fig. 2, XRD result shows the pure AlOOH (consistent with the 21-1307JCPDS card) of being of product.
Embodiment two: concrete steps are as follows:
A. 0.5mmol Tai-Ace S 150 is dissolved in the 20ml deionized water, forms the solution that mixes;
B. stir down, add the 20ml dehydrated alcohol and mix;
C. under the stirring at room, the Trisodium Citrate of 0.5mmol is joined in the above-mentioned solution, continue to stir the solution that 30min mixes with formation;
D. the above-mentioned solution that mixes is transferred in the water heating kettle, screws kettle cover, place 180 ℃ of reactions of baking oven 6-18h.After reaction finishes, centrifugal, with deionized water and absolute ethanol washing several.
E. with the sample of steps d gained at 60 ℃ of dry 12h, promptly get the boehmite of solid sphere structure.
The present embodiment products therefrom is scattered in the dehydrated alcohol, characterizes, from Fig. 3, can know and see that diameter is approximately the boehmite solid sphere of 1 μ m with the pattern of transmission electron microscope (TEM) to product.
Embodiment three: concrete steps are as follows:
A. with in the 2mmol aluminum nitrate dissolving 20ml deionized water, form the solution that mixes;
B. stir down, add 20ml acetone and mix;
C. under the stirring at room, the Trisodium Citrate of 0.5mmol is joined in the above-mentioned solution, continue to stir the solution that 30min mixes with formation;
D. the above-mentioned solution that mixes is transferred in the water heating kettle, screws kettle cover, place 200 ℃ of reactions of baking oven 24h.After reaction finishes, centrifugal, with deionized water and absolute ethanol washing several.
E. with the sample of steps d gained at 60 ℃ of dry 12h, promptly get the boehmite of nucleocapsid structure.
The present embodiment products therefrom is scattered in the dehydrated alcohol, characterize with the pattern of transmission electron microscope (TEM) product, from Fig. 4, can know see products therefrom be outside about 2～3 μ m of spherical diameter, interior spherical diameter is the nucleocapsid structure of 1 μ m, and outer shell is piled up by compact nm crystal and formed.
Embodiment four: concrete steps are as follows:
A. 1mmol aluminum chloride is dissolved in the 20ml deionized water, forms the solution that mixes;
B. stir down, add 20ml ethylene glycol and mix, do not add the morphology control agent;
C. the above-mentioned solution that mixes is transferred in the water heating kettle, screws kettle cover, place 200 ℃ of reactions of baking oven 24h.After reaction finishes, centrifugal, with deionized water and absolute ethanol washing several.
D. with the sample of steps d gained at 60 ℃ of dry 12h, promptly get the boehmite of fiber bundle-like structure.
The present embodiment products therefrom is scattered in the dehydrated alcohol, characterizes, can know from Fig. 5 and see that length is approximately 200nm that diameter is approximately the boehmite fiber of 5～10nm with the pattern of transmission electron microscope (TEM) to product.
Embodiment five: concrete steps are as follows:
A. the 2mmol aluminum nitrate is dissolved in the 10ml deionized water, forms the solution that mixes;
B. stir down, add the 30ml dehydrated alcohol and mix;
C. under the stirring at room, the Trisodium Citrate of 1.5mmol is joined in the above-mentioned solution, continue to stir the solution that 30min mixes with formation;
D. the above-mentioned solution that mixes is transferred in the water heating kettle, screws kettle cover, place 200 ℃ of reactions of baking oven 6-18h.After reaction finishes, centrifugal, with deionized water and absolute ethanol washing several.
E. with the sample of steps d gained at 60 ℃ of dry 12h, promptly get the boehmite of hollow ball structure.
The present embodiment products therefrom is scattered in the dehydrated alcohol, characterizes, from Fig. 6, can know and see that diameter is approximately the boehmite hollow ball of 0.5～1 μ m with the pattern of transmission electron microscope (TEM) to product.
Embodiment six: concrete steps are as follows:
A. 2mmol aluminum chloride is dissolved in the 40ml deionized water;
B. under the stirring at room, the disodium ethylene diamine tetraacetate (EDTA-2Na) that adds 0.2mmol joins in the above-mentioned solution, continues to stir 30min and mixes equal solution to form;
C. the above-mentioned solution that mixes is transferred in the water heating kettle, screws kettle cover, place 200 ℃ of reactions of baking oven 12h.After reaction finishes, centrifugal, with deionized water and absolute ethanol washing several.
D. with the sample of steps d gained at 60 ℃ of dry 12h, promptly get the boehmite of fiber bundle-like structure.
The present embodiment products therefrom is scattered in the dehydrated alcohol, characterizes, can know from Fig. 7 and see that length is approximately 500nm that diameter is approximately the boehmite nanometer rod of 5～20nm with the pattern of transmission electron microscope (TEM) to product.
Embodiment seven: concrete steps are as follows:
A. the 2mmol aluminum nitrate is dissolved in the 40ml deionized water;
B. under the stirring at room, the sodium tartrate of 0.5mmol is joined in the above-mentioned solution, continue to stir the solution that 30min mixes with formation;
C. the above-mentioned solution that mixes is transferred in the water heating kettle, screws kettle cover, place 200 ℃ of reactions of baking oven 24h.After reaction finishes, centrifugal, with deionized water and absolute ethanol washing several.
D. with the sample of steps d gained at 60 ℃ of dry 12h, promptly get the boehmite of fiber bundle-like structure.
The present embodiment products therefrom is scattered in the dehydrated alcohol, characterizes, can know from Fig. 8 and see that length is approximately 200nm that diameter is approximately the boehmite fibrous bundle of 10～40nm ordered arrangement with the pattern of transmission electron microscope (TEM) to product.
Claims (1)
1. the preparation method of one kind of multiple pattern nm boehmite is characterized in that having following process and step:
A. a certain amount of aluminum soluble salt is dissolved in a certain amount of water, forming concentration is the solution of 0.01～0.2mol/L;
B. under agitation, add organic secondary solvent of 0～30ml, and mix;
C. under stirring at room, a certain amount of morphology control agent is joined in the above-mentioned solution, continue to stir to form uniform solution;
D. above-mentioned mixed solution is transferred in the water heating kettle, screws kettle cover, place baking oven, under 160～250 ℃ of temperature, react 2～60h, after reaction finishes, centrifugation, throw out is used deionized water and absolute ethanol washing for several times;
E. the clean throw out with above-mentioned gained descended dry 12 hours at 60～80 ℃, promptly got the boehmite of specific morphology;
Described aluminum soluble salt is any in aluminum nitrate, aluminum chloride, the Tai-Ace S 150;
Described organic assisted solution is any in methyl alcohol, ethanol, acetone, tetracol phenixin, the ethylene glycol;
Described morphology control agent is any in Citrate trianion, tartrate, oxalate, disodium ethylene diamine tetraacetate, the sodium alginate; The add-on of morphology control agent is 0～2mmol.
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| CN102179247A (en) * | 2011-03-21 | 2011-09-14 | 上海大学 | Method for preparing hollow spherical nickel-based catalyst for catalytic pyrolysis of oil tar |
| CN103011215A (en) * | 2012-12-10 | 2013-04-03 | 中国科学院合肥物质科学研究院 | Boehmite micro-nano structure sphere and preparation method thereof |
| CN103553097A (en) * | 2013-10-29 | 2014-02-05 | 华东理工大学 | Preparation method of nano-fiber boehmite material |
| CN103771470A (en) * | 2014-01-20 | 2014-05-07 | 绍兴文理学院 | Synthesis method for aluminium oxide nano hollow ball-in-ball |
| CN104445318A (en) * | 2014-11-17 | 2015-03-25 | 济南大学 | Sea-urchin-shaped hydroxyl alumina sphere and preparation method thereof |
| CN107879368A (en) * | 2017-12-06 | 2018-04-06 | 宁波爱克创威新材料科技有限公司 | Nano aluminium oxide and preparation method thereof |
| CN107913665A (en) * | 2017-11-29 | 2018-04-17 | 中南大学 | A kind of metal-doped boehmite and its preparation method and application |
| CN109574051A (en) * | 2019-01-15 | 2019-04-05 | 吉林大学 | A kind of preparation method of γ-AlOOH nanotube |
| CN109694096A (en) * | 2019-01-15 | 2019-04-30 | 吉林大学 | A kind of γ-AlOOH platy-monocrystal and preparation method thereof |
| CN111333128A (en) * | 2020-03-05 | 2020-06-26 | 西北工业大学 | Preparation method of high-uniformity nickel oxide |
| CN115259235A (en) * | 2021-04-30 | 2022-11-01 | 遵义师范学院 | Simple synthesis method of three-dimensional ferric oxide with haystack structure formed by stacking nano short rods |
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2008
- 2008-05-20 CN CNA2008100377318A patent/CN101279754A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102179247A (en) * | 2011-03-21 | 2011-09-14 | 上海大学 | Method for preparing hollow spherical nickel-based catalyst for catalytic pyrolysis of oil tar |
| CN103011215A (en) * | 2012-12-10 | 2013-04-03 | 中国科学院合肥物质科学研究院 | Boehmite micro-nano structure sphere and preparation method thereof |
| CN103011215B (en) * | 2012-12-10 | 2014-11-26 | 中国科学院合肥物质科学研究院 | Boehmite micro-nano structure sphere and preparation method thereof |
| CN103553097A (en) * | 2013-10-29 | 2014-02-05 | 华东理工大学 | Preparation method of nano-fiber boehmite material |
| CN103553097B (en) * | 2013-10-29 | 2015-04-15 | 华东理工大学 | Preparation method of nano-fiber boehmite material |
| CN103771470B (en) * | 2014-01-20 | 2015-06-03 | 绍兴文理学院 | Synthesis method for aluminium oxide nano hollow ball-in-ball |
| CN103771470A (en) * | 2014-01-20 | 2014-05-07 | 绍兴文理学院 | Synthesis method for aluminium oxide nano hollow ball-in-ball |
| CN104445318B (en) * | 2014-11-17 | 2016-05-25 | 济南大学 | A kind of sea urchin shape aluminum oxyhydroxide ball and preparation method thereof |
| CN104445318A (en) * | 2014-11-17 | 2015-03-25 | 济南大学 | Sea-urchin-shaped hydroxyl alumina sphere and preparation method thereof |
| CN107913665A (en) * | 2017-11-29 | 2018-04-17 | 中南大学 | A kind of metal-doped boehmite and its preparation method and application |
| CN107879368A (en) * | 2017-12-06 | 2018-04-06 | 宁波爱克创威新材料科技有限公司 | Nano aluminium oxide and preparation method thereof |
| CN109574051A (en) * | 2019-01-15 | 2019-04-05 | 吉林大学 | A kind of preparation method of γ-AlOOH nanotube |
| CN109694096A (en) * | 2019-01-15 | 2019-04-30 | 吉林大学 | A kind of γ-AlOOH platy-monocrystal and preparation method thereof |
| CN109574051B (en) * | 2019-01-15 | 2021-01-19 | 吉林大学 | Preparation method of gamma-AlOOH nanotube |
| CN109694096B (en) * | 2019-01-15 | 2021-06-01 | 吉林大学 | Gamma-AlOOH flaky monocrystal and preparation method thereof |
| CN111333128A (en) * | 2020-03-05 | 2020-06-26 | 西北工业大学 | Preparation method of high-uniformity nickel oxide |
| CN111333128B (en) * | 2020-03-05 | 2021-04-13 | 西北工业大学 | Preparation method of high-uniformity nickel oxide |
| CN115259235A (en) * | 2021-04-30 | 2022-11-01 | 遵义师范学院 | Simple synthesis method of three-dimensional ferric oxide with haystack structure formed by stacking nano short rods |
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Open date: 20081008 |