CN101417341A

CN101417341A - Method for preparing metal nickel nano hollow bal

Info

Publication number: CN101417341A
Application number: CNA2008102350606A
Authority: CN
Inventors: 曹霞
Original assignee: Jiangsu University of Science and Technology
Current assignee: Jiangsu University of Science and Technology
Priority date: 2008-11-07
Filing date: 2008-11-07
Publication date: 2009-04-29

Abstract

The invention discloses a preparation method of metallic nickel hollow nanospheres. Nickel salts and polyvinylpyrroidone are dissolved in ethylene glycol according to the mass ratio of 1:0.5 to 1:20, hydrazine hydrate is added according to the mole ratio of hydrazine hydrate to nickel salts equaling to 2 to 20:1 and 5ml to 15ml of ethanol is added, the reaction lasts for 3 to 48h while heating until black precipitation is generated in the solution, and the black precipitation is washed and dried to obtain loosened black powdery metallic nickel hollow nanospheres or metallic nickel hollow nanosphere chains. In solution environment, nanocrystal grains are assembled at the interface between a surfactant capsule and the solution for secondary crystallization, and the metallic nickel hollow nanospheres with high specific surface area and hollow structure can be obtained after the surfactant is removed by washing. The method has simple process and low cost.

Description

The method for preparing metal nickel nano hollow bal

Technical field

The present invention relates to a kind of manufacture method of metallic nickel, particularly a kind of nano level preparation method who is widely used in preparing the metallic nickel in fields such as battery, sensor, catalyst.

Background technology

Have the hollow ball of nanostructured because have that density is low, filterability good, specific polarity and optical property, thereby have specific use.Be applied to fields such as medical science, pharmaceutics, material science, can be used as the carrier, capsule and the supporter that add dress thing, coating, pigment, catalyst and drug delivery, and can be used as cage shape reactor and make and be reflected at limited space and carry out.In the past few years, nano-hollow ball prepared swift and violent development, wherein template is the nano-hollow sphere structured the most frequently used preparation method of present core-shell type.Template commonly used comprises gold, silver, CdS, SiO ₂The polymer microsphere of nano colloidal particles microballoon, monodispersity and other some polymer etc.Except template, self assembly also is a kind of effective method for preparing hollow ball structure of development in recent years.It generally is to utilize macromolecular template to induce and control inorganic matter formation and growth that self assembly prepares hollow ball, its maximum characteristics are controlled deposition process with regard to the formwork structure molecule, utilize between rigging and the nano particle and they self mutual recognition reaction, make assembly have more abundant pattern, as hollow ball, nanotube, particle and they in the superstructure of different dimensions assembling etc.In these superstructures, the one dimension assembly of magnetic particle is subjected to increasing attention because of it at the new kink characteristics of magnetic aspect transporting, wherein relatively more excellent work comprises the hollow ball semiconductor-mounted device that utilizes the intrinsic dipole moment of magnetic particle to make particle formation one-dimentional structure, thereby and utilizes the Kirkendall effect on the nanoscale to obtain the magnetic template is transcribed the one dimension hollow-core construction that obtains nickel under higher temperature.

Nickel is a class important strategic metal material, almost obtains to use widely in all modern industry fields.The micro-/ nano multilevel hierarchy is constructed technology and traditional handicraft combines; by component, size, shape and organizational form the character of assembly is carried out more accurate regulation and control, can greatly change the performance of metallic nickel in applications such as catalysis, electrode, chemoproection coating, soft magnetic materials and low temperature superplasticity material from molecular level adjusted construction unit.The preparation method of metal nickel nano structure has obtained significant progress recently, and synthetic nanostructured comprises the nanosphere of chemical reduction method, electrochemistry template depositing nano ring etc.The nickel hollow ball generally is to utilize the method for template to prepare, and the template of employing comprises silicon dioxide microsphere, polymer microsphere and some precious metal nano colloidal particles microballoons etc.Though these methods can access high-quality metal nickel nano hollow bal, but cost height, productive rate is low, how can produce that metallic nickel is hollow nanostructured to have great economic worth and scientific meaning in practical application with in producing with cost-effective method on a large scale.

Summary of the invention

In order to solve the production cost height that prior art exists, the shortcoming that productive rate is low the present invention proposes a kind of method for preparing metal nickel nano hollow bal, has the advantage that technology is simple, cost of material is cheap.

Technical scheme of the present invention is: a kind of method for preparing metal nickel nano hollow bal, is that the ratio of 1:0.5～1:20 is dissolved in the ethylene glycol with nickel salts and polyvinylpyrrolidone in mass ratio, the mol ratio of pressing hydrazine hydrate: nickel salts=2-20:1 again adds hydrazine hydrate and 5ml～15ml ethanol, add thermal response 3～48h, to solution, produce black precipitate, with dry black powder shape metal nickel nano hollow bal or the metal nickel nano hollow bal chain that obtains loosening of black precipitate washing.Described nickel salts is any one in nickel acetate, nickelous sulfate, nickel chloride or the nickel nitrate.The molar concentration of described nickel salts in ethylene glycol is 0.001～0.1mol/L.Heating can adopt boiling reflux or temperature control to stir in the course of reaction, between temperature control 60-197 ℃, and mixing speed 100-10,000 rev/min of mode obtains even product.The molecular weight of described polyvinylpyrrolidone is between 30,000 to 50,000.Nanocrystal is at the assembling at the interface and the secondary crystallization of surface-active agent capsules and solution in solution environmental, and surfactant can obtain to have the metal nickel nano hollow bal or the one dimension hollow ball chain of the hollow-core construction of high-specific surface area after washing is removed.This method technology is simple, with low cost,

Beneficial effect: 1. the metal nickel nano particle of the present invention's preparation has hollow-core construction, prolong the reaction time, strengthen the one dimension package assembly that dosage of surfactant can also form nano-hollow ball, than before solid construction, this hollow-core construction has features such as density is low, surface area is big, be suitable for as carrier, capsule and the supporter of loading thing, coating, pigment, catalyst, sensor, battery and drug delivery, and can be used as cage shape reactor etc. and be applied to fields such as medical science, pharmaceutics, material science.

2. it is with low cost that this method prepares the metallic nickel hollow nano-sphere, and technology is simple.

Description of drawings:

Fig. 1 is the XRD spectrum of hollow ball chain.

Fig. 2 is the low power SEM image of (a) pure nickel nano chain; (b) the SEM image of sample under the multiplication factor;

(c) the low power SEM image of pure nickel hollow ball

The specific embodiment

Embodiment 1

At first with 0.27g NiCl ₂6H ₂O and 1g polyvinylpyrrolidone PVP (molecular weight MW30,000) are dissolved into (EG) in the 75ml ethylene glycol, then hydrazine hydrate: NiCl in molar ratio in above-mentioned solution ₂6H ₂The ratio of O=2:1 adds hydrazine hydrate and 5ml ethanol, is heated to boiling point then and refluxes 4 hours, and solution becomes from initial blueness and becomes yellow green and finally have the black hollow ball to produce.To precipitate with behind the absolute ethanol washing 6 times 80 ℃ of oven dry down, the black powder shape metal nickel nano hollow bal that obtains loosening, hollow ball diameter are about 1 micron, are about 10 nanometers as the metallic nickel nano granule particle diameter of basic construction unit.

Embodiment 2

At first with 0.27g NiCl ₂6H ₂O and 1g PVP (MW40,000) are dissolved into (EG) in the 75ml ethylene glycol under strong agitation, then hydrazine hydrate: NiCl in molar ratio in above-mentioned solution ₂6H ₂The ratio of O=20:1 adds hydrazine hydrate and 5ml ethanol, so is heated to boiling point and refluxes 48 hours, has a large amount of black hollow ball chains to produce at the bottom of bottle.

Embodiment 3

At first in the ratio of mass ratio 1:4 with 0.5g nickelous sulfate and 2g polyvinylpyrrolidone PVP (molecular weight MW30,000) is dissolved into (EG) in the 75ml ethylene glycol, in above-mentioned solution, add 1.5ml hydrazine hydrate (50% Vol.A.R.) and 5ml ethanol then, temperature control is at 180 ℃ then, reacted 6 hours, solution becomes from initial blueness and becomes yellow green and finally have the black hollow ball to produce.To precipitate with behind the absolute ethanol washing 6 times at 80 ℃ of oven dry down, the black powder that obtains loosening.

Embodiment 4

At first in the ratio of mass ratio 1:20 with 0.3g nickel nitrate and 6g polyvinylpyrrolidone PVP (molecular weight MW30,000) is dissolved into (EG) in the 1032ml ethylene glycol, then in above-mentioned solution in molar ratio the ratio of hydrazine hydrate: nickel nitrate=12:1 add hydrazine hydrate and 5ml ethanol, be warming up to boiling then, reacted 12 hours, solution becomes from initial blueness and becomes yellow green and finally have the black hollow ball to produce.To precipitate with behind the absolute ethanol washing 6 times at 80 ℃ of oven dry down, the black powder that obtains loosening.Gained hollow ball diameter is about 300 nanometers, is about 6 nanometers as the metallic nickel nano granule particle diameter of basic construction unit.

Embodiment 5

At first in the ratio of mass ratio 1:10 with 0.3g nickel acetate and 3g polyvinylpyrrolidone PVP (molecular weight MW50,000) is dissolved into (EG) in the 12ml ethylene glycol, in above-mentioned solution, add 2ml hydrazine hydrate (50% Vol.A.R.) and 15ml ethanol then, be heated to boiling then and reacted 48 hours, solution becomes from initial blueness and becomes yellow green and finally have black hollow ball chain to produce.To precipitate with behind the absolute ethanol washing 6 times at 80 ℃ of oven dry down, the black powder that obtains loosening.

Embodiment 6

At first with 0.27g NiCl ₂6H ₂O and 1g PVP (MW40,000) under strong agitation, is dissolved into (EG) in the 75ml ethylene glycol, in above-mentioned solution, add 1.25ml hydrazine hydrate (50% Vol.A.R.) and 10ml ethanol then, temperature control is at 60 ℃ then, 100 rev/mins of reactions of mixing speed 48 hours have a large amount of black hollow ball chains to produce at the bottom of bottle.

Embodiment 7

At first with 0.27g NiCl ₂6H ₂O and 1g PVP (MW40,000) under strong agitation, is dissolved into (EG) in the 75ml ethylene glycol, in above-mentioned solution, add 1.25ml hydrazine hydrate (50% Vol.A.R.) and 5ml ethanol then, temperature control is at 100 ℃ then, 7000 rev/mins of reactions of mixing speed 48 hours have a large amount of black hollow ball chains to produce at the bottom of bottle.

We can find from the metallic nickel hollow nano-sphere EM figure that above embodiment obtains, resulting metallic nickel has controlled nanostructured, can produce monodispersed hollow metal nickel nanosphere or hollow metal nickel nano-line as required, these metal nickel nano structure and morphologies are controlled, the size homogeneous, the well-crystallized can fully satisfy existing industrial requirement, and is expected to obtain extensive use in a plurality of fields.

Claims

1. method for preparing metal nickel nano hollow bal, it is characterized in that, is that the ratio of 1:0.5～1:20 is dissolved in the ethylene glycol with nickel salts and polyvinylpyrrolidone in mass ratio, the mol ratio of pressing hydrazine hydrate: nickel salts=2-20:1 again adds hydrazine hydrate and 5ml～15ml ethanol, add thermal response 3～48h, to solution, produce black precipitate, with dry black powder shape metal nickel nano hollow bal or the metal nickel nano hollow bal chain that obtains loosening of black precipitate washing.

2. by the described method for preparing metal nickel nano hollow bal of claim 1, it is characterized in that described nickel salts is any one in nickel acetate, nickelous sulfate, nickel chloride or the nickel nitrate.

3. by the described method for preparing metal nickel nano hollow bal of claim 1, it is characterized in that the molar concentration of described nickel salts in ethylene glycol is 0.001～0.1mol/L.

4. by the described method for preparing metal nickel nano hollow bal of claim 1, it is characterized in that heating can adopt boiling reflux or temperature control to stir in the course of reaction, between temperature control 60-197 ℃, mixing speed 100-10,000 rev/min of mode obtains even product.

5. by the described method for preparing metal nickel nano hollow bal of claim 1, the molecular weight that it is characterized in that described polyvinylpyrrolidone is between 30,000 to 50,000.