CN104289724B - A kind of preparation method of Hemicentrotus seu Strongylocentrotus shape amorphous Ni-B alloy nano-material - Google Patents
A kind of preparation method of Hemicentrotus seu Strongylocentrotus shape amorphous Ni-B alloy nano-material Download PDFInfo
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- CN104289724B CN104289724B CN201410465167.5A CN201410465167A CN104289724B CN 104289724 B CN104289724 B CN 104289724B CN 201410465167 A CN201410465167 A CN 201410465167A CN 104289724 B CN104289724 B CN 104289724B
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Abstract
The invention discloses the preparation method of a kind of Hemicentrotus seu Strongylocentrotus shape amorphous Ni B alloy nano-material, the present invention uses liquid phase plasma body technique successfully to synthesize the Hemicentrotus seu Strongylocentrotus shape Ni B granule with meso-hole structure.Compared with amikacin and kanamycin, especially Pseudomonas aeruginosa is shown higher antibacterial activity.Compared with conventional Ni B, the Ni B magnetic of Hemicentrotus seu Strongylocentrotus shape is higher.Meanwhile, Hemicentrotus seu Strongylocentrotus shape Ni B is compared with Raney Ni and traditional Ni B, and it is at catalysis N2H4The performance of dehydrogenation is higher.Strengthening owing to high specific surface area and the intrinsic activity of its unique texture decision enhancing of catalytic performance.In current result of study, Hemicentrotus seu Strongylocentrotus shape Ni B has fungistatic effect, magnetic and catalytic dehydrogenation performance, will be hopeful to widen its range of application, is coated with from medical apparatus and instruments and expects directly treatment wound or burn, and magnetic apparatus and catalytic field.
Description
Technical field
The present invention relates to Ni-B alloy nano-material technical field, particularly relate to a kind of Hemicentrotus seu Strongylocentrotus shape without
The preparation method of setting Ni-B alloy nano-material.
Background technology
In recent years, due to the peculiar property of amorphous Ni-B alloy, such as substantial amounts of coordination insatiable hunger
And position, chemical stability and isotropic structure so that it is the most potential is applied to catalyst,
Coating, magnetic material and anti-biotic material, thus cause widely studied to it of people.Many institutes
Known, the microstructure of amorphous metal boride alloy plays vital in its character
Effect.But, up to now, seldom have successfully to prepare there is good microstructure Ni-B
The example of alloy, is likely to be due to and BH4 -Strong exothermal reaction so that in preparation process Ni sun
Uncontrollable minimizing of ion.Therefore, there is erose conventional Ni-B and have low
Specific surface area so that its performance is relatively low.
Liquid phase plasma body technique (SPP, solution plasma process), i.e. at water
In solution environmental introduce plasma, its have proven to one prepare have good microcosmic knot
The effective way of the amorphous metal boride of structure.Such as, passed through SPP technology successfully to prepare
Co-B-N-H nano wire, honeycomb Co-B and nanosphere are gone out.Simultaneously, it was reported that Co-B
Shape can regulate by changing the stabilizer in liquid phase plasma processing procedure.
Summary of the invention
The present invention uses SPP technology, by Ni (NH3)6 2+With the mixed solution of PVA, close first
Become out amorphous Hemicentrotus seu Strongylocentrotus shape Ni-B alloy, and it has high specific surface area (224.67m2g-1),
There is good antibacterial activity, magnetic property, and dehydrogenation simultaneously.
The present invention adopts the following technical scheme that
The concrete step of the preparation method of the Hemicentrotus seu Strongylocentrotus shape amorphous Ni-B alloy nano-material of the present invention
Rapid as follows:
(1) by NH3H2O solution mixes with Nickel dichloride., to form Ni (NH3)6 2+Mixed liquor, NH3H2O
It is 0.4-0.7 with the mol ratio of Nickel dichloride.: 0.0085；
(2) add in the mixed liquor of step (1) at a temperature of argon shield and 250-350K
KBH4Aqueous solution and polyvinyl alcohol, KBH4Aqueous solution and polyvinyl alcohol with the mol ratio of Nickel dichloride. are
0.5-2∶0.001-0.003∶0.0085；
(3) mixed solution using liquid phase plasma body device to prepare step (2) processes
Ni-B amorphous Hemicentrotus seu Strongylocentrotus crude product is obtained after 2-8min；
(4) product is washed with deionized once, then with absolute ethanol washing three times, is stored in
In ethanol standby.
In step (1), NH3H2The volumetric concentration of O solution is 25%.
In step (1), preferably NH3H2O is 0.53: 0.0085 with the mol ratio of Nickel dichloride..
In step (2), preferably toward step (1) at a temperature of argon shield and 298K
Mixed liquor adds KBH4Aqueous solution and polyvinyl alcohol.
In step (2), preferably KBH4Aqueous solution and polyvinyl alcohol with the mol ratio of Nickel dichloride. are
1∶0.002∶0.0085。
In step (3), using tungsten filament in liquid phase plasma body device is positive and negative electrode, tungsten filament
A diameter of 2mm, two interelectrode distances are 1mm, and the running voltage of DC pulse high tension generator is
225V, frequency is 12KHz.
In step (3), described liquid phase plasma body device patent applied for, details
Asking for an interview application number: 2014203010301, a kind of liquid phase plasma method prepares nano material
Device.
The positive effect of the present invention is as follows:
1) present invention is by using simple Ni (NH3)6 +With mixing of polyvinyl alcohol (PVA)
Close solution methods, the most successfully synthesize Hemicentrotus seu Strongylocentrotus shape amorphous Ni-B alloy.
2) with conventional Ni-B contrast, the specific surface area of Hemicentrotus seu Strongylocentrotus shape Ni-B is bigger.
3) with conventional Ni-B contrast, the magnetic of Hemicentrotus seu Strongylocentrotus shape Ni-B is higher.
4) with conventional Ni-B contrast, Hemicentrotus seu Strongylocentrotus shape Ni-B Compounds with Hydrazine Hydrate Catalyzed (N2H4) decompose
Time, selectivity is higher.
5) Hemicentrotus seu Strongylocentrotus shape Ni-B is compared with amikacin and kanamycin, to Aerugo vacation list
During born of the same parents bacterium (P.aeruginosa) processes, show great antibacterial activity.
Accompanying drawing explanation
Fig. 1 is the low range STEM photo that embodiment 1 prepares amorphous Ni-B alloy nano-material.
Fig. 2 is the expansion STEM photo that embodiment 1 prepares amorphous Ni-B alloy nano-material.Figure
Fig. 3 is the high magnification STEM photo that embodiment 1 prepares amorphous Ni-B alloy nano-material.
Fig. 4 is the electronogram that embodiment 1 prepares amorphous Ni-B alloy nano-material.
Fig. 5 is N2 adsorption-desorption isotherm that embodiment 1 prepares amorphous Ni-B alloy nano-material
Figure.
Fig. 6 is the X ray diffracting spectrum that embodiment 1 prepares amorphous Ni-B alloy nano-material.
Fig. 7 is the Ni2p XPS spectrum that embodiment 1 prepares amorphous Ni-B alloy nano-material.
Fig. 8 is the Bl that embodiment 1 prepares amorphous Ni-B alloy nano-materialSXPS spectrum figure.
Fig. 9 is hysteresis curve and the magnetic characteristic that embodiment 1 prepares amorphous Ni-B alloy nano-material
Figure.
Figure 10 is the catalysis N that embodiment 1 prepares amorphous Ni-B alloy nano-material2H4Dehydrogenation time
Between graph of a relation.
Figure 11 is the cycle performance figure that embodiment 1 prepares amorphous Ni-B alloy nano-material.
Detailed description of the invention
The following examples are that the present invention is described in further detail.
Experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, all can be from business
Approach obtains.
Embodiment 1
For achieving the above object, the preparation process of the amorphous Hemicentrotus seu Strongylocentrotus of concrete Ni-B is:
1)40mL NH3H2O solution (25%) mixes with 10mL Nickel dichloride. (0.0085mol),
To form Ni (NH3)6 2+Mixed liquor；
2) at a temperature of 298K, 32mL KBH4Aqueous solution (1.0M) and PVA0.001M exist
Add under argon atmospher；
3) after liquid phase plasma technical finesse 5min, obtain the product of preparation；
4) by its deionized water wash once, then with absolute ethanol washing three times；
5) sample is stored in ethanol until using.
Embodiment 2
1)40mL NH3H2O solution (25%) mixes with 10mL Nickel dichloride. (0.0085mol),
To form Ni (NH3)6 2+Mixed liquor；
2) at a temperature of 298K, 32mL KBH4Aqueous solution (1.0M) and PVA0.002M exist
Add under argon atmospher；
3) after liquid phase plasma technical finesse 5min, obtain the product of preparation；
4) by its deionized water wash once, then with absolute ethanol washing three times；
5) sample is stored in ethanol until using.
Embodiment 3
1)40mL NH3H2O solution (25%) mixes with 10mL Nickel dichloride. (0.0085mol),
To form Ni (NH3)6 2+Mixed liquor；
2) at a temperature of 298K, 32mL KBH4Aqueous solution (1.0M) and PVA 0.003M exist
Add under argon atmospher；
3) after liquid phase plasma technical finesse 5min, obtain the product of preparation；
4) by its deionized water wash once, then with absolute ethanol washing three times；
5) sample is stored in ethanol until using.
The performance of the Hemicentrotus seu Strongylocentrotus shape amorphous Ni-B alloy nano-material of the present invention:
Using STEM to be characterized material prepared by embodiment 1, Fig. 1 is the low of sample
Multiplying power STEM image, it can be seen that Hemicentrotus seu Strongylocentrotus shape Ni-B particle successfully prepares, its average particle
Footpath is about 240nm, and it is to be assembled (Fig. 2) by nanometer rods.High-resolution STEM
Image shows, nanometer rods forms these nanoparticles, and presents and have the thick of many nano-pores
Rough surface (Fig. 3).
Using SAED (JEOL-2100F) to carry out material structure sign, it is amorphous is by selecting
The halation of district's electronogram (Fig. 4) is confirmed.
Use N2 adsorption-desorption isotherm to the meso-hole structure of sea urchin type Ni-B by demonstrate,proving further
Real (Fig. 5).Its average pore size is 3.1nm, and specific surface area is 224.67m2g-1。
Use ICP-AES (Irris, Advantage) analyze show, prepared product with
Conventional Ni-B atom forms identical (Ni66.7B33.3).
Use XRD (Philips, XPERT-PRO, CuK α) that material crystals character is carried out
Analyzing, in collection of illustrative plates, the Ni-B of Hemicentrotus seu Strongylocentrotus shape is as conventional Ni-B material, at 45 °
There is a broad peak, further demonstrate that its amorphous character (Fig. 6).
XPS (Perkin-Elmer 5000C ESCA, AlK α) collection of illustrative plates (Fig. 7 and Fig. 8)
Showing, in the Ni-B of Hemicentrotus seu Strongylocentrotus shape, Ni and B exists with elementary state.
The antibacterial activity of Hemicentrotus seu Strongylocentrotus shape Ni-B has been also carried out studying (table 1).Use colorimetric method for determining
Mlc (MICs, μ gmL-1) method, measure material to staphylococcus aureus
(S.aureus), Candida albicans (C.albicans), escherichia coli (E.coli), Mus
Salmonella typhi (S.typhmurium) and the antibacterial activity of Pseudomonas aeruginosa.As than
Relatively, the antibacterial activity of amikacin and kanamycin is also found in table.
The antibacterial activity of table 1 sample
Magnetic Measurement is at room temperature, and the magnetic testing Hemicentrotus seu Strongylocentrotus shape Ni-B and conventional Ni-B is special
Property (Fig. 9).The coercivity (Hc) of Hemicentrotus seu Strongylocentrotus shape Ni-B, saturation magnetization (Ms) and surplus
The quantity of magnetism (Mr) is respectively 209.40e, 42.4emug-1And 12.1emug-1。
The Ni-B of Hemicentrotus seu Strongylocentrotus shape is decomposed N2H4Dehydrogenation activity done and evaluated (Figure 10).As ginseng
Examining, nickel and conventional Ni-B are also used for being catalyzed N2H4Dehydrogenation is evaluated.After 32 minutes, N2H4Complete
Full decomposition, the H of the Ni-B of Hemicentrotus seu Strongylocentrotus shape2Selectivity reaches 90%, and Ni and conventional Ni-B
To N2H4Selectivity decompose only reach 40% and 55% (Figure 10) respectively.
When adding 0.05M NaOH, the H of Hemicentrotus seu Strongylocentrotus shape Ni-B2Selectivity brings up to 100% (figure
10).Meanwhile, the existence of NaOH is catalyzed activity not impact (Figure 10) to the Ni-B of Hemicentrotus seu Strongylocentrotus shape.
The magnetic of the Ni-B of Hemicentrotus seu Strongylocentrotus shape makes it can efficiently separate (in Figure 11 when using Magnet
Illustration), thus reach recycle purpose.
Made stability of material is listed in Figure 11, recycles for continuous 5 times, Hemicentrotus seu Strongylocentrotus shape Ni-B's
Catalysis activity is kept essentially constant (Figure 11).
The present invention uses liquid phase plasma body technique successfully to synthesize to have meso-hole structure
Hemicentrotus seu Strongylocentrotus shape Ni-B granule.Compared with amikacin and kanamycin, especially to Aerugo
Pseudomonas shows higher antibacterial activity.Compared with conventional Ni-B, the Ni-B of Hemicentrotus seu Strongylocentrotus shape
Magnetic is higher.Meanwhile, Hemicentrotus seu Strongylocentrotus shape Ni-B is compared with Raney Ni and traditional Ni-B, and it is catalyzed
N2H4The performance of dehydrogenation is higher.Strengthening owing to high specific surface area and its uniqueness of catalytic performance
The intrinsic activity that structures shape strengthens.In current result of study, Hemicentrotus seu Strongylocentrotus shape Ni-B has antibacterial
Effect, magnetic and catalytic dehydrogenation performance, will be hopeful to widen its range of application, from medical apparatus and instruments
Directly treatment wound or burn are expected in painting, and magnetic apparatus and catalytic field.
Although an embodiment of the present invention has been shown and described, for the ordinary skill of this area
For personnel, it is possible to understand that without departing from the principles and spirit of the present invention can be to this
A little embodiments carry out multiple change, revise, replace and modification, and the scope of the present invention is by appended power
Profit requires and equivalent limits.
Claims (7)
1. the preparation method of a Hemicentrotus seu Strongylocentrotus shape amorphous Ni-B alloy nano-material, it is characterised in that:
Specifically comprising the following steps that of described preparation method
(1) by NH3H2O solution mixes with Nickel dichloride., to form Ni (NH3)6 2+Mixed liquor,
NH3H2O is 0.4-0.7 with the mol ratio of Nickel dichloride.: 0.0085；
(2) add in the mixed liquor of step (1) at a temperature of argon shield and 250-350K
KBH4Aqueous solution and polyvinyl alcohol, KBH4Aqueous solution and polyvinyl alcohol and Nickel dichloride. mole
Ratio is for 0.5-2: 0.001-0.003: 0.0085；
(3) mixed solution using liquid phase plasma body device to prepare step (2) processes
Ni-B amorphous Hemicentrotus seu Strongylocentrotus crude product is obtained after 2-8min；
(4) product is washed with deionized once, then with absolute ethanol washing three times, is stored in
In ethanol standby.
2. the preparation method of Hemicentrotus seu Strongylocentrotus shape amorphous Ni-B alloy nano-material as claimed in claim 1,
It is characterized in that: in step (1), NH3H2The volumetric concentration of O solution is 25%.
3. the preparation method of Hemicentrotus seu Strongylocentrotus shape amorphous Ni-B alloy nano-material as claimed in claim 1,
It is characterized in that: in step (1), NH3H2O is 0.53 with the mol ratio of Nickel dichloride.:
0.0085。
4. the preparation method of Hemicentrotus seu Strongylocentrotus shape amorphous Ni-B alloy nano-material as claimed in claim 1,
It is characterized in that: in step (2), toward step (1) at a temperature of argon shield and 298K
Mixed liquor in add KBH4Aqueous solution and polyvinyl alcohol.
5. the preparation method of Hemicentrotus seu Strongylocentrotus shape amorphous Ni-B alloy nano-material as claimed in claim 1,
It is characterized in that: in step (2), KBH4Aqueous solution and polyvinyl alcohol and Nickel dichloride. mole
Ratio is 1: 0.002: 0.0085.
6. the preparation method of Hemicentrotus seu Strongylocentrotus shape amorphous Ni-B alloy nano-material as claimed in claim 1,
In step (3), solution plasma treatment time is 5min.
7. the preparation method of Hemicentrotus seu Strongylocentrotus shape amorphous Ni-B alloy nano-material as claimed in claim 1,
In step (3), using tungsten filament in liquid phase plasma body device is positive and negative electrode, tungsten filament diameter
For 2mm, two interelectrode distances are 1mm, and the running voltage of DC pulse high tension generator is
225V, frequency is 12KHz.
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