CN101538692B - Method for preparing two-dimensional Ni-based amorphous alloy nanophase material by soft and hard composite template method - Google Patents
Method for preparing two-dimensional Ni-based amorphous alloy nanophase material by soft and hard composite template method Download PDFInfo
- Publication number
- CN101538692B CN101538692B CN200910049956XA CN200910049956A CN101538692B CN 101538692 B CN101538692 B CN 101538692B CN 200910049956X A CN200910049956X A CN 200910049956XA CN 200910049956 A CN200910049956 A CN 200910049956A CN 101538692 B CN101538692 B CN 101538692B
- Authority
- CN
- China
- Prior art keywords
- aqueous solution
- preparation
- product
- amorphous alloy
- micro emulsion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention belongs to the technical field of materials, in particular relates to a method for preparing a two-dimensional Ni-based amorphous alloy nanophase material by the method of soft and hard composite templates. The method adopts the soft and hard composite template method and uses a reducing agent to reduce soluble metal salt so as to realize the preparation of the amorphous alloy nanophase material. The method includes the following steps: preparing a collodion membrane; preparing an M<2+> aqueous solution; preparing M<2+> inverse microemulsion; adding a reducing agent to reduce M<2+>, and forming a black product; and rinsing the black product, clarifying the black product by centrifugate, and removing the centrifugate to obtain the required product. The reaction can choose thesoluble M<2+> aqueous solution or adopt the M<2+> aqueous solution and control water, oil and surface active agent with a certain proportion to prepare the clear and transparent inverse microemulsionwhich is used as a soft template, and the collodion membrane is used as a hard template to realize the control of the appearance of the product; and the prepared amorphous alloy nanophase material has unique appearance and excellent physicochemical property.
Description
Technical field
The invention belongs to the material technology field, relate to the method for preparing amorphous alloy nano material.
Background technology
Nanoscale science and technology (Nano-ST) is the new science and technology that late 1980s is born and is emerging, and its basic connotation is at nano-scale (10
-9-10
-7M) understanding and nature remodeling in the scope are by direct control and arrange atom, molecule to create new material.Nano material is meant to have at least one dimension to be in the nanoscale scope in three-dimensional space, or the material that is made of as elementary cell them.The special construction of nano material makes the property of nano material produce four big effects: i.e. small-size effect, quantum effect (containing macro quanta tunnel effect), surface effects and interfacial effect etc., the characteristic of these a series of novelties, make it in various fields, particularly there is great application value aspects such as light, electricity, magnetic, catalysis, nanomaterial science is a branch of nanosecond science and technology, but it is the basis of Nano-technology Development.
Amorphous alloy also claims amorphous alloy, be under the cooling rate that is exceedingly fast (106 ℃/S), by liquid alloy directly " freezing " form, amorphous alloy is a kind of material that is different from the completely isotropic of crystal alloy.Because it is unordered and constructional feature short range order makes it have the unapproachable high strength of crystalline state metal, high rigidity, high ductibility, excellent soft magnetic performance, high anti-corrosion and excellent electric performance, anti-irradiation ability and catalysis preferably and hydrogen storage ability that amorphous alloy has long-range.Because amorphous alloy nano material has been gathered the double dominant of amorphous alloy and nano material, therefore be given increasing concern, especially Ni base amorphous alloy nano material, excellent catalytic performance and magnetic property that it has, can be applied to magnetic recording material, transmitter, catalyzer, fields such as nano-electrode material have caused people's extensive studies interest.Although there have been a lot of researchs to relate to Ni base amorphous alloy nano material at present, yet to the research of the structure of the Ni base noncrystal alloy of two-dimensional nanostructure and the properties further investigation that awaits.
Summary of the invention
The objective of the invention is to propose that controlled, the decrystallized state of pattern under a kind of room temperature is controlled, good stability, easy to operate, the preparation method that is easy to industrialized Ni matrix series non-crystalline state alloy nano-material, extend to large-scale industrial application.
The present invention introduced a kind of based on artificial active collodion liquid film as hard template and microemulsion as the composite shuttering method of soft template, make divalent metal salt at normal temperatures by KBH
4Reduction.Thereby obtain the two-dimensional Ni-based amorphous alloy nano material.
Reaction can be selected soluble M
2+The aqueous solution perhaps adopts M
2+The aqueous solution is also by controlling water, oil, the tensio-active agent of certain proportioning, the reverse micro emulsion that configures clear is as soft template, and utilize the collodion liquid film to be the control of hard template realization to the product pattern, prepare Ni and Ni matrix series non-crystalline state alloy nano-material, nano material has unique pattern and has excellent physico-chemical property, for example at magnetic, catalytic, there is excellent performance aspects such as storage hydrogen and wave absorbtion and uses widely.
The present invention adopts the soft and hard composite template method, realizes the preparation of amorphous alloy nano material with reductive agent reduction soluble metal salt.Collodion is usually used in the preparation of semi-permeable membranes, and the semi-permeable membranes aperture that makes is arrived between the hundreds of nanometer tens.This film is compared with general polymeric membrane, has the adjustable advantage in thickness and effective pore radius, and contains a large amount of active nitro (NO on the film
2) and the duct, have the template control action kou.Microemulsion method is a kind of heterogeneous liquid phase synthesizing method, be two kinds of immiscible solvents, under Action of Surfactant, form emulsion, in microvesicle through nucleation, condense, obtain nanostructure after the reunion, thermal treatment, with sol-gel method, coprecipitation method, other wet chemical method such as hydrothermal method is compared, and it has particulate and is difficult for coalescent, controlled amount, good dispersity, narrow particle size distribution, easy to operate, the characteristics that do not need special conditionss such as High Temperature High Pressure.
A kind of preparation method of amorphous alloy nano material adopts the soft and hard composite template method, realizes may further comprise the steps the preparation of amorphous alloy nano material with reductive agent reduction soluble metal salt:
Preparation collodion liquid film;
Preparation M
2+The aqueous solution;
Preparation M
2+Reverse micro emulsion;
Add reductive agent reduction M
2+, have the black product to generate;
This black product washing is reached the centrifugate clarification, discard centrifugate and promptly get desired product.
Further: may further comprise the steps:
Make the collodion liquid film:
Drip collodion liquid on the silicon substrate in the rotation, make the film natural air drying after rotating certain hour (10-15s) simultaneously, take off, standby;
Preparation M
2+The aqueous solution:
Get metal-salt and place container, add deionized water, fully stir and make its dissolving, be configured to M
2+The aqueous solution;
Preparation M
2+Reverse micro emulsion:
Get CTAB and place container, add normal hexane, n-hexyl alcohol and M
2+The aqueous solution is configured to M after fully stirring
2+Reverse micro emulsion;
Add reductive agent reduction M
2+: (get the Glass tubing of a both ends open, and the one end is sealed with the collodion liquid film) is with above-mentioned M
2+The aqueous solution or M
2+In the Glass tubing that seals with the collodion liquid film bottom reverse micro emulsion is packed into, vertically be immersed in and fill KBH
4React in the beaker of solution, the NaOH solution that adds 0.2mol/L is regulated reductive agent KBH
4The pH value of solution, alkaline condition can find that collodion liquid film bottom has the black product to generate after reaction for some time down;
The aftertreatment of product:
Reverse micro emulsion carries out breakdown of emulsion earlier to be handled, and this black product washing is reached the centrifugate clarification, discards centrifugate and promptly gets desired product.
Wherein: make the collodion liquid film:
Adopt equal glue machine to prepare the collodion liquid film that thickness is 0.12mm-0.18mm, at first with the rotating speed of 1000r/min-1200r/min rotation silicon substrate, drip collodion liquid on the silicon substrate in the rotation then, after rotating 15-20s under this rotating speed, make the film natural air drying, take off, standby;
Preparation M
2+The aqueous solution:
Get metal-salt and place container, add deionized water, fully stir and make its dissolving, be configured to M
2+The aqueous solution: Ni wherein
2+And Co
2+Mol ratio be 4: 1, Ni
2+And Cu
2+Mol ratio be 1: 1;
Preparation M
2+Reverse micro emulsion:
Get CTAB and place container, add normal hexane, n-hexyl alcohol and M
2+The aqueous solution is configured to Ni after fully stirring, NiCo and NiCu reverse micro emulsion;
Add reductive agent reduction M
2+:
With above-mentioned M
2+The aqueous solution or M
2+In the Glass tubing that seals with the collodion liquid film bottom reverse micro emulsion is packed into, vertically be immersed in and fill 50mmol/L-1mol/LKBH
4React in the beaker of solution, the NaOH solution that adds 0.2mol/L is regulated reductive agent KBH
4The pH value of solution can find that after the pH value is for reaction for some time under the alkaline condition of 10-12 collodion liquid film bottom has the black product to generate;
The aftertreatment of product:
Reverse micro emulsion carries out breakdown of emulsion earlier to be handled, then the atrament in the film is transferred in the centrifuge tube, generally respectively wash 3 times with deionized water and absolute ethanol washing product respectively,, discard centrifugate and promptly get desired product then with the rotating speed centrifugation of 4000rpm/min-5000rpm/min; At last, the product that newly makes is dissolved in the dehydrated alcohol, sealing is stored in the sample hose.
Described M
2+The aqueous solution is that the metal inorganic salt of solubility divalence Ni, Co, Cu makes, and purity is analytical pure; The purity of described CTAB, normal hexane, n-hexyl alcohol is analytical pure, and the purity of described dehydrated alcohol is chemical pure; Described KBH
4With the purity of NaOH be analytical pure.
The stirring of mentioning in described each step is undertaken by mechanical stirring or sonic oscillation mode.
Described preparation M
2+The stirring of mentioning in the reverse micro emulsion step, the required time is to make microemulsion reach the degree of transparent and homogeneous.
In the post-processing step of described product, after each washing is finished, separate with centrifuge separator and to wash again after removing deionized water and dehydrated alcohol next time.
The described sonic oscillation time is 10-30 minute.
Concrete, can
May further comprise the steps:
(1) makes the collodion liquid film
Adopt the equal glue machine of CHEMAT TECHNOLOGY SPIN-COATER KW-4A to prepare thickness greatly about the collodion liquid film of 0.12mm-0.18mm, adopt dropping collodion liquid on the silicon substrate in the rotation, make the film natural air drying behind the rotating speed rotation 15s with 1000r/min-1200r/min simultaneously, take off, standby.
(2) preparation Ni
2+The aqueous solution
Take by weighing 11.88mg NiCl
26H
2O places beaker, adds the 10ml deionized water, fully stirs to make its dissolving, is configured to the Ni of 0.005mol/L
2+The aqueous solution;
(3) preparation Ni
2+Reverse micro emulsion
Take by weighing 1.28g CTAB and place Erlenmeyer flask, add the 50ml normal hexane, 2.5ml n-hexyl alcohol and 2ml, 0.1mol/LNiCl
26H
2The O aqueous solution fully stirs and forms Ni
2+Reverse micro emulsion.
(4) the preparation NiCo aqueous solution
Take by weighing 9.50mgNiCl
26H
2O and 2.38mgCoCl
26H
2O places beaker, adds the 10ml deionized water, fully stirs and makes its dissolving, is configured to the NiCo aqueous solution.
(5) preparation NiCo reverse microemulsion solution
Take by weighing 1.28g CTAB and place Erlenmeyer flask, add the 50ml normal hexane, 2.5ml n-hexyl alcohol, 1.6ml, 0.1mol/LNiCl
26H
2The O aqueous solution, 0.4ml, 0.1mol/LCoCl
26H
2The O aqueous solution fully stirs and forms the NiCo reverse micro emulsion.
(6) the preparation NiCu aqueous solution
Take by weighing 7.27mgNi (NO
3)
26H
2O and 7.4mgCu (NO
3)
26H
2O places beaker, adds the 10ml deionized water, fully stirs and makes its dissolving, is configured to the NiCu aqueous solution.
(7) preparation NiCu reverse micro emulsion
Take by weighing 1.28g CTAB and place Erlenmeyer flask, add the 50ml normal hexane, 2.5ml n-hexyl alcohol, 1.0ml, 0.1mol/LNi (NO
3)
26H
2The O aqueous solution, 1.0ml, 0.1mol/LCu (NO
3)
26H
2The O aqueous solution fully stirs and forms the NiCu reverse micro emulsion.
(8) add reductive agent KBH
4Reduction M
2+
In the Glass tubing that will seal with the collodion liquid film bottom will packing into according to the 10ml solution that above-mentioned (2), (3), (4), (5), (6), (7) method make, vertically be immersed in and fill the KBH that 10ml contains 50mmol/L-1mol/L
4React in the beaker of solution (PH=12), can find after reaction for some time that collodion liquid film bottom has the black product to generate.
(9) aftertreatment of product
Atrament in the film is transferred to (reverse micro emulsion will carry out breakdown of emulsion earlier to be handled) in the centrifuge tube, use deionized water and washing with alcohol product (generally respectively washing 3 times) respectively, with the rotating speed centrifugation of 4500rpm/min, discard centrifugate and promptly get desired product then.At last, the product that newly makes is dissolved in the 15ml ethanol, sealing is stored in the sample hose.
Among the present invention, the described M that contains
2+Inorganic salt be the divalent metal inorganic salt of all solubilities, purity is not less than chemical pure.
Among the present invention, the purity of described CTAB, normal hexane, n-hexyl alcohol and dehydrated alcohol is not less than chemical pure.
Among the present invention, described KBH
4Be not less than chemical pure with the purity of NaOH.
Among the present invention, the stirring of mentioning in each step can be undertaken by modes such as mechanical stirring or vibration, sonic oscillations.
Among the present invention, the stirring of mentioning in step (3), (5), (7), the required time is good for making microemulsion reach transparent and homogeneous.
Among the present invention, the KBH of adding
4Amount look M
2+The kind of the aqueous solution and reverse micro emulsion and deciding, the scope of add-on is at 0.5-10mmol, and this scope can either satisfy the reductive needs can not cause the wasting of resources again.
Among the present invention, after each washing is finished, with wash again after the centrifuge separator separation next time.
Among the present invention, the described sonic oscillation time can suitably be adjusted according to the power of ultrasonic generating unit, and ultrasonic time is 10-30 minute usually.
Owing to adopt such scheme, the invention has the beneficial effects as follows:
1. the present invention has realized utilizing metal-salt soluble in water under the normal temperature presoma for reduction reaction, be equipped with amorphous metal and alloy nano-material by the soft and hard composite template legal system, break through single in the past template synthetic classical mode, inorganic synthetic a kind of new route of synthesis that provides is provided.
2. present method can be controlled the pattern of product, has very high practicality.
3. the present invention adopts simple inorganic salt as reactant respectively, has very strong versatility.
4. the present invention is that the employing reverse micro emulsion is the method for soft template, is different from the positive microemulsion method, and the water nuclear that contains metal ion is wrapped up by organic solvent, forms a micronucleus reactor, can further optimize the pattern of product.
5. the present invention is applied widely, can be used for the synthetic of multiple transition metal oxide and alloy material, by changing reductive agent, kinds of surfactants and consumption, crystal formation, pattern, particulate size to product are regulated and control, thereby obtain nano level different crystal forms, different-shape to the micron order material.
6. the portion of product of the present invention's preparation has good magnetic performance, can be used as magnetic head materials, piezomagnetic material, magnetic recording material etc., and comparatively vast potential for future development and application space are arranged.
7. technology of the present invention is simple, and whole preparation system makes up easily, and easy and simple to handle, condition is easily controlled, and is with low cost, and product pattern, size are easily controlled, the purity height, and the product processing is convenient succinct, is suitable for large-scale commercial production.
Description of drawings
Product TEM photo and the electron-diffraction diagram (lower right corner) thereof of Fig. 1 under the multiple of 50nm, obtaining among the embodiment 1.
The product TEM photo of Fig. 2 under the multiple of 50nm, obtaining among the embodiment 2
The product TEM photo of Fig. 3 under the multiple of 50nm, obtaining among the embodiment 3.
The product TEM photo of Fig. 4 under the multiple of 50nm, obtaining among the embodiment 4.
The product TEM photo of Fig. 5 under the multiple of 50nm, obtaining among the embodiment 5.
The product TEM photo of Fig. 6 under the multiple of 50nm, obtaining among the embodiment 6.
Embodiment
It is as follows to the present invention includes step:
(1) makes the collodion liquid film
Can adopt CHEMAT TECHNOLOGY SPIN-COATER KW-4A (a kind of concrete model, on instrument, have and indicate) all the glue machine prepare thickness greatly about the collodion liquid film of 0.12mm-0.18mm, adopt in the rotation dropping collodion liquid on the silicon substrate, make the film natural air drying behind the rotating speed rotation 15s with 1000r/min-1200r/min simultaneously, take off, standby;
(2) preparation M
2+The aqueous solution
Take by weighing a certain amount of metal-salt and place beaker, add the 10ml deionized water, fully stir and make its dissolving, be configured to Ni, the NiCo and the NiCu aqueous solution, for example: 10ml, 5mmol/L NiCl
26H
2The O aqueous solution, 10ml, 5mmol/L NiCl
26H
2O and CoCl
26H
2The mixing solutions of O, wherein Ni
2+And Co
2+Mol ratio be about 4: 1,10ml, 5mmol/L Ni (NO
3)
26H
2O and Cu (NO
3)
26H
2The mixing solutions of O, wherein Ni
2+And Cu
2+Mol ratio be about 1: 1.
(3) preparation M
2+Reverse microemulsion solution
Take by weighing 1.28g CTAB (cetyl trimethylammonium bromide) and place Erlenmeyer flask, add the 50ml normal hexane, the M of 2.5ml n-hexyl alcohol and certain volume 0.1mol/L
2+The aqueous solution is configured to Ni after fully stirring, NiCo and NiCu reverse micro emulsion, for example: 2ml, 0.1mol/LNiCl
26H
2The O aqueous solution, 1.6ml, 0.1mol/LNiCl
26H
2O and 0.4ml, 0.1mol/LCoCl
26H
2The mixing solutions of O, 1.0ml, 0.1mol/LNi (NO
3)
26H
2O and 1.0ml, 0.1mol/LCu (NO
3)
26H
2The mixing solutions of O.
(4) add reductive agent reduction M
2+
With the above-mentioned M of 10ml
2+Solution or M
2+In the Glass tubing that seals with the collodion liquid film bottom reverse micro emulsion is packed into, vertically be immersed in the KBH of the 50mmol/L-1mol/L that fills 10ml
4React in the beaker of solution, the pH value is under the alkaline condition of 10-12; For the metal ion aqueous solution, the concentration of used reductive agent is: 50mmol/L, and for the metal ion reverse micro emulsion, the concentration of used reductive agent is: 1mol/L;
Can find after reaction for some time that collodion liquid film bottom has the black product to generate;
(5) aftertreatment of product
Atrament in the film (reverse micro emulsion will carry out breakdown of emulsion earlier to be handled) is transferred in the centrifuge tube, use deionized water and washing with alcohol product (generally respectively to wash 3 times respectively, reach the centrifugate clarification), then with the rotating speed centrifugation of 4500rpm/min, discard centrifugate and promptly get desired product; At last, the product that newly makes is dissolved in the 15ml ethanol, sealing is stored in the sample hose.
The stirring of mentioning in the described step (3), the required time is good for making microemulsion reach transparent and homogeneous.
The invention is further illustrated by the following examples.
Embodiment 1:Ni two dimension amorphous nano material
The first step takes by weighing 11.88mg NiCl
26H
2O places beaker, adds the 10ml deionized water, fully stirs to make its dissolving, is configured to the Ni of 0.005mol/L
2+The aqueous solution;
Second step, accurately weighing 27mgKBH
4Place beaker, add the 10ml deionized water, fully stir and make its dissolving, be configured to the KBH of 0.05mol/L
4The aqueous solution, the NaOH solution of adding finite concentration (for example 0.2mol/L) is regulated its pH value and is about 12;
The 3rd step is Ni
2+In the Glass tubing that seals with the collodion liquid film bottom the aqueous solution is packed into, vertically be immersed in and fill KBH
4React in the beaker of solution, can find after reaction for some time that collodion liquid film bottom has atrament to generate;
The 4th step, after reaction finishes, shift black precipitate in centrifuge tube, give a baby a bath on the third day after its birth all over reaching the centrifugate clarification with deionized water and ethanol respectively, go out to precipitate with the rotating speed centrifugation of 4000rpm/min, discard centrifugate, promptly get desired product; At last, in 15ml ethanol, sealing is stored in the sample hose with the resolution of precipitate that newly makes.
The ultra-fine two-dimentional amorphous nano material of embodiment 2:Ni
The first step takes by weighing 1.28g CTAB and places Erlenmeyer flask, adds the 50ml normal hexane, 2.5ml n-hexyl alcohol and 2ml, 0.1mol/LNiCl
26H
2The O aqueous solution fully stirs and forms Ni
2+Reverse micro emulsion.
Second step, accurately weighing 0.54gKBH
4Place beaker, add the 10ml deionized water, fully stir and make its dissolving, be configured to the KBH of 1.0mol/L
4Solution, the NaOH solution of adding finite concentration (for example 0.2mol/L) is regulated its pH value and is about 12.
In the 3rd step, measure 10mLNi
2+In the Glass tubing that seals with the collodion liquid film bottom reverse micro emulsion is packed into, vertically be immersed in and fill KBH
4React in the beaker of solution, can find after reaction for some time that collodion liquid film bottom has atrament to generate;
The 4th step, after reaction finishes, microemulsion carried out breakdown of emulsion after, shift black precipitate in centrifuge tube, give a baby a bath on the third day after its birth time with deionized water and ethanol respectively, reach centrifugate and clarify, rotating speed centrifugation with 4000rpm/min goes out precipitation, discards centrifugate, promptly gets desired product.At last, in 15ml ethanol, sealing is stored in the sample hose with the resolution of precipitate that newly makes.
Embodiment 3:NiCo two dimension amorphous alloy nano material
The first step takes by weighing 9.50mgNiCl
26H
2O and 2.38mgCoCl
26H
2O places beaker, adds the 10ml deionized water, fully stirs and makes its dissolving, is configured to the NiCo aqueous solution.
Second step, accurately weighing 27mgKBH
4Place beaker, add the 10ml deionized water, fully stir and make its dissolving, be configured to the KBH of 0.05mol/L
4Solution, the NaOH solution of adding finite concentration (for example 0.2mol/L) is regulated its pH value and is about 12.
In the 3rd step, in the Glass tubing that seals with the collodion liquid film bottom the NiCo aqueous solution is packed into, vertically be immersed in and fill KBH
4React in the beaker of solution, can find after reaction for some time that collodion liquid film bottom has atrament to generate.
The 4th step, after reaction finishes, shift black precipitate in centrifuge tube, give a baby a bath on the third day after its birth time with deionized water and ethanol respectively, reach the centrifugate clarification, go out to precipitate with the rotating speed centrifugation of 4000rpm/min, discard centrifugate, promptly get desired product.At last, in 15ml ethanol, sealing is stored in the sample hose with the resolution of precipitate that newly makes.
The ultra-fine two-dimentional amorphous alloy nano material of embodiment 4:NiCo
The first step takes by weighing 1.28g CTAB and places Erlenmeyer flask, adds the 50ml normal hexane, 2.5ml n-hexyl alcohol, 1.6ml, 0.1mol/LNiCl
26H
2The O aqueous solution, 0.4ml, 0.1mol/LCoCl
26H
2The O aqueous solution fully stirs and forms the NiCo reverse micro emulsion.
Second step, accurately weighing 0.54gKBH
4Place beaker, add the 10ml deionized water, fully stir and make its dissolving, be configured to the KBH of 1.0mol/L
4Solution, the NaOH solution of adding finite concentration (for example 0.2mol/L) is regulated its pH value and is about 12.
The 3rd step, measure the 10mLNiCo reverse micro emulsion and pack in the Glass tubing that the bottom seals with the collodion liquid film, vertically be immersed in and fill KBH
4React in the beaker of solution, can find after reaction for some time that collodion liquid film bottom has atrament to generate.
The 4th step, after reaction finishes, microemulsion carried out breakdown of emulsion after, shift black precipitate in centrifuge tube, give a baby a bath on the third day after its birth time with deionized water and ethanol respectively, reach centrifugate and clarify, rotating speed centrifugation with 4000rpm/min goes out precipitation, discards centrifugate, promptly gets desired product.At last, in 15ml ethanol, sealing is stored in the sample hose with the resolution of precipitate that newly makes.
Embodiment 5:NiCu two dimension amorphous alloy nano material
The first step takes by weighing 7.27mgNi (NO
3)
26H
2O and 7.4mgCu (NO
3)
26H
2O places beaker, adds the 10ml deionized water, fully stirs and makes its dissolving, is configured to the NiCu aqueous solution.
Second step, accurately weighing 27mgKBH
4Place beaker, add the 10ml deionized water, fully stir and make its dissolving, be configured to 0.05mol/LKBH
4Solution, adding finite concentration (for example 0.2mol/L) NaOH solution is regulated its pH value and is about 12.
In the 3rd step, in the test tube that seals with the collodion liquid film bottom the NiCu aqueous solution is packed into, be immersed in and fill KBH
4React in the beaker of solution, can find after reaction for some time that collodion liquid film bottom has atrament to generate.
The 4th step, after reaction finishes, shift black precipitate in centrifuge tube, give a baby a bath on the third day after its birth time with deionized water and ethanol respectively, reach the centrifugate clarification, go out to precipitate with the rotating speed centrifugation of 4000rpm/min, discard centrifugate, promptly get desired product.At last, in 15ml ethanol, sealing is stored in the sample hose with the resolution of precipitate that newly makes.
The ultra-fine two-dimentional amorphous alloy nano material of embodiment 6:NiCu
The first step takes by weighing 1.28g CTAB and places Erlenmeyer flask, adds the 50ml normal hexane, 2.5ml n-hexyl alcohol, 1.0ml, 0.1mol/LNi (NO
3)
26H
2The O aqueous solution, 1.0ml, 0.1mol/LCu (NO
3)
26H
2The O aqueous solution fully stirs and forms the NiCu reverse micro emulsion.
Second step, accurately weighing 0.54gKBH
4Place beaker, add the 10ml deionized water, fully stir and make its dissolving, be configured to the KBH of 1.0mol/L
4Solution, adding finite concentration (for example 0.2mol/L) NaOH solution is regulated its pH value and is about 12.
The 3rd step, measure the 10mLNiCu reverse micro emulsion and pack in the Glass tubing that the bottom seals with the collodion liquid film, vertically be immersed in and fill KBH
4React in the beaker of solution, can find after reaction for some time that collodion liquid film bottom has atrament to generate.
The 4th step, after reaction finishes, microemulsion carried out breakdown of emulsion after, shift black precipitate in centrifuge tube, give a baby a bath on the third day after its birth all over reaching the centrifugate clarification with deionized water and ethanol respectively), go out precipitation with the rotating speed centrifugation of 4000rpm/min, discard centrifugate, promptly get desired product.At last, in 15ml ethanol, sealing is stored in the sample hose with the resolution of precipitate that newly makes.
Above embodiment is under laboratory condition, and the consumption of raw material is less, and industrial production only needs the raw material consumption is doubled to get final product accordingly.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (7)
1. the preparation method of an amorphous alloy nano material is characterized in that: may further comprise the steps:
Make the collodion liquid film:
Drip collodion liquid on the silicon substrate in the rotation, make the film natural air drying after the rotation simultaneously, take off, standby;
Preparation M
2+The aqueous solution:
Get metal-salt and place container, add deionized water, fully stir and make its dissolving, be configured to M
2+The aqueous solution;
Preparation M
2+Reverse micro emulsion:
Get CTAB and place container, add normal hexane, n-hexyl alcohol and M
2+The aqueous solution is configured to M after fully stirring
2+Reverse micro emulsion;
Add reductive agent reduction M
2+: with above-mentioned M
2+The aqueous solution or M
2+In the Glass tubing that seals with the collodion liquid film bottom reverse micro emulsion is packed into, vertically be immersed in and fill KBH
4React in the beaker of solution, the NaOH solution that adds 0.2mol/L is regulated reductive agent KBH
4The pH value of solution, alkaline condition can find that collodion liquid film bottom has the black product to generate after reaction for some time down;
The aftertreatment of product:
Reverse micro emulsion carries out breakdown of emulsion earlier to be handled, and this black product washing is reached the centrifugate clarification, discards centrifugate and promptly gets desired product.
2. the preparation method of amorphous alloy nano material according to claim 1, it is characterized in that: step is as follows:
Make the collodion liquid film:
Adopt equal glue machine to prepare the collodion liquid film that thickness is 0.12mm-0.18mm, adopt on the silicon substrate in the rotation and drip collodion liquid, make the film natural air drying after rotating 15-20s with the rotating speed of 1000r/min-1200r/min simultaneously, take off, standby; Preparation M
2+The aqueous solution:
Get metal-salt and place container, add deionized water, fully stir and make its dissolving, be configured to M
2+The aqueous solution: Ni wherein
2+And Co
2+Mol ratio be 4: 1, Ni
2+And Cu
2+Mol ratio be 1: 1;
Preparation M
2+Reverse micro emulsion:
Get CTAB and place container, add normal hexane, n-hexyl alcohol and M
2+The aqueous solution is configured to Ni after fully stirring, NiCo and NiCu reverse micro emulsion;
Add reductive agent reduction M
2+:
With above-mentioned M
2+The aqueous solution or M
2+In the Glass tubing that seals with the collodion liquid film bottom reverse micro emulsion is packed into, vertically be immersed in and fill 50mmol/L-1mol/LKBH
4React in the beaker of solution, the NaOH solution that adds 0.2mol/L is regulated reductive agent KBH
4The pH value of solution can find that after the pH value is for reaction for some time under the alkaline condition of 10-12 collodion liquid film bottom has the black product to generate;
The aftertreatment of product:
Black product in the film is transferred in the centrifuge tube, uses deionized water and absolute ethanol washing product respectively, each washs 3 times, then with the rotating speed centrifugation of 4000rpm/min-5000rpm/min, discards centrifugate and promptly gets desired product; At last, the product that newly makes is dissolved in the dehydrated alcohol, sealing is stored in the sample hose.
3. the preparation method of amorphous alloy nano material according to claim 2 is characterized in that: described M
2+The aqueous solution is that the metal inorganic salt of solubility divalence Ni, Co, Cu makes, and purity is analytical pure; The purity of described CTAB, normal hexane, n-hexyl alcohol is analytical pure, and the purity of described dehydrated alcohol is chemical pure; Described KBH
4With the purity of NaOH be analytical pure.
4. the preparation method of amorphous alloy nano material according to claim 1 and 2 is characterized in that: the stirring of mentioning in described each step, undertaken by mechanical stirring or sonic oscillation mode.
5. the preparation method of amorphous alloy nano material according to claim 1 and 2 is characterized in that: described preparation M
2+The stirring of mentioning in the reverse micro emulsion step, the required time is to make microemulsion reach the degree of transparent and homogeneous.
6. the preparation method of amorphous alloy nano material according to claim 1 and 2, it is characterized in that: in the post-processing step of described product, after each washing is finished, separate with centrifuge separator and to wash again after removing deionized water and dehydrated alcohol next time.
7. the preparation method of amorphous alloy nano material according to claim 4, it is characterized in that: the described sonic oscillation time is 10-30 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910049956XA CN101538692B (en) | 2009-04-24 | 2009-04-24 | Method for preparing two-dimensional Ni-based amorphous alloy nanophase material by soft and hard composite template method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910049956XA CN101538692B (en) | 2009-04-24 | 2009-04-24 | Method for preparing two-dimensional Ni-based amorphous alloy nanophase material by soft and hard composite template method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101538692A CN101538692A (en) | 2009-09-23 |
| CN101538692B true CN101538692B (en) | 2011-01-19 |
Family
ID=41122075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910049956XA Expired - Fee Related CN101538692B (en) | 2009-04-24 | 2009-04-24 | Method for preparing two-dimensional Ni-based amorphous alloy nanophase material by soft and hard composite template method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101538692B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104966841B (en) * | 2015-05-11 | 2017-03-01 | 同济大学 | A kind of preparation method of Pd/NiCu two-dimensional nano composite |
| CN105834446B (en) * | 2016-04-12 | 2017-12-26 | 同济大学 | A kind of synthetic method of ultra-thin stratiform NiO CoOx nanometer sheets load NiCo nano compositions |
| CN109261156B (en) * | 2018-10-26 | 2021-08-10 | 同济大学 | Nickel film and zinc oxide nanorod composite material as well as preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101053906A (en) * | 2006-04-11 | 2007-10-17 | 三星电机株式会社 | Method for manufacturing nickel nanoparticles |
| CN101168196A (en) * | 2006-10-27 | 2008-04-30 | 同济大学 | Method for preparing nickel-base amorphous nano particles |
-
2009
- 2009-04-24 CN CN200910049956XA patent/CN101538692B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101053906A (en) * | 2006-04-11 | 2007-10-17 | 三星电机株式会社 | Method for manufacturing nickel nanoparticles |
| CN101168196A (en) * | 2006-10-27 | 2008-04-30 | 同济大学 | Method for preparing nickel-base amorphous nano particles |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平8-109454A 1996.04.30 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101538692A (en) | 2009-09-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103193273B (en) | Preparation method of extra-long manganese dioxide nanowires | |
| Lu et al. | Redox cycles promoting photocatalytic hydrogen evolution of CeO 2 nanorods | |
| Zhang et al. | Facile electrochemical synthesis of CeO 2 hierarchical nanorods and nanowires with excellent photocatalytic activities | |
| CN101746837B (en) | Preparation method of cobalt sulfide micro tube with hiberarchy structure | |
| CN107262116B (en) | Hierarchical structure MoS2/Cu2S composite material and preparation method thereof | |
| CN103030169B (en) | Shape-controlled preparation method of nanometer copper oxide | |
| CN104538200A (en) | Graphene / Fe-MOFs composite material and preparation method thereof | |
| CN109536991A (en) | A kind of application of the preparation method and cuprous oxide of loose porous cuprous oxide material in electro-catalysis reduction carbon dioxide | |
| CN101538692B (en) | Method for preparing two-dimensional Ni-based amorphous alloy nanophase material by soft and hard composite template method | |
| CN104817120A (en) | Preparation method of sea urchin-like Ni/Co composite basic carbonate | |
| CN102583353B (en) | Hydrothermal method for preparing graphene | |
| CN104787806B (en) | A kind of rose-shaped nano Cobalto-cobaltic oxide and preparation method thereof | |
| CN100503094C (en) | A method for preparing Co-Ni-Cu architecture amorphous alloy monodispersity nanometer particle | |
| CN103985560A (en) | Hydrotalcite/carbon nano-tube/nickel multi-level structure thin film and preparation method and application thereof | |
| CN101486494B (en) | Method for synthesizing cobalt carbonate hydroxide nano material | |
| CN101805009A (en) | Simple and controllable method for preparing lobate micron/nano copper oxide two-dimensional assembly | |
| CN103771490B (en) | A kind of simple and easy stirring at room temperature prepares the method for micro-/ nano zinc oxide | |
| CN101736332B (en) | Method for synthesizing amorphous nickel-cobalt alloy nano-film loaded with platinum particles | |
| CN103342396A (en) | Method for microwave liquid-phase synthesis of graphene-like two-dimensional nickel hydroxide nano material | |
| CN103387228B (en) | Preparation method for graphene scrolls | |
| Wu et al. | Advances in Chemical Synthesis of Nb-Containing Oxides | |
| Hu et al. | Novel synthesis of CuO nanofiber balls and films and their UV–visible light filteration property | |
| CN102786038B (en) | Hydro-thermal synthesis method of cubic phase InSe nano sheet | |
| Stoica et al. | Two-dimensional coordination polymers containing permethylated motifs-promising candidates for 2D emerging materials. Structural, behavioral and functional particularities | |
| CN102179525B (en) | Controllable synthesis method for preparing nickel platinum double-layered nanometer bowl at room temperature |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110119 Termination date: 20130424 |