CN100368281C - Preparation method of nanometer metal oxide and composite metal oxide - Google Patents
Preparation method of nanometer metal oxide and composite metal oxide Download PDFInfo
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- CN100368281C CN100368281C CNB2005101266253A CN200510126625A CN100368281C CN 100368281 C CN100368281 C CN 100368281C CN B2005101266253 A CNB2005101266253 A CN B2005101266253A CN 200510126625 A CN200510126625 A CN 200510126625A CN 100368281 C CN100368281 C CN 100368281C
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Abstract
The present invention discloses a method for preparing nanometer metal oxides and mixed metal oxides. Aiming at overcoming shortcomings or defects of the prior art of long producing cycle, high material cost, unfit industrialization and low powder particle quality, the present invention is characterized in that the present invention combines a macromolecule network gelatinization process and a micro-zone precipitation process, and thereby, the nanometer spherical powder of high-purity metal oxides and/or mixed metal oxides with uniform granularity, narrow distribution, less aggregation and controllable particle diameter can be obtained at a lower temperature. The basic technology uses net macromolecules formed by that small molecule organic matter is polymerized in situ under certain conditions, and the aqueous solution containing soluble metal salts and urea is directly converted into wet gel; then, the urea is hydrolyzed in moist steam at a certain temperature, precipitation reaction occurs in a three-dimensional network micro-zone, and finally, the nanometer powder is obtained by heat treatment. The preparation method has the advantages of simple technology, high yield, energy saving, water saving and easy industrialization.
Description
Technical field
The present invention relates to nanotechnology, relate in particular to the preparation method of a kind of nano-metal-oxide or complex metal oxides.
Background technology
Nanotechnology is the crystallization of 20th century development in science and technology, is one of three big science and technology of 21 century.The preparation of nano-powder and complete processing and applied research are the important branch fields of nanotechnology, have contained each crossing domains such as chemical industry, material, electronics, military affairs, manufacturing, industry, and the aspects such as social concern that caused by nanotechnology.Nano-powder be meant grain size at 1nm to the nanoparticle between the 100nm.Owing to itself have surface effects, small-size effect, quantum size effect and macroscopical tunnel effect etc., make it show the property that is different from conventional material at aspects such as light, electricity, magnetic, mechanics and catalysis.Nano-metal-oxide and composite metal oxide powder have broad application prospects in fields such as chemical industry, electronics, metallurgy, aerospace, biology and medical science as an important class material.
The preparation method that nano-metal-oxide or complex metal oxides are commonly used is an alkaline chemical precipitation method in the soluble metal salts solution, through filtration, dry, calcining, obtains nano-powder.As publication number is the patent document disclosed " composite oxide semiconductor preparation of nanomaterials " of CN1622283A, and this method technology is simple, easily suitability for industrialized production.But well-known, because the precipitated product that this method generates is gluey oxyhydroxide mostly, filtration time is long, has correspondingly increased the production cycle; Moreover easily form hydrogen bond between the throw out, and when filtration, drying, high-temperature calcination, easily cause powder granule to reunite, grow up, be difficult to obtain the powder of uniform particles, good dispersity, hard aggregation-free.Though (Liu Jun etc., vacuum freeze-drying method prepare the research of nano aluminium oxide ceramics powder to some scholar, vacuum, 2004,41 (4): 80-83; Cao Aihong, the precipitator method prepare TiO
2The research of nano-powder and microwave drying, Henan chemical industry, 2002 (6): 9-11) adopt ways such as lyophilize, microwave drying to reduce reunion, but these measures need task equipment, and output is little, lacks practicality in industrial production.
Sol-gel method is a lot of method for preparing nano-metal-oxide or composite metal oxide powder of another research.It mainly adopts the organism of metal that hydrolysis formation colloidal sol takes place in the aqueous solution, and then polymerization reaction take place generates the gel with certain space structure, through super-dry, obtain nano-metal-oxide or composite metal oxide powder after the calcining at a certain temperature then.As (O.Varnier etc., Sol-gelsynthesis of magnesium aluminum spinel from a heterometallic alkoxide, Mat Res Bull, 1994,29:479-488; ).But as we all know, this kind method shortcoming is that cost of material is relatively more expensive, and the production cycle is long.
People such as A.Douy (A.Douy et al, The polyacrylamide gel:Anovel route to ceramicand glassy oxide powders, Materials Research Bulletin, 1989,24 (9): 1119-1126) and people (Wu Yanchun etc. such as Wu Yanchun, the chemical soft of nano NiO ultrafine powder synthesized, HeFei University of Technology's journal (natural science edition), 2003,26 (3): 404-406) with nitrate be raw material, in its aqueous solution, add acrylamide monomer, N, N '-methylene-bisacrylamide is as linking agent, obtain polyacrylamide-gel, drying in action of evocating, the calcining back obtains nano composite metal oxide or metal-oxide powder.Because the grid that forms can not stop metal ion to move in drying process, powder granule is reunited still relatively more serious.
(Zhao Jiupeng etc., organic gel method low temperature synthesizes Sr to people such as Zhao Jiupeng
xBa
1-xNb
2O
5Powder, Journal of Inorganic Materials, 2004,19 (1): 75-80) and people (Zhang Bangqiang etc. such as Zhang Bangqiang, organic gel method prepares doping chromic acid lanthanum nano-powder, silicate journal, 2005,33 (4): 447-451) utilize organic gel method to synthesize nano-metal-oxide and composite oxide of metal powder, it is raw material that this method adopts metal nitrate, in its aqueous solution, add citric acid as complexing agent and ethylene glycol as linking agent, water-bath gel after drying, in low-temperature ignition, obtain nano-powder at last.This method gel, time of drying are long, and burning is violent, and powder granule size and pattern are difficult to control.
Summary of the invention
In view of the existing in prior technology shortcoming and defect, the object of the present invention is to provide a kind of preparation high quality nano level, epigranular, narrowly distributing, it is few to reunite, the method for size-controllable spherical metal oxide or composite metal oxide powder.
Technical solution of the present invention is achieved in that
The preparation method of a kind of nano-metal-oxide or complex metal oxides, it is characterized in that it combines polyacrylamide-gelization with the microcell precipitation process, preparation nano-metal-oxide or complex metal oxides, its technological process is as follows: one or more soluble metallic salt and urea are dissolved in the deionized water, stir, add monomer and linking agent again, be made into mixing solutions, and place and stir the initiator that the back adds gelation on the agitator, polymerization reaction take place forms macromolecule network wet gel body in 35-75 ℃ of temperature range then, it is heated in 80-120 ℃ of saturated steam, urea generation hydrolysis, form precipitation with the metal ion in the network microcell, last, according to the difference of final generation product, the wet gel of gained is directly calcined, making particle diameter is 10～100 nanometers, epigranular, size-controllable spherical metal oxide or composite metal oxide powder;
Described soluble metallic salt is meant to generate sedimentary soluble metal nitrate or vitriol with the hydrolysate of urea that its consumption calculates by the content of each metal ion species in the desired final product; Urea is as the precipitation agent of microcell precipitin reaction, and its consumption is 1.2～3 times of mole numbers pressing the effective metal total ion concentration of reaction ratio calculating; Monomer is selected acrylamide for use, and linking agent is selected N for use, and N '-methylene-bisacrylamide, both consumptions are 10: 1～3: 1 by weight; The initiator of gelation is selected ammonium persulphate for use, and its adding proportion is 10～20wt% ammonium persulfate solution that every 100ml mixing solutions drips 2～1ml.
Described mixing solutions can adopt one or more soluble metallic salt and urea is dissolved in and contain acrylamide monomer and N, and is formulated in the aqueous solution of N '-methylene-bisacrylamide.
Described soluble metallic salt employing can generate sedimentary soluble metal nitrate with the hydrolysate of urea preferable, and it forms corresponding ammonium nitrate by product when forming precipitation by metallic ion in the microcell precipitation process.
Described concrete calcining temperature and time need to decide according to the final product that generates, and residual byproduct of reaction C and N are eliminated in the calcining back when obtaining required nano-powder.
Described various raw material comprises soluble metal nitrate, urea, acrylamide monomer, N, N '-methylene-bisacrylamide, ammonium persulphate, and its purity is more than the chemical pure.
The present invention proposes a kind of polymer-network gel method and the microcell precipitator method are combined and prepare the method for nanosize metal oxide or complex metal oxides.It is utilize small organic molecule under certain condition in-situ polymerization reticulate polymer, the aqueous solution that will contain soluble metallic salt and urea directly becomes wet gel, make hydrolysis of urea in the saturated steam at a certain temperature then, in the three-dimensional network microcell precipitin reaction taking place, obtains nano-powder through calcining at last.Soluble metallic salt is introduced required metal ion in the final product; Urea is the precipitation agent as the microcell precipitin reaction; Small organic molecule, as acrylamide monomer, N, N '-methylene-bisacrylamide is as forming the high molecular raw material of network.The incinerating purpose is to obtain Single Phase Metal oxide compound or complex metal oxides in order to guarantee, and eliminates residual C and N.Calcining temperature is decided according to the product of ultimate demand.Because the effect of grid, being deposited in of generation is not easy to pass grid in the calcination process, the difficult reunion, thereby obtain particle tiny, reunite less, the powder of good dispersity.
With the powder that method provided by the present invention obtains, synthesis temperature is lower relatively, and powder granularity is little, and the sintering activity height is suitable for preparing high performance agglomerated material; Simultaneously, this method have technology simple, fast, cost is low, process is easy to control, be easy to advantage such as suitability for industrialized production.
Description of drawings
2 in accompanying drawing of the present invention, wherein
Fig. 1 is the XRD figure spectrum of embodiment 1 gained powder;
Fig. 2 is the transmission electron microscope photo of embodiment 1 gained powder.
Wherein, Fig. 2 is a Figure of abstract of the present invention.
Embodiment
Embodiment 1 gets 7.503g Al (NO
3)
39H
2O, 2.564gMg (NO
3)
26H
2O and 4.805g urea are dissolved in 80ml and contain the 5wt% acrylamide, acrylamide and N, N '-methylene-bisacrylamide mass ratio is in 5: 1 the mixing solutions, and then drip the ammonium persulfate solution of 0.8ml 20wt%, after stirring, be placed in 63 ℃ the water-bath heating until forming gel.Wet gel was placed in 110 ℃ the saturated steam heating 2 hours, and placed it in then in the box-type furnace, be warming up to 1000 ℃ of calcining 2h, promptly obtain white, particle diameter is the MgAl of 40～50nm
2O
4Nano-powder.As Fig. 1 is the XRD figure spectrum of product, shows that product is single magnesium-aluminium spinel phase; Fig. 2 is the transmission electron microscope photo of prepared powder, shows that powder granule is a nano level, epigranular, and it is less to reunite.
Embodiment 2 and embodiment 3 compare with embodiment 1, and technological process is identical, and related parameter changes as shown in the table:
Claims (5)
1. the preparation method of nano-metal-oxide or complex metal oxides, it is characterized in that it combines polyacrylamide-gelization with the microcell precipitation process, preparation nano-metal-oxide or complex metal oxides, its technological process is as follows: one or more soluble metallic salt and urea are dissolved in the deionized water, stir, add monomer and linking agent again, be made into mixing solutions, and place and stir the initiator that the back adds gelation on the agitator, polymerization reaction take place forms macromolecule network wet gel body in 35-75 ℃ of temperature range then, it is heated in 80-120 ℃ of saturated steam, urea generation hydrolysis, form precipitation with the metal ion in the network microcell, last, according to the difference of final generation product, the wet gel of gained is directly calcined, making particle diameter is 10～100 nanometers, epigranular, size-controllable spherical metal oxide or composite metal oxide powder;
Described soluble metallic salt is meant to generate sedimentary soluble metal nitrate or vitriol with the hydrolysate of urea that its consumption calculates by the content of each metal ion species in the desired final product; Urea is as the precipitation agent of microcell precipitin reaction, and its consumption is 1.2～3 times of mole numbers pressing the effective metal total ion concentration of reaction ratio calculating; Monomer is selected acrylamide for use, and linking agent is selected N for use, and N '-methylene-bisacrylamide, both consumptions are 10: 1～3: 1 by weight; The initiator of gelation is selected ammonium persulphate for use, and its adding proportion is 10～20wt% ammonium persulfate solution that every 100ml mixing solutions drips 2～1ml.
2. the preparation method of a kind of nano-metal-oxide according to claim 1 or complex metal oxides, it is characterized in that described mixing solutions adopts soluble metallic salt and urea with one or more to be dissolved in and to contain acrylamide monomer and N, formulated in the aqueous solution of N '-methylene-bisacrylamide.
3. the preparation method of a kind of nano-metal-oxide according to claim 1 and 2 or complex metal oxides, it is characterized in that described soluble metallic salt employing can generate sedimentary soluble metal nitrate with the hydrolysate of urea, it forms corresponding ammonium nitrate by product when forming precipitation by metallic ion in the microcell precipitation process.
4. the preparation method of a kind of nano-metal-oxide according to claim 1 and 2 or complex metal oxides, it is characterized in that described concrete calcining temperature and time needs decide according to the final product that generates, the calcining back is residual byproduct of reaction C and the N of elimination when obtaining required nano-powder.
5. the preparation method of a kind of nano-metal-oxide according to claim 1 and 2 or complex metal oxides, it is characterized in that described various raw material, comprise soluble metal nitrate, urea, acrylamide monomer, N, N '-methylene-bisacrylamide, ammonium persulphate, its purity is more than the chemical pure.
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| JP6399656B2 (en) * | 2015-02-05 | 2018-10-03 | 国立大学法人広島大学 | Method for producing metal oxide nanoparticles |
| CN107285391A (en) * | 2017-06-01 | 2017-10-24 | 苏州乔纳森新材料科技有限公司 | A kind of preparation method of magnetic Nano material |
| CN107986630A (en) * | 2017-11-30 | 2018-05-04 | 华南协同创新研究院 | A kind of preparation method of nano-bioactive glass powder |
| CN111613453B (en) * | 2020-05-29 | 2022-02-08 | 大连交通大学 | Preparation method of porous nickel cobaltate/graphene nano composite electrode material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237558A (en) * | 1998-05-28 | 1999-12-08 | 中国科学技术大学 | Method for preparing composite metal oxide ceramic powder material by using organic polymerization auxiliary prosess |
| JP2001353442A (en) * | 2001-04-04 | 2001-12-25 | Sumitomo Seika Chem Co Ltd | Salt-resistant water absorbent |
| CN1587058A (en) * | 2004-08-09 | 2005-03-02 | 武汉大学 | Process for preparing nano metal oxide material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237558A (en) * | 1998-05-28 | 1999-12-08 | 中国科学技术大学 | Method for preparing composite metal oxide ceramic powder material by using organic polymerization auxiliary prosess |
| JP2001353442A (en) * | 2001-04-04 | 2001-12-25 | Sumitomo Seika Chem Co Ltd | Salt-resistant water absorbent |
| CN1587058A (en) * | 2004-08-09 | 2005-03-02 | 武汉大学 | Process for preparing nano metal oxide material |
Non-Patent Citations (1)
| Title |
|---|
| 纳米NiO超细粉的软化学合成. 吴春艳等.合肥工业大学学报（自然科学版），第26卷第3期. 2003 * |
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