CN102259932A - Method for preparing one-dimensional metal oxide nano material - Google Patents
Method for preparing one-dimensional metal oxide nano material Download PDFInfo
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- CN102259932A CN102259932A CN2011102044532A CN201110204453A CN102259932A CN 102259932 A CN102259932 A CN 102259932A CN 2011102044532 A CN2011102044532 A CN 2011102044532A CN 201110204453 A CN201110204453 A CN 201110204453A CN 102259932 A CN102259932 A CN 102259932A
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Abstract
The invention discloses a method for preparing a one-dimensional metal oxide nano material, which comprises the following steps of: (1) putting a transition metal source into a heating zone of an electric heating plate; (2) starting the electric heating plate, raising the temperature to be between 200 and 600 DEG C, and preserving heat for 1 to 96 hours; and (3) switching off a power supply, and cooling to room temperature along with the electric heating plate, wherein oxide on the surface of the metal source at the moment is a target product. The process and equipment are simple, the method is low in cost, suitable for large-area preparation and various transition metals and high in yield, the preparation temperature is low, and the prepared metal oxide nano material has high crystallization property.
Description
Technical field
The present invention relates to the preparation method of low-dimension nano material, particularly the preparation method of transition metal oxide nano line, nano belt, nanometer sheet.
Background technology
Development Trend of Electronic Technology requirement device and system are littler, faster, colder, and for present silicon integrated circuit, when it further develops live width again less than 100nm, promptly when " nano electron device ", to propose higher requirement to equipment and manufacturing process, cost increases huge, and the limitation of traditional technology is more and more obvious, for this reason, low-dimension nano material has all been invested with the research sight of nano electron device of future generation in the whole world.Low-dimension nano material is owing to have small-size effect, surface effects, quantum tunneling effect etc., and its magnetic, light, electricity, power, chemistry and thermal properties and block materials take place significantly to change.Especially the nano materials such as nano wire, nano belt, nanometer sheet and nanotube that have one dimension Nano structure, because of the characteristic of particular structure and a series of excellences, they are had extensively and important use in fields such as microelectromechanical-systems, solar energy converting, Chu Qing, gas sensing, catalyzer, information storage and demonstration and emissions.
The oxidic transition metal species class is various, as CuO, ZnO, Fe
2O
3, Co
3O
4, Ga
2O
3Deng, have the character of semiconductor energy gap, and its metal component majority can show the characteristic of appraising at the current rate, can form various structure, formed metal oxide semiconductor shows unique character in various fields.For this reason, " nano electron device " based on the one dimension oxide-based nanomaterial has irreplaceable advantage: be difficult for the unique advantage that macroscopical devices such as oxidation, size small (nanometer scale), power consumption are little, reflection sensitivity do not have fully in applied environment.
Develop many prepared metal oxide nanostructure at present, comprised organic auxiliary synthetic, carbo-thermal process, gas-liquid-solid (VLS) technology and gas-solid (VS) technology etc.In these methods, VLS relatively is fit to preparation monocrystal nanostructure and relative big quantity with VS technology.Ga for example
2O
3Can heat these material powders by tube furnace with the ZnO nano wire synthesizes; The oxide nano thread of low melting point metal such as Zn, Mg and Ge can obtain by heating of metal powder under oxygen atmosphere.Conventional VS and VLS processing requirement are accurately controlled preparation condition, produce the gaseous metal as demanding temperature (〉=1000 ℃), also want control growing atmosphere, flow rate and substrate position; For VLS technology, also to adopt appropriate catalyst, thereby the influence of the catalyzer that may be introduced of the performance of the nano material that obtains.Though the preparation remarkable progress of nanostructured oxide material, but also there are some problems: 1) in most of the cases, prepare large-scale nano material and still have certain difficulty, how to utilize simple prepared decimetre, centimetre in addition millimeter magnitude range scale in equally distributed nano material obviously be still a challenge; 2) preparation technology of material also relative complex usually needs well preparation and operating device; 3) preparation technology's stability is still waiting further improvement.Because the generation of nano material is chemistry even the biological process of the very physics of complexity, its character depends on these generations or preparation process to a great extent.
Summary of the invention
The object of the present invention is to provide a kind of can mass production, grow, need not wide, low growth temperature of catalyzer, suitable material ranges and synthesis technique cheaply fast.
Purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method of one-dimensional metal oxide nano-material adopts the common electrical hot plate to make it with airborne oxygen reaction and at source metal surface generation one-dimensional metal oxide nano-material array by the heating of metal source under air atmosphere.Concrete processing step is as follows:
(1) transition metal source is placed the hot plate heating zone;
(2) open hot plate and be warming up to 200～600 ℃, then soaking time 1～96h;
(3) powered-down is cooled to room temperature with hot plate, and this moment, the oxide compound on source metal surface was the purpose product.
Preferably, transition metal source is iron, cobalt, copper, zinc or manganese described in the step (1).
Preferably, transition metal source described in the step (1) be shaped as paillon foil, block, powder or sedimentary metallic film, the area size is arbitrarily.
Preferably, temperature is 400 ℃ described in the step (2).
Preferably, the time is 24h described in the step (2).
The process of growth of one-dimensional metal oxide nano-material is divided two steps as shown in Figure 1 in the technology of the present invention: the i) formation of the different oxide compounds of surperficial multilayer.Oxygen in air atmosphere generates loose metal oxide mixture to surface, metallic surface initial oxidation, along with time lengthening forms the surface gradually for being followed successively by high valence state metal oxide and corresponding lower valency metal oxide layer; The ii) growth of one-dimensional metal nanostructure.The inner layer metal atom diffuses to outside surface by the body phase lattice of outermost zone of oxidation and the border or the defective of crystal grain, when the metal oxide on surface reaches hypersaturated state, this moment, atoms metal contacted forming core gradually with airborne oxygen, along with internal layer under the effect of long-time temperature constantly diffuses to Sauerstoffatom reaction in surperficial atoms metal and the air, will finally grow into metal oxide nano-material in institute's minimum direction of energy requirement.
The present invention compared with prior art has the following advantages and effect:
(1) the metal oxide nano-material crystal property of the present invention's preparation is good.
(2) preparation temperature of the present invention is low, and 200 ℃ can obtain.
(3) the present invention is applicable to large-area preparation, the productive rate height.
(4) the applicable multiple transition metal of the present invention.
(5) processing unit of the present invention is simple, and is with low cost, uses hot plate directly to heat under air atmosphere and can obtain.
Description of drawings
Fig. 1 is an one dimension oxide-based nanomaterial growth synoptic diagram;
Fig. 2 is embodiment one a product iron oxide nano-wire scanned photograph;
Fig. 3 is embodiment one a product iron oxide nano-wire Raman spectrum;
Fig. 4 is embodiment two product ferric oxide nano band fronts (a) and cross section (b) scanned photograph;
Fig. 5 is the Raman spectrum of embodiment two product ferric oxide nano bands;
Fig. 6 is embodiment two product ferric oxide nano band high-resolution-ration transmission electric-lens and corresponding electron-diffraction diagrams;
Fig. 7 is embodiment two product ferric oxide nano band M-T curves;
Fig. 8 is the scanned photograph of embodiment three product cobaltosic oxide nano sheets;
Fig. 9 is the Raman spectrum of embodiment three product cobaltosic oxide nano sheets;
Figure 10 is the magnetic hysteresis loop of embodiment three product cobaltosic oxide nano sheets;
Figure 11 is the scanned photograph of embodiment four product cupric oxide nano lines.
Embodiment
The employing hot plate is a heating unit, and the Heating temperature stepping is adjustable.The heating of metal source directly prepares corresponding one-dimensional metal oxide nano-material under air atmosphere.
Embodiment 1
Prepare iron oxide nano-wire on the ferrous powder granules
1, iron powder evenly is tiled in the hot plate heating zone;
2, open the hot plate heating unit, be rapidly heated to 330 ℃; Be incubated 24h then;
3, powered-down, hot plate slowly cooling naturally cool to room temperature, and can observe this moment has one deck sorrel material to generate on the particle surface, and this sorrel material is the purpose product.
Product to preparation carries out scanning electron microscopic observation, and Fig. 2 shows the vertical particle surface growth of the iron oxide nano-wire of preparation, and its diameter is 20～40nm, and length is 2～4 μ m.Sample Raman spectrum (Fig. 3) analysis is shown 225 in collection of illustrative plates and 498cm
-1The A of the corresponding ferric oxide in the spectrum peak at place
1gRaman modes, 246,293,410 and 612cm
-1The E of the corresponding ferric oxide in spectrum peak
gRaman modes, and 668cm
-1The spectrum peak at place derives from the Z 250 that iron powder surface initial oxidation generates.The high-resolution-ration transmission electric-lens result shows that iron oxide nano-wire is the α-Fe of monocrystalline
2O
3, and grow along [110] direction.
Embodiment 2
Preparation ferric oxide nano band on the sedimentary iron thin film
1, on silicon substrate, deposits one deck iron thin film by magnetron sputtering;
2, iron thin film is placed acetone, dehydrated alcohol ultrasonic cleaning 15 minutes and oven dry respectively;
3, the iron thin film substrate after the above-mentioned oven dry is placed the hot plate heating zone;
4, open the hot plate heating unit, be rapidly heated to 400 ℃; Be incubated 24h then;
5, powered-down is cooled to room temperature with the hot plate cooling, and can observe film and become sorrel this moment, and this sorrel material is the purpose product.
Scanning electron microscope result (Fig. 4) shows sharp-pointed ferric oxide nano band vertical thin-film surface growth, the about 10-40nm in its end, and the bottom is that thickness is about 30nm about 100-200nm, mean length is about 1 μ m.Sample Raman spectrum (Fig. 5) demonstration 223 and 495cm
-1The A of corresponding ferric oxide
1gThe Raman active film, 243,290,408 and 611cm
-1The E of corresponding ferric oxide
gThe Raman active mould, and be positioned at 665cm
-1Locating small and weak peak comes to Fe
3O
4The high resolution analysis of sample (Fig. 6) shows that fringe spacing is (110) crystal face of the corresponding ferric oxide of 0.252nm, and diffraction spot shows that also iron oxide nano-wire is along the growth of [110] direction simultaneously.M-T curve (Fig. 7) shows that the Morin temperature of sample is about 113K, has reduced about 150K than the block ferric oxide.
Preparation molybdenum trioxide nano sheet on the cobalt thin film
1, on silicon substrate, deposits one deck cobalt thin film by magnetron sputtering;
2, cobalt thin film is placed acetone, dehydrated alcohol ultrasonic cleaning 15 minutes and oven dry respectively;
3, the cobalt thin film substrate after the above-mentioned oven dry is placed the hot plate heating zone;
4, open the hot plate heating unit, be rapidly heated to 400 ℃; Be incubated 24h then;
5, powered-down is cooled to room temperature with the hot plate cooling, and the atrament that film surface generates is the sample of preparation.
Scanned photograph (Fig. 8) shows that cobaltosic oxide nano sheet thickness is about 80nm, and length is about 1 μ m.Raman result (Fig. 9) shows, 482,521,619 and 692cm
-1The spectrum peak of position is the E of corresponding tricobalt tetroxide respectively
g, F
2g 1, F
2g 2And A
1gRaman modes.Room temperature magnetic hysteresis loop (Figure 10) shows that the coercive force of tricobalt tetroxide is about 350Oe.
Embodiment 4
Preparation cupric oxide nano line on the Copper Foil
1, with pollutent and the zone of oxidation of sand papering with the removing copper foil surface, ultrasonic cleaning 15 minutes and oven dry respectively in acetone, dehydrated alcohol respectively then;
2, the Copper Foil after the above-mentioned oven dry is placed the hot plate heating zone;
3, open the hot plate heating unit, be rapidly heated, be incubated 72h then to 450 ℃;
4, powered-down is cooled to room temperature with the hot plate cooling, and the atrament that copper foil surface generates is the sample of preparation.
Scanned photograph (as Figure 11) shows, the growth of big area nanowire array of copper oxide, with the difference of preparation temperature, it directly is 30-200nm, length is several microns and does not wait to tens microns that the high-resolution-ration transmission electric-lens result shows that the cupric oxide nano line is along the growth of [111] direction.
Claims (6)
1. the preparation method of an one-dimensional metal oxide nano-material is characterized in that, concrete processing step is as follows:
(1) transition metal source is placed the hot plate heating zone;
(2) open hot plate and be warming up to 200～600 ℃, then soaking time 1～96h;
(3) powered-down is cooled to room temperature with hot plate, and this moment, the oxide compound on source metal surface was the purpose product.
2. preparation method according to claim 1 is characterized in that, transition metal source is iron, cobalt, copper, zinc or manganese described in the step (1).
3. preparation method according to claim 1 and 2 is characterized in that, transition metal source described in the step (1) be shaped as paillon foil, block, powder or sedimentary metallic film.
4. preparation method according to claim 3, it is characterized in that, in the step (1) when described transition metal be shaped as paillon foil, block the time, also carry out following pre-treatment, to remove the pollutent and the zone of oxidation of metallic surface, in acetone, dehydrated alcohol, distinguish ultrasonic cleaning 15 minutes with sand papering then respectively.
5. preparation method according to claim 4 is characterized in that, temperature is 400～430 ℃ described in the step (2).
6. preparation method according to claim 5 is characterized in that, the time described in the step (2) is 24h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103065916A (en) * | 2012-12-27 | 2013-04-24 | 青岛艾德森能源科技有限公司 | Copper oxide nanowire field emission cathode |
| CN107004548A (en) * | 2014-11-26 | 2017-08-01 | 光学实验室公司（瑞典） | Method for manufacturing nanostructured |
| CN108977846A (en) * | 2018-06-21 | 2018-12-11 | 太原理工大学 | A kind of preparation method of the ferric oxide nano with array film |
Citations (2)
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| WO2006071199A1 (en) * | 2004-12-28 | 2006-07-06 | Nanoscience Innovation Pte Ltd | Nanostructured zinc oxide and a method of producing the same |
| CN101041469A (en) * | 2007-03-22 | 2007-09-26 | 武汉大学 | Preparation method for one-dimensional metallic oxide nano needle material |
-
2011
- 2011-07-21 CN CN2011102044532A patent/CN102259932A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006071199A1 (en) * | 2004-12-28 | 2006-07-06 | Nanoscience Innovation Pte Ltd | Nanostructured zinc oxide and a method of producing the same |
| CN101041469A (en) * | 2007-03-22 | 2007-09-26 | 武汉大学 | Preparation method for one-dimensional metallic oxide nano needle material |
Non-Patent Citations (5)
| Title |
|---|
| XUCHUAN JIANG ET AL.: "CuO Nanowires Can Be Synthesized by Heating Copper Substrates in Air", 《NANO LETTERS》 * |
| Y W ZHU ET AL.: "Large-scale synthesis and field emission properties of vertically oriented CuO nanowire films", 《NANOTECHNOLOGY》 * |
| ZHE ZHENG ET AL.: "Ultra-sharp α-Fe2O3 nanoflakes: growth mechanism and field-emission", 《APPLIED PHYSICS A》 * |
| 余雯 等: "热氧化法制备ZnO 纳米针的微结构与场发射性质研究", 《电子显微学报》 * |
| 王光毅 等: "CuO纳米线的热氧化制备及其表面的ZnO纳米颗粒修饰", 《武汉大学学报(理学版)》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103065916A (en) * | 2012-12-27 | 2013-04-24 | 青岛艾德森能源科技有限公司 | Copper oxide nanowire field emission cathode |
| CN107004548A (en) * | 2014-11-26 | 2017-08-01 | 光学实验室公司（瑞典） | Method for manufacturing nanostructured |
| CN108977846A (en) * | 2018-06-21 | 2018-12-11 | 太原理工大学 | A kind of preparation method of the ferric oxide nano with array film |
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Application publication date: 20111130 |