CN100553833C - The method for preparing metallic simple substance nano-crystal material - Google Patents
The method for preparing metallic simple substance nano-crystal material Download PDFInfo
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- CN100553833C CN100553833C CNB2008100692416A CN200810069241A CN100553833C CN 100553833 C CN100553833 C CN 100553833C CN B2008100692416 A CNB2008100692416 A CN B2008100692416A CN 200810069241 A CN200810069241 A CN 200810069241A CN 100553833 C CN100553833 C CN 100553833C
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Abstract
A kind of method for preparing metallic simple substance nano-crystal material is fit to the preparation of metal nanocrystal materials such as copper, silver, lead, palladium, tin, antimony.Composite alkali metal hydrate dissolvent with fusion, synthetic by chemical reaction under normal pressure and 100～300 ℃, used raw material is solvable inorganic metal salt and zinc powder or iron powder, cost is low in the building-up process, various parameters in the course of reaction are easy to monitoring and control, and are low in the pollution of the environment, the reaction system good uniformity, technology is simple, produces easily and amplifies; And resulting metallic crystal advantages of good crystallization, surface cleaning, size are even, are fit to its function of carrying out the research of intrinsic performance and bringing into play nano crystal material to greatest extent.Metal nanocrystal material metal simple substance nanometer material has characteristics such as metallicity, Electrical and Electronic performance, magnetic, chemical property, hot property and photism, is widely used in industries such as superconduction, chemical industry, medical science, optics, electronics, electrical equipment.
Description
Technical field
The present invention relates to a kind of preparation method of method of nano crystal material, specifically, relate to and utilize the composite alkali metal hydrate dissolvent synthesis method, under the low-temperature atmosphere-pressure condition, prepare the method for metal simple-substance nano material.
Background technology
The metal simple-substance nano material has characteristics such as metallicity (as the good conductor of hardness height, glossy, opaque, easy heat transfer, electricity etc.), Electrical and Electronic performance, magnetic, chemical property, hot property and photism, is widely used in industries such as superconduction, chemical industry, medical science, optics, electronics, electrical equipment.The modification that argent can be used for biomarker, sterilization, lubricant, catalyst, gives plastics, rubber, coating and paint, occupy very consequence in research fields such as SERS, surface enhanced resonant scattering spectrum, molecular biology, supramolecular systems, have broad application prospects.Metallic lead has the quite high life-span in many media, for example plumbous in sulfuric acid below 200 ℃ and hydrochloric acid also quite stable.Plumbous militarily also have an important meaning, for example lead be the base of manufacturing bullet and bullet metal, can make accumulator plate etc.Plumbous have good absorbability to X-ray and gamma-radiation, can be used in medical treatment and the nuclear industry.Lead has good running-in ability and self lubricity, is used to make bearing metal in that military and civilian is industrial.Metal Sn is the soft metal, has low, the low-melting characteristics of shear strength, can be used as the antifriction antiwear material.And nano metal material is compared with ordinary metallic material, has a lot of good character, and for example, experiment shows that the Au fusing point of 2nm only is 330 ℃, and is lower more than 700 ℃ than the fusing point of common Au; And nanometer Ag powder fusing point is low to moderate 100 ℃ unexpectedly; The about 29%-54% of heat capacity ratio coarse-grain height of nanometer Pd (6nm, 80% solid density), the thermal coefficient of expansion of nanocrystalline Cu (8nm, 90% solid density) is higher more than 1 times than coarse-grain Cu.In the method for existing synthetic metal simple-substance, as Chinese patent CN101024251, the method that a kind of double solvents legal system is equipped with nano metal is disclosed, adopt the chemical pure slaine to be dissolved in and form the slaine ethylene glycol solution in the ethylene glycol, the chemical pure polyvinylpyrrolidone is dissolved in forms the polyvinylpyrrolidone ethylene glycol solution in the ethylene glycol; Ethylene glycol is put into heating and insulation in the reaction vessel; Aforementioned metal salt ethylene glycol solution and polyvinylpyrrolidone ethylene glycol solution slowly are injected in the reaction vessel by syringe simultaneously, after injection finishes, continue reactant liquor is heated.The multiple organic polar solvent that relates in building-up process of this method mixes, and causes synthetic cost higher, and easily environment is formed pollution.Liu Hong, Hu Chenguo and Wang Zhonglin had reported in 2006 once that composite alkali metal hydroxide mediator method synthesized complex oxide (Nano Letters, 6,1535) method, it is reaction dissolvent that this method adopts the composite alkali metal hydroxide of fusion, and metal inorganic salt and oxide are reaction raw materials synthetic complex oxide and other oxygenatedchemicals under low-temperature atmosphere-pressure.Yet there are no report for preparing metallic simple substance nano-crystal with composite alkali metal hydroxide mediator method.
Summary of the invention
The present invention is directed to the deficiency in the existing synthetic metallic simple substance nano-crystal material technology, a kind of method of utilizing the synthetic metallic simple substance nano-crystal material of composite alkali metal hydrate dissolvent is provided.
For achieving the above object, the present invention adopts in the composite alkali metal hydroxide of fusion NaOH and potassium hydroxide as reaction dissolvent, raw material with chemical pure slaine and zinc powder or the synthetic metallic simple substance nano-crystal material of iron powder reaction conduct obtains metal simple-substance nano particle and nano wire behind chemical reaction.The present invention's step in the following order is prepared:
Step 1, preparation reaction dissolvent are 10～90% solid-state NaOH with percentage by weight with percentage by weight is that 10～90% potassium hydroxide evenly mixes; Being characterized as of this reaction dissolvent at normal temperatures for solid-state, but be heated under 100～300 ℃ and become molten state, because this reaction dissolvent is strong polar solvent, a lot of chemical reactions that adopt the aqueous solution or organic solvent could take place under cryogenic high pressure only need just can take place under the low-temperature atmosphere-pressure state in this solvent.
Step 3, add thermal response, with percentage by weight is that 0.5%～50% reaction raw materials and percentage by weight are 50%～99.5% reaction dissolvent, insert in the reaction vessel together, add a cover sealing, then reaction vessel is put into the firing equipment that is heated to 100～300 ℃, pre-heat fusing 20～60 minutes, after solid complex hydroxide in the question response device melts fully, reaction vessel is opened, stir with agitator, reactant is evenly distributed in the reaction dissolvent of molten state, closed container once more, and 100～300 ℃ of following heated at constant temperature 1～100 hour;
Step 4, cooling are cooled to room temperature with the reaction vessel after the isothermal reaction.
Step 5, washing, being that 1～5 diluted acid is first with product with cold or hot deionized water or pH value earlier dissolves, be 1000～20000 rev/mins centrifuge with rotating speed again or filter with pumping and filtering device, then product centrifugal or that filter is disperseed in cold or hot deionized water, ethanol or diluted acid again, repeating then to dewater and clean 3～5 times, is neutral until the pH of product value.
Then product is identified crystalline phase with X-ray diffraction (XRD), characterize its pattern and size with ESEM or transmission electron microscope.
Reaction vessel in the above-mentioned steps 3 prepares container or precious metal vessel for the organic polymer that alkali metal hydroxide is had inertia.
Firing equipment in the above-mentioned described step 3 is Muffle furnace or resistance furnace or baking oven.
The present invention has following beneficial effect:
1, cost is low, and the synthetic metallic simple substance nano-crystal material of complex hydroxide solvent method only needs to carry out chemical synthesis under normal pressure, and synthesis temperature does not need high pressure and pyroreaction system at 100～300 ℃; And used raw material is cheap inorganic metal salt and zinc powder or iron powder, because be that a step is synthetic, promptly raw material and reaction dissolvent are inserted the reaction of heating in the constant temperature oven after once adding reactor, and operation sequence is simple, controllable parameter is less in the building-up process, and synthetic cost is low.
2, the various parameters in the course of reaction (temperature, pressure etc.) are easy to monitoring and control, and this makes us can easier research reaction mechanism, finds out the influence factor of most critical, provides the technology basis for we effectively control crystallite dimension.
3, low in the pollution of the environment, to compare with other synthetic methods, because do not introduce surfactant or template agent, pollution abatement basically helps environmental protection in the building-up process of the present invention.
4, product cleaning, in the building-up process of the present invention because do not introduce surfactant or template agent, the surface cleaning of nano crystal material is fit to its function of carrying out the research of intrinsic performance and bringing into play nano crystal material is to greatest extent also carried out simultaneously surface modification easily.
Description of drawings
Fig. 1 is the XRD of the copper nanostructured of the embodiment of the invention 1 preparation; Fig. 2 is the sem photograph of this copper nanostructured;
Fig. 3 is the silver nanostructured XRD of the embodiment of the invention 2 preparations; Fig. 4 is this silver nanostructured sem photograph;
Fig. 5 is the XRD of the plumbous nanostructured of the embodiment of the invention 3 preparations; Fig. 6 is the sem photograph of this lead nanostructured;
Fig. 7 is the XRD of the sijna rice structure of the embodiment of the invention 4 preparations; Fig. 8 is the sem photograph of this sijna rice structure.
Fig. 9 is the XRD of the antimony nanostructured of the embodiment of the invention 5 preparations; Figure 10 is the sem photograph of this antimony nanostructured.
Figure 11 is the XRD of the palladium nanostructured of the embodiment of the invention 6 preparations; Figure 12 is the sem photograph of this palladium nanostructured.
The specific embodiment
Embodiment 1:
The concrete synthetic method of copper nano crystal material
The raw material of synthetic copper nano crystal material is KOH, NaOH, copper chloride (CuCl
2.2H
2O), iron powder, the stepwise reaction of generation is as follows:
(a)CuCl
2.2H
2O→Cu
++2Cl
-+2H
2O
(b)Fe+2NaOH→FeO+H
2+Na
2O
(c)H
2+Cu
2++2OH
-→Cu+2H
2O
The concrete operations step is as follows:
Step 1, KOH=57% and NaOH=43% weighing by weight percentage mix as reaction dissolvent.
Step 3, the reaction raw materials and the reaction dissolvent in the above-mentioned steps 1 of above-mentioned steps 2 are inserted in the polytetrafluoroethylene (PTFE) reaction vessel, the percentage by weight of reactant is 8.1%, will gather then four not the ethene container add a cover sealing to insert temperature be in 200 ℃ the constant temperature Muffle furnace.After making reaction vessel in stove, be incubated 40 minutes, open the reaction vessel stirring reaction dissolvent of molten state is evenly mixed with reactant.Add a cover closed reaction vessel once more, and under the state of 200 ℃ of constant temperature, continue insulation 16 hours.
Step 4, reaction vessel is taken out from Muffle furnace, be chilled to room temperature naturally.
Step 5, product is dissolved with deionized water; Separate, clean with centrifuge, promptly get nano-metallic copper.Repeating above-mentioned steps 5～10 times, is neutral until product pH value.
As shown in Figure 1, X-ray diffraction (XRD) result, it shows that synthetic product is the copper of single-phase cubic crystal structure; Shown in Figure 2, scanning electron microscopy is observed and is shown that copper crystal is wide to be that 50 nanometer to 200 nanometers, length are 2 microns to 5 microns linear structure.
Embodiment 2:
Synthesizing of silver nanocrystalline structure
The raw material of synthetic silver-colored nano crystal material is KOH, NaOH, silver nitrate (AgNO
3), zinc powder, the stepwise reaction of generation is as follows:
(a)AgNO
3→Ag
++NO
3 -
(b)Zn+2NaOH?→ZnO+H
2+Na
2O
(c)H
2+2Ag
++2OH
-→2Ag+2H
2O
The concrete operations step is as follows:
Step 1, KOH=57% and NaOH=43% weighing by weight percentage mix as reaction dissolvent.
Step 3, the reaction raw materials and the reaction dissolvent in the above-mentioned steps 1 of above-mentioned steps 2 are inserted in the polytetrafluoroethylene (PTFE) reaction vessel, the percentage by weight of reactant is 4.6%, will gather then four not the ethene container add a cover sealing to insert temperature be in 200 ℃ the constant temperature Muffle furnace.After making reaction vessel in stove, be incubated 40 minutes, open the reaction vessel stirring reaction dissolvent of molten state is evenly mixed with reactant.Add a cover closed reaction vessel once more, and under the state of 200 ℃ of constant temperature, continue insulation 6 hours.
Step 4, reaction vessel is taken out from Muffle furnace, be chilled to room temperature naturally.
Step 5, product is dissolved with deionized water; Separate, clean with centrifuge, promptly get nanometer metallic silver.Repeating above-mentioned steps 5～10 times, is neutral until product pH value.
As shown in Figure 3, the X-ray diffraction result, the powder that obtains is the silver of single-phase cubic crystal structure; As shown in Figure 4, scanning electron microscopy is observed and is shown that silver-colored crystal is for being of a size of 50-100 Nanoparticulate structure.
Embodiment 3:
The synthetic method of plumbous (Pb) nano crystal material
The raw material of synthetic plumbous nano crystal material is KOH, NaOH, plumbi nitras (Pb (NO
3)
2), zinc powder, the stepwise reaction of generation is as follows:
(a)Pb(NO
3)
2→Pb
2++2NO
3 -
(b)Zn+2NaOH→ZnO+H
2+Na
2O
(c)H
2+Pb
2++2OH
-→Pb+2H
2O
The concrete operations step is as follows:
Step 1, KOH=57% and NaOH=43% weighing by weight percentage mix as reaction dissolvent.
Step 3, the reaction raw materials and the reaction dissolvent in the above-mentioned steps 1 of above-mentioned steps 2 are inserted in the polytetrafluoroethylene (PTFE) reaction vessel, the percentage by weight of reactant is 4.1%, will gather then four not the ethene container add a cover sealing to insert temperature be in 200 ℃ the constant temperature Muffle furnace.After making reaction vessel in stove, be incubated 40 minutes, open the reaction vessel stirring reaction dissolvent of molten state is evenly mixed with reactant.Add a cover closed reaction vessel once more, and under the state of 200 ℃ of constant temperature, continue insulation 16 hours.
Step 4, reaction vessel is taken out from Muffle furnace, be chilled to room temperature naturally.
Step 5, product is dissolved with deionized water; Separate, clean with centrifuge, promptly get nano metal lead.Repeating above-mentioned steps 5～10 times, is neutral until product pH value.
As shown in Figure 5, X-ray diffraction is the result show, the powder that obtains is the lead of single-phase cubic crystal structure; Shown in Figure 6, sem observation shows, leading crystal is wide to be that 500 nanometers to 5 micron, length are several 10 microns club shaped structures.
Embodiment 4:
The synthetic method of sijna rice crystalline material
The raw material of synthetic sijna rice crystalline material is KOH, NaOH, stannic chloride (SnCl
2.2H
2O), zinc powder, the stepwise reaction of generation is as follows:
(a)SnCl
2.2H
2O→Sn
2++2Cl
-+2H
2O
(b)Zn+2NaOH→ZnO+H
2+Na
2O
(c)H
2+Sn
2++2OH
-→Sn+2H
2O
The concrete operations step is as follows:
Step 1, KOH=57% and NaOH=43% weighing by weight percentage mix as reaction dissolvent.
Step 3, the reaction raw materials and the reaction dissolvent in the above-mentioned steps 1 of above-mentioned steps 2 are inserted in the polytetrafluoroethylene (PTFE) reaction vessel, will gather then four not the ethene container add a cover sealing to insert temperature be in 200 ℃ the constant temperature Muffle furnace.After making reaction vessel in stove, be incubated 40 minutes, open the reaction vessel stirring reaction dissolvent of molten state is evenly mixed with reactant.Add a cover closed reaction vessel once more, and under the state of 200 ℃ of constant temperature, continue insulation 6 hours.
Step 4, reaction vessel is taken out from Muffle furnace, be chilled to room temperature naturally.
Step 5, product is dissolved with deionized water; Separate, clean with centrifuge, promptly get nano metal tin.Repeating above-mentioned steps 5～10 times, is neutral until product pH value.
As shown in Figure 7, X-ray diffraction is the result show, the powder that obtains is the tin of single-phase cubic crystal structure; Shown in Figure 8, sem observation shows that the tin crystal is 2 to 3 microns an isometric particle structure.
Embodiment 5:
The synthetic method of antimony nanocrystalline structure
The raw material of synthetic antimony nano crystal material is KOH, NaOH, antimony chloride (SbCl
3), zinc powder, the stepwise reaction of generation is as follows:
(a)SbCl
3→Sb
3++3Cl
-
(b)Zn+2NaOH→ZnO+H
2+Na
2O
(c)3H
2+2Sb
3++6OH
-→2Sb+6H
2O
The concrete operations step is as follows:
Step 1, KOH=57% and NaOH=43% weighing by weight percentage mix as reaction dissolvent.
Step 3, the reaction raw materials and the reaction dissolvent in the above-mentioned steps 1 of above-mentioned steps 2 are inserted in the polytetrafluoroethylene (PTFE) reaction vessel, the percentage by weight of reactant is 5.8%, will gather then four not the ethene container add a cover sealing to insert temperature be in 200 ℃ the constant temperature Muffle furnace.After making reaction vessel in stove, be incubated 40 minutes, open the reaction vessel stirring reaction dissolvent of molten state is evenly mixed with reactant.Add a cover closed reaction vessel once more, and under the state of 200 ℃ of constant temperature, continue insulation 24 hours.
Step 4, reaction vessel is taken out from Muffle furnace, be chilled to room temperature naturally.
Step 5, product is dissolved with deionized water; Separate, clean with centrifuge, promptly get nano metal antimony.Repeating above-mentioned steps 5～10 times, is neutral until product pH value.
As shown in Figure 9, X-ray diffraction is the result show, the powder that obtains is the antimony of single-phase trigonal system; Shown in Figure 10, scanning and transmission electron microscopy are observed and are shown that the antimony crystal is thickness 10 to 20 nano-sheet structures.
Embodiment 6:
Synthesizing of palladium nano-crystal body structure
The raw material of synthetic palladium nano-crystal body material is KOH, NaOH, palladium (Pd (NO
3)
2.2H
2O), zinc powder, the stepwise reaction of generation is as follows:
(d)Pd(NO
3)
2.2H
2O→Pd
2++2NO
3 -+2H
2O
(e)Zn+2NaOH?→ZnO+H
2+Na
2O
(f)H
2+Pd
2++2OH
-→Pd+2H
2O
The concrete operations step is as follows:
Step 1, KOH=57% and NaOH=43% weighing by weight percentage mix as reaction dissolvent.
Step 3, the reaction raw materials and the reaction dissolvent in the above-mentioned steps 1 of above-mentioned steps 2 are inserted in the polytetrafluoroethylene (PTFE) reaction vessel, the weight of reactant and the percentage by weight of reactant+reaction dissolvent are 3.4%, will gather then four not the ethene container add a cover sealing to insert temperature be in 200 ℃ the constant temperature Muffle furnace.After making reaction vessel in stove, be incubated 40 minutes, open the reaction vessel stirring reaction dissolvent of molten state is evenly mixed with reactant.Add a cover closed reaction vessel once more, and under the state of 200 ℃ of constant temperature, continue insulation 24 hours.
Step 4, reaction vessel is taken out from Muffle furnace, be chilled to room temperature naturally.
Step 5, product is dissolved with deionized water; Separate, clean with centrifuge, promptly get nanometer metal palladium.Repeating above-mentioned steps 5～10 times, is neutral until product pH value.
As shown in figure 11, X-ray diffraction is the result show, the powder that obtains is the palladium of single-phase hexagonal structure; As shown in figure 12, the apparent mirror microcosmic of scanning electron is examined and is shown that the palladium crystal is 10 to 40 nanoparticle structure.
Claims (3)
1. method for preparing metallic simple substance nano-crystal material is characterized in that: may further comprise the steps:
Step 1, preparation reaction dissolvent are 10～90% solid-state NaOH with percentage by weight with percentage by weight is that 10～90% potassium hydroxide evenly mixes;
Step 2, preparation reaction raw materials are that 10～90% soluble metallic salt powder that contains any one or two kinds of silver or palladium or copper or lead or antimony or tin and percentage by weight are that 10～90% zinc powder or iron powder mix and obtain reaction raw materials with percentage by weight;
Step 3, add thermal response, be that the reaction raw materials of 0.5%～50% step 2 and percentage by weight are the reaction dissolvent of 50%～99.5% step 1 with percentage by weight, insert in the reaction vessel together, add a cover sealing, then reaction vessel is put into the firing equipment that is heated to 100～300 ℃, pre-heat fusing 20～60 minutes, after solid complex hydroxide in the question response device melts fully, reaction vessel is opened, stir with agitator, reactant is evenly distributed in the reaction dissolvent of molten state, closed container once more, and 100～300 ℃ of following heated at constant temperature 1～100 hour;
Step 4, cooling are cooled to room temperature with the reaction vessel after the isothermal reaction;
Step 5, washing, being that 1～5 diluted acid is first with product with cold or hot deionized water or pH value earlier dissolves, be centrifugal under 1000～20000 rev/mins the speed at rotating speed with centrifuge again, or filter with pumping and filtering device, then product centrifugal or that filter is disperseed in cold or hot deionized water, ethanol or diluted acid again, repeating then to dewater and clean 3～5 times, is neutral until the pH of product value.
2. the method for preparing metallic simple substance nano-crystal material according to claim 1 is characterized in that: the reaction vessel in the described step 3 prepares container or precious metal vessel for the organic polymer that alkali metal hydroxide is had inertia.
3. the method for preparing metallic simple substance nano-crystal material according to claim 1 is characterized in that: the firing equipment in the described step 3 is Muffle furnace or resistance furnace or baking oven.
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| CN1389597A (en) * | 2001-06-01 | 2003-01-08 | 中国科学院金属研究所 | High-strength and high-conductivity nanometer crystal copper material and its prepn. |
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| CN1896341A (en) * | 2006-06-20 | 2007-01-17 | 山东大学 | Low-temperature alkaline-solution synthesis of oxygen metal inorganic compound monocrystal nano-material |
| CN101024251A (en) * | 2007-03-08 | 2007-08-29 | 西北工业大学 | Method for preparing nano metal |
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2008
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Patent Citations (4)
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| CN1389597A (en) * | 2001-06-01 | 2003-01-08 | 中国科学院金属研究所 | High-strength and high-conductivity nanometer crystal copper material and its prepn. |
| CN1662331A (en) * | 2002-06-19 | 2005-08-31 | 耐诺泡德斯工业(以色列)有限公司 | Method for the production of highly pure metallic nano-powders and nano-powders produced thereby |
| CN1896341A (en) * | 2006-06-20 | 2007-01-17 | 山东大学 | Low-temperature alkaline-solution synthesis of oxygen metal inorganic compound monocrystal nano-material |
| CN101024251A (en) * | 2007-03-08 | 2007-08-29 | 西北工业大学 | Method for preparing nano metal |
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