CN103071788A - Method of preparing nickel-silver nuclear shell structure nano-particles - Google Patents
Method of preparing nickel-silver nuclear shell structure nano-particles Download PDFInfo
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- CN103071788A CN103071788A CN2012104269198A CN201210426919A CN103071788A CN 103071788 A CN103071788 A CN 103071788A CN 2012104269198 A CN2012104269198 A CN 2012104269198A CN 201210426919 A CN201210426919 A CN 201210426919A CN 103071788 A CN103071788 A CN 103071788A
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Abstract
The invention relates to the field of preparation of functional nanometer materials and materials, in particular to a method of preparing nickel-silver nuclear shell structure nano-particles. The method specifically comprises the following steps of: dissolving silver nitrate into water as plating solution; clearly cleaning nanometer nickel powder which is sensitized by sub-tin ions, adding plating solution, stirring and dispersing, after a certain time, titrating clear liquid through diluted hydrochloric acid to observe whether white precipitate is generated, and checking existence of Ag<+> so as to judge whether reaction is complete; after reacting completely, separating a product through a magnet, washing by deionized water and absolute ethyl alcohol, and drying in vacuum at 40 DEG C for 12 hours. According to the invention, the nickel-silver nuclear shell structure nano-particles can be synthesized on the basis of the prepared nanometer nickel particles, the operating method is simple and practicable, moderate in reaction conditions and simple in required devices, the prepared nickel-silver nuclear shell structure nano-particles has the advantages of strong binding force, good dispersibility and compact coating, and furthermore, the thickness of a silver shell can be controlled through changing additive amount of the silver nitrate.
Description
Technical field
The present invention relates to function nano material and field of material preparation, refer in particular to the preparation method of nickel-galactic nucleus shell structural nano particle.
Background technology
Composite nanoparticle comprises the component of two or more, has unique or various character, therefore has wider application than single nano particle; Therefore, in recent years, in the persistent exploration process to the high-performance new material, synthesizing of composite nanoparticle, preparation and application more and more attract much attention, a noticeable study hotspot is exactly the nuclear shell structure nano bimetallic material in the field, for single metal and traditional double metal component (alloy or binary metal) nano particle, nucleocapsid structure bimetallic particle has special electronic structure and surface nature, it has not only kept the physical and chemical performance of original metal core, but also have the good metallic character of clad, so the nuclear shell structure nano bimetallic material is at electronics, biology sensor, the field such as optics and catalysis has a wide range of applications.
Hud typed nickel-Yin composite micro-powder refers to take a kind of metal nickel powder particulate as nuclear, and in its surperficial structure that coats another kind of argent formation shell, the development of this composite particles is to be based upon on the basis of nickel powder microparticle surfaces passivation.Because there is large specific area in the nickel powder particulate, the surface state of particulate has important impact to chemistry, the physical property of particulate, utilize various organic and inorganic material that the nickel powder surface is modified, can effectively eliminate blemish, thereby realize the macro-control to nickel powder character, this nucleocapsid structure has not only kept the physical and chemical performance of original metallic nickel core, also has the good metallic character of silver coating, improve non-oxidizability and the heat endurance of simple nickel powder, kept the high conductivity of nickel and silver; And nickel can suppress silver-colored dissolving in the coated composite powder; can overcome the defective of silver migration in the silver conductive adhesive; reach the purpose of saving noble metal, protection of the environment; therefore; all have a good application prospect in many fields such as optics, magnetics, catalysis, biochemistry, biomedical sector, electric slurry, conductive filler, electrically-conducting paint, electronic shield materials; but because in most cases metal-back coating degree is lower; coat inhomogeneous; therefore, the nickel for preparing evenly, coats fully-galactic nucleus shell structure remains a kind of challenge.
The preparation method of nuclear shell structure nano metal powder comprises thermal decomposition-reducing process, electroless plating method, colloidal particle template, polyol reduction method, co-electrodeposition method, displacement method, electrochemical process etc.; Wherein, displacement plating method is in the situation that there is not impressed current; utilize the reproducibility of parent metal atom itself that the metal ion in the solution is cemented out and be deposited on the matrix surface formation coat of metal; this method is easy to operate; technique is simple; thickness of coating evenly and be easy to control; outward appearance is good; at present; the report of relevant nano nickel galactic nucleus shell structure preparation is less; it is lower that prepared nano particle coats degree; and need to add protective agent in the course of reaction; the present invention is not adding the nano nickel that prepared good dispersion under protectant condition-galactic nucleus shell structural nano particle with displacement method on existing basis, and the employing X-ray diffraction; the various modern analysis means such as transmission electron microscope characterize its structure.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing the nickeline core-shell structure nanometer particle.
Concrete operation step is as follows: the 1) activation of nickel powder: nickel powder clean is removed oxide with watery hydrochloric acid, and joining mass fraction later through the deionization washing is 5 ~ 15% SnCl
2Hydrochloric acid solution in soak, the time is 5 ~ 15min, then with deionized water washing to without Cl
-The nickel powder that 2) will activate joins the AgNO of silver ion
3Ultrasonic 30 ~ 60min is uniformly dispersed nickel powder in solution or the silver ammino solution in solution, mechanical agitation is until react completely, and the ratio of nickeline amount of substance is respectively 1:04 ~ 1:1.1, and reaction temperature is 20 ~ 40 ℃, whether the adularescent precipitation generates supernatant with the watery hydrochloric acid titration, and check has or not Ag
+Exist, thereby judge whether reaction is complete; 3) use the magnet products of separated, with deionized water, absolute ethanol washing, vacuum drying.
AgNO in the described step 2
3The concentration of the silver ion in solution or the silver ammino solution is 0.04 ~ 0.10mol/L.
The nickel powder that preferably will activate in the described step 2 joins that ultrasonic 30 ~ 60min is uniformly dispersed nickel powder in the silver ammino solution of silver ion in solution.
Reaction temperature is preferred 20 ~ 30 ℃ in the described step 2.
Vacuum drying condition is 40 ℃ of vacuum drying 12h in the described step 3.
Among the above-mentioned preparation method, used nickel powder average grain diameter is 104nm.
Among the above-mentioned preparation method, after the nickel powder washing after the sensitization, filter liquor AgNO
3Whether the adularescent precipitation generates in the solution titration, can check to have or not Cl
-Exist;
Among the above-mentioned preparation method, whether the adularescent precipitation generates with the watery hydrochloric acid titration to separate the supernatant that obtains with magnet after reaction finishes, and can check to have or not Ag
+Exist, thereby judge whether reaction is complete; With having or not the Ag nano particle to exist in the atomic absorption spectrophotometer test supernatant, can check Ag whether to wrap in Ni nuclear surface fully.
Description of drawings
Fig. 1 is according to example 1, the XRD spectra of the prepared sample of different solutions system;
A:AgNO
3Solution; B: silver ammino solution;
Fig. 2 is according to example 1, the transmission electron microscope picture of the prepared sample of different solutions system;
A:AgNO3 solution; B: silver ammino solution;
Fig. 3 is according to example 2, the XRD figure of preparation sample under the different nickeline mol ratios;
a：1:0.3；b：1:0.5；c：1:0.8；
Fig. 4 is according to example 2, the transmission electron microscope picture of preparation sample under the different nickeline mol ratios;
a：1:0.3；b：1:0.5；c：1:0.8；
Fig. 5 is according to example 3, the XRD of the sample for preparing under different temperatures figure;
a：20℃；b：30℃；c：40℃；
Fig. 6 is according to example 3, the transmission electron microscope picture of the sample for preparing under the different temperatures.
a：20℃；b：30℃；c：40℃；
The specific embodiment
The present invention will be further described below in conjunction with the implementation example.
Embodiment 1:20 ℃, 30 ℃, 40 ℃
Nickel powder clean is removed oxide with watery hydrochloric acid, and joining mass fraction later through the deionization washing is 5% SnCl
2Hydrochloric acid solution in soak activation, the time is 5min, then with the deionized water washing to without Cl
-The AgNO that nickel powder after the activation is added 50mL 0.04 ~ 0.08mol/L
3Ultrasonic 30min in solution or the silver ammino solution, the ratio of nickeline amount of substance is 1:0.4, and nickel powder is uniformly dispersed in solution, mechanical agitation 24 hours, whether the adularescent precipitation generates supernatant with the watery hydrochloric acid titration, can check to have or not Ag
+Exist, thereby judge whether reaction is complete; After reacting completely, use the magnet products of separated, with deionized water, absolute ethanol washing, 40 ℃ of vacuum drying 12h obtain product, and the complexing agent of investigating in this experiment is ammoniacal liquor.
Adopt XRD, transmission electron microscope characterizes sample: Fig. 1 is the XRD spectra of the sample of two kinds of reaction system preparations, can find out by checking the card of answering, the characteristic peak that has nickel and silver in the spectrogram, the characteristic peak that does not have its oxide, it is 38.2 ° at 2 θ wherein, 44.4 °, 64.6 °, 77.6 ° characteristic peak is (111) of corresponding A g respectively, (200), (220), (311) diffraction crystal face, 2 θ are (200) diffraction crystal face of 51.8 ° the corresponding Ni of characteristic peak, and 2 θ are 44.5 ° (111), the characteristic peak of the nickel of ° 76.4 (220) is 44.4 ° (200) with silver-colored 2 θ respectively, the characteristic peak overlaid of 77.6 ° (311), and this shows that the sample of preparation is the mixed metal powder of nickeline, cleaning surfaces, oxide-free existence.
Adopt transmission electron microscope that sample is characterized:
The transmission electron microscope picture of the sample of two kinds of reaction system preparations of Fig. 2, as can be seen from the figure, the sample topography of silver nitrate system preparation is irregular, and has the silver of more free state to exist; And the sample topography of silver ammino solution system preparation rule, free state silver-colored less, and coating is comparatively even, and therefore, displacement method prepares nickel-galactic nucleus shell structural nano particle selection silver ammino solution system.
Embodiment 2:
Nickel powder clean is removed oxide with watery hydrochloric acid, and joining mass fraction later through the deionization washing is 15% SnCl
2Hydrochloric acid solution in soak activation, the time is 5min, then with the deionized water washing to without Cl
-With ultrasonic 30 ~ 60min in the silver ammino solution of the adding of the nickel powder after activation 50mL 0.04 ~ 0.08mol/L, nickel powder is uniformly dispersed in solution, the nickeline mol ratio is respectively 1:0.3,1:0.5,1:0.8, mechanical agitation 24 hours, whether the adularescent precipitation generates supernatant with the watery hydrochloric acid titration, can check to have or not Ag
+Exist, thereby judge whether reaction is complete; After reacting completely, use the magnet products of separated, with deionized water, absolute ethanol washing, 40 ℃ of vacuum drying 12h obtain product.
Adopt XRD that sample is characterized:
The XRD spectra of the sample of for a change nickeline mol ratio preparation of Fig. 3, as can be seen from the figure, prepared sample had the characteristic peak of nickel and silver when the nickeline mol ratio was 1:0.3, was Ni-Ag bimetallic powder; And the nickeline mol ratio is 1:0.8,1:0.5 the time prepared sample have four characteristic peaks, it is 38.2 ° at 2 θ wherein, 44.4 °, 64.6 °, 77.6 ° characteristic peak (111) of corresponding A g respectively, (200), (220), (311) diffraction crystal face is because sample is magnetic, can judge that in conjunction with XRD spectra sample is the nickeline metal powder, not occurring the nickel powder characteristic peak in the spectrogram, may be because the content of nickel is lower than 5% in the sample, also may be because silverskin to the shielding action of ray so that X ray can not reach silver-nickel at the interface, therefore, the characteristic peak that does not occur nickel in the XRD spectra.
Adopt transmission electron microscope that sample is characterized: Fig. 4 is the TEM figure of the sample for preparing under the different nickeline mol ratios, as can be seen from the figure, along with reducing of nickel-Yin mol ratio, less, the silver-colored shell of nickel nuclear of prepared nucleocapsid structure is thicker, therefore, the nickel in the change reaction system-Yin mol ratio can effectively be regulated the silver-colored thickness of the shell of product.
Embodiment 3:
Nickel powder clean is removed oxide with watery hydrochloric acid, and joining mass fraction later through the deionization washing is 10% SnCl
2Hydrochloric acid solution in soak activation, the time is 8min, then with the deionized water washing to without Cl
-Nickel powder after the activation is added in the flask of the silver ammino solution that fills 50mL 0.06 ~ 0.10mol/L, the ratio of nickeline amount of substance is 1:0.4, ultrasonic 30 ~ 60min under the water-bath, bath temperature is respectively 20 ℃, and 30 ℃, 40 ℃, nickel powder is uniformly dispersed in solution, mechanical agitation 24 hours, whether the adularescent precipitation generates supernatant with the watery hydrochloric acid titration, can check to have or not Ag
+Exist, thereby judge whether reaction is complete; After reacting completely, use the magnet products of separated, with deionized water, absolute ethanol washing, 40 ℃ of vacuum drying 12h obtain product.
Adopt XRD that sample is characterized:
Fig. 5 is the XRD spectra of the sample for preparing under the different temperatures, as can be seen from the figure, three kinds of samples all have the characteristic peak of nickel, silver and do not have the characteristic peak of other oxide or magazine, are Ni-Ag bimetallic powder, show under three kinds of temperature that oxidation does not all occur for nickel, silver in the course of reaction.
Utilize transmission electron microscope that sample is characterized: Fig. 6 is the TEM figure of the sample for preparing under three kinds of temperature, as seen from the figure, increase along with reaction temperature, the silver of free state increases in the sample, when reaction temperature is 40 ℃, there is hardly nickel-galactic nucleus shell structure in the sample, this may be because of the rising along with reaction temperature, reaction speed is accelerated, thereby so that the speed of silver-colored nucleation is accelerated, finally make the silver that has occurred more free state in the sample, therefore, displacement method prepares nickel-galactic nucleus shell structural nano particle temperature should not be too high.
Claims (8)
1. a method for preparing the nickeline core-shell structure nanometer particle is characterized in that comprising the steps:
1) activation of nickel powder: nickel powder clean is removed oxide with watery hydrochloric acid, and joining mass fraction later through the deionization washing is 5 ~ 15% SnCl
2Hydrochloric acid solution in soak, the time is 5 ~ 15min, then with deionized water washing to without Cl
-
The nickel powder that 2) will activate joins the AgNO of silver ion
3Ultrasonic 30 ~ 60min is uniformly dispersed nickel powder in solution or the silver ammino solution in solution, and mechanical agitation is until react completely, and the ratio of nickeline amount of substance is respectively 1:04 ~ 1:1.1, and reaction temperature is 20 ~ 40 ℃;
3) use the magnet products of separated after reaction finishes, with deionized water, absolute ethanol washing, vacuum drying.
2. a kind of method for preparing the nickeline core-shell structure nanometer particle as claimed in claim 1 is characterized in that: AgNO in the described step 2
3The concentration of the silver ion in solution or the silver ammino solution is 0.04 ~ 0.10mol/L.
3. a kind of method for preparing the nickeline core-shell structure nanometer particle as claimed in claim 1 is characterized in that: the nickel powder that will activate in the described step 2 joins that ultrasonic 30 ~ 60min is uniformly dispersed nickel powder in the silver ammino solution of silver ion in solution.
4. a kind of method for preparing the nickeline core-shell structure nanometer particle as claimed in claim 1, it is characterized in that: reaction temperature is 20 ~ 30 ℃ in the described step 2.
5. a kind of method for preparing the nickeline core-shell structure nanometer particle as claimed in claim 1, it is characterized in that: vacuum drying condition is 40 ℃ of vacuum drying 12h in the described step 3.
6. a kind of method for preparing the nickeline core-shell structure nanometer particle as claimed in claim 1, it is characterized in that: the average grain diameter of described nickel powder is 104nm.
7. a kind of method for preparing the nickeline core-shell structure nanometer particle as claimed in claim 1 is characterized in that: after the nickel powder washing after the activation, and filter liquor AgNO
3Whether the adularescent precipitation generates in the solution titration, and check has or not Cl
-Exist.
8. a kind of method for preparing the nickeline core-shell structure nanometer particle as claimed in claim 1 is characterized in that: whether the adularescent precipitation generates with the watery hydrochloric acid titration to separate the supernatant that obtains with magnet after reaction finishes, and check has or not Ag
+Exist, thereby judge whether reaction is complete; With having or not the Ag nano particle to exist in the atomic absorption spectrophotometer test supernatant, whether check Ag has wrapped in Ni nuclear surface fully.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106181132A (en) * | 2016-07-15 | 2016-12-07 | 哈尔滨工业大学深圳研究生院 | A kind of high-temp solder preparation method based on Ag@Sn nucleocapsid structure |
| CN108284224A (en) * | 2018-03-18 | 2018-07-17 | 中船重工黄冈贵金属有限公司 | A kind of preparation method of sheet silver coated nickel powder body |
| CN111468739A (en) * | 2020-03-26 | 2020-07-31 | 浙江师范大学 | Magnetic recyclable Ni-coated Ag core-shell structure composite nanoparticle, preparation method thereof and dye degradation method |
| CN116618674A (en) * | 2023-05-11 | 2023-08-22 | 湖北银科新材料股份有限公司 | Preparation method of surface high-activity modified silver powder |
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| CN111468739A (en) * | 2020-03-26 | 2020-07-31 | 浙江师范大学 | Magnetic recyclable Ni-coated Ag core-shell structure composite nanoparticle, preparation method thereof and dye degradation method |
| CN116618674A (en) * | 2023-05-11 | 2023-08-22 | 湖北银科新材料股份有限公司 | Preparation method of surface high-activity modified silver powder |
| CN116618674B (en) * | 2023-05-11 | 2024-02-02 | 湖北银科新材料股份有限公司 | Preparation method of surface high-activity modified silver powder |
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Application publication date: 20130501 |