CN105420761B - Method for preparing various metal Janus particles by self-reducing on aluminum oxide template - Google Patents
Method for preparing various metal Janus particles by self-reducing on aluminum oxide template Download PDFInfo
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- CN105420761B CN105420761B CN201510746413.9A CN201510746413A CN105420761B CN 105420761 B CN105420761 B CN 105420761B CN 201510746413 A CN201510746413 A CN 201510746413A CN 105420761 B CN105420761 B CN 105420761B
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- metal
- janus particles
- aluminum oxide
- janus
- autoreduction
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
Abstract
The invention provides a method for preparing various metal Janus particles by self-reducing on an aluminum oxide template. The method comprises the following steps: taking a clean aluminum foil as an anode, taking a lead plate as a cathode, electrolyzing in a phosphoric acid solution, enabling the surface of the aluminum coil to generate a layer of aluminum oxide film; then, soaking the oxidized aluminum coil into the phosphoric acid solution to obtain an expanded aluminum oxide template; then, putting the oxidized aluminum foil into a chlorine salt solution of metal; after reducing slat ions of the metal into metal simple substances on the aluminum oxide template, carrying out ultrasonic treatment on a sample in an alcohol solution, and collecting metal Janus particles, wherein one side of each collected metal Janus particle is planar, and the other side of each collected metal Janus particle is in the shape of a sphere or a petal and the like; dissolving the aluminum oxide sample with self-reduced metal salt ions by use of a sodium hydroxide solution, thereby obtaining the metal Janus particles, one half of which are in the shapes of spheres or petals while the rest are in the shapes of rods. The method is simple, economical and environmentally-friendly, and can stably prepare various metal Janus particles, which are smaller than 10 microns, uniform and various in morphology, in a large area.
Description
Technical field
The invention belongs to chemical field, is related to a kind of preparation method of Janus particles, specifically one kind is in aluminum oxide
The method that autoreduction prepares various metals Janus particles in template.
Background technology
Janus is god's (Janus) in ancient Roman's mythology with two faces in front and back.De Gennes were in Nobel in 1991
Borrow Janus in prize-winning speech first and represent the particle with 2 kinds of different qualities.Later academia continued to use this title,
Non-centrosymmetrical particle with different qualities is referred to as Janus particles by visualization ground.The raw material for building Janus particles can
Being organic (polymer), inorganic compound and organic-inorganic hybrid material.2 hemisphere of Janus particles can have respectively not
With pattern and (or) different chemical compositions, so as to different property, such as hydrophilic/hydrophobic, positive/negative electric charge, polarity/
Nonpolar, light or magnetic etc..Its particle size is generally micron or nanoscale.In sensing, surfactant, Electronic Paper, medicine
The field such as carrier and catalysis has practical application or with potential using value, has been a great concern in recent years.
The preparation method of Janus particles can substantially be divided into two classes：One kind is balanced method.Balanced method is gone mainly to include
Two kinds, one kind is selective surface modification；Another kind is control phase separation method.Balanced method is gone mainly to synthesize first uniform
Nanoscale or micron particles, are then selectively modified with some way on the surface of particle, non-equal for synthesizing
Even or asymmetry particle.This method can synthesize substantial amounts of with heterogeneity or different structure feature
Janus particles.But this method use it is relative complex, especially with respect to the scope of surface modification, it is difficult to control, therefore
Using not being especially extensive.Another kind of method is direct synthesis technique, and this method is a lot, mainly including self assembly, control surface
The preparation of nucleation and microfluid.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides prepared by one kind autoreduction on alumina formwork
The method of various metals Janus particles, the described this autoreduction on alumina formwork prepares various metals Janus particles
Method solves the method complex process for preparing various metals Janus particles of the prior art, and the scope of surface modification is difficult to
The technical problem of control.
The invention provides a kind of method that autoreduction on alumina formwork prepares various metals Janus particles, including
Following steps：
1) the step of anodised aluminium, aluminium foil is cleaned by ultrasonic at ambient temperature, and deionized water is rinsed, will
Aluminium foil is placed on alkaline etching in sodium hydroxide solution, and then deionized water is rinsed, and is subsequently placed in acid etching in salpeter solution, will be above-mentioned clear
Clean aluminium foil, with stereotype as negative electrode, is electrolysed, electrolyte constant temperature so as to one layer of oxygen of Surface Creation as anode in phosphoric acid solution
Change aluminium film；
2) the step of aluminum oxide reaming, reacted aluminium foil is immersed in phosphoric acid solution；
3) the step of deposited metal, the alumina foil after above-mentioned process is inserted in the salting liquid of metal, described
Metal is nickel, cobalt, copper, tin, palladium, gold or platinum, and the anion in described salting liquid is chlorion, is taken out after reaction；
4) the step of collection Janus particle, ultrasonic again by the sample after above-mentioned deposited metal, collects metal Janus
Particle, or the sample after deposited metal is dissolved in sodium hydroxide solution, metal Janus particles are collected after washing.
Further, step 1）The concentration of middle phosphoric acid solution is 2.5-4mol/L；0 ~ 5 DEG C of reaction temperature；Reaction time is
5min-24h, voltage is 30-60V；Most preferably 0 DEG C of reaction temperature.
Further, step 2）The mass fraction 3 ~ 8% of middle phosphoric acid solution, reaction time 5-25min, reaction temperature be 25 ~
35℃；Optium concentration is mass fraction 5%；Optimum temperature is 30 DEG C.
Further, in step 4）Reaction temperature is normal temperature, and the example reaction time is 10s-30min.
Further, step 4）The time of ultrasound is in 10-24h；The mass fraction 20% of sodium hydroxide solution, dissolving oxidation
The aluminum alloy pattern plate time is in more than 2h.
Further, step 1）In, it is cleaned by ultrasonic with acetone and ethanol successively.
Further, described metal is nickel, cobalt, copper, tin, palladium, gold or platinum.
Further, step 3）Middle plating solution is NiCl2·6H2O, SnCl2·2H2O, CuCl2·2H2O, CoCl2·
6H2O, PdCl2, HAuCl4·4H2O and H2PtCl6·6H2O。
Specifically, the concentration of above-mentioned plating solution is 0.1 ~ 5mol/L.
The present invention proposes the porous oxidation that a kind of simple and environmentally-friendly method prepares various metals Janus particles, will prepare
Aluminium is put into the salting liquid of metal（Chlorion is anion）, take out for a period of time, can collect metal Janus after ultrasound
Particle.The method is easy to operate, can prepare in a large number including various even particle sizes such as nickel, cobalt, copper, tin, palladium, gold, platinum
Janus particles, and other things can be prepared by the method for the metal spraying on the alumina formwork of deposited metal and Erodent Algorithm
Change the different Janus particles of property.
The present invention is compared with prior art, and its technological progress is significant.The method of the present invention is simple, economic and environment-friendly, can
Stable large-area preparation is less than 10 microns, and particle is uniform, the different various metals Janus particles of pattern, including nickel,
Cobalt, copper, tin, palladium, gold, platinum.Janus particle prepared by this method also can be used as the Janus for preparing other different physico-chemical properties
The raw material of particle, and in catalysis, there are many potential using values in electronics, magnetomechanics field.Using the method for the present invention, it is not required to
Power supply is wanted, simple to operate, solution composition is single, and the even particle size for generating.
Description of the drawings
Fig. 1 is that nickel is deposited on electron microscope on alumina formwork in embodiment 1.
Fig. 2 is the nickel Janus particle electron microscopes collected after ultrasound in embodiment 1.
Fig. 3 is the nickel Janus particle electron microscopes collected after NaOH dissolving alumina formwork in embodiment 1.
Fig. 4 is the energy spectrum diagram of single nickel Janus particles in embodiment 1.
Specific embodiment
Embodiment 1
First, by aluminium flake（Aluminium element content is 99,99%）Cleaned with acetone, EtOH Sonicate successively, and deionized water is rushed
Wash and dry up.It is subsequently dipped to be processed in the sodium hydrate aqueous solution of 1mol/L, the time is 1min, and deionized water is rinsed after taking-up,
And dry up, 1min in the salpeter solution of mass fraction 10% is next immersed again, deionized water is rinsed after taking-up, is dried up.Prepare
Used as electrolyte, then with aluminium sheet as anode, stereotype is reacted the phosphoric acid solution of 2.7mol/L for cathodal closing.Control reaction
Temperature is 0 DEG C, and constant voltage 50V, the reaction time is 2h.Reacted aluminium flake deionized water is cleaned and dried up, and will oxidation
Aluminium foil immersion mass fraction 5% phosphoric acid solution in 10 minutes, obtain reaming after alumina formwork, next by oxidation
Aluminium foil is put into the NiCl of 1mol/L2Solution 12min, take out sample deionized water clean and after drying up by sample in ethanol solution
Interior ultrasonic 12h, you can collect one side for plane, be simultaneously spherical nickel Janus particles.By autoreduction nickel alumina foil sample
Dissolved with the sodium hydroxide solution of mass fraction 20%, it is spherical that can obtain half, the nickel Janus particles that second half is bar-like.
Embodiment 2
First, by aluminium flake（Aluminium element content is 99,99%）Cleaned with acetone, EtOH Sonicate successively, and deionized water is rushed
Wash and dry up.It is subsequently dipped to be processed in the sodium hydrate aqueous solution of 1mol/L, the time is 1min, and deionized water is rinsed after taking-up,
And dry up, 1min in the salpeter solution of mass fraction 10% is next immersed again, deionized water is rinsed after taking-up, is dried up.Prepare
Used as electrolyte, then with aluminium sheet as anode, stereotype is reacted the phosphoric acid solution of 3.0mol/L for cathodal closing.Control reaction
Temperature is 2 DEG C, and constant voltage 45V, the reaction time is 2.5h.Reacted aluminium flake deionized water is cleaned and dried up, and by oxygen
15 minutes in the phosphoric acid solution of the aluminium foil immersion mass fraction 5% of change, the alumina formwork after reaming is obtained, next will oxidation
Aluminium foil be put into the CoCl of 1mol/L2Solution 13min, takes out sample deionized water and cleans and sample is molten in ethanol after drying up
Ultrasound 15h in liquid, you can collect one side for plane, be simultaneously spherical cobalt Janus particles.By from the alumina foil sample of former cobalt
The product sodium hydroxide solution of mass fraction 20% dissolves, and it is spherical that can obtain half, the cobalt Janus particles that second half is bar-like.
Embodiment 3
First, by aluminium flake（Aluminium element content is 99,99%）Cleaned with acetone, EtOH Sonicate successively, and deionized water is rushed
Wash and dry up.It is subsequently dipped to be processed in the sodium hydrate aqueous solution of 1mol/L, the time is 1.5min, deionized water punching after taking-up
Wash, and dry up, 1.5min in the salpeter solution of mass fraction 10% is next immersed again, deionized water is rinsed after taking-up, is blown
It is dry.The phosphoric acid solution of 2.9mol/L is prepared as electrolyte, then with aluminium sheet as anode, stereotype is reacted for cathodal closing.
Controlling reaction temperature is 0 DEG C, and constant voltage 55V, the reaction time is 3h.Reacted aluminium flake deionized water is cleaned and dried up,
And by 20 minutes in the phosphoric acid solution of the aluminium foil immersion mass fraction 5% of oxidation, the alumina formwork after reaming is obtained, next
The aluminium foil of oxidation is put into into the CuCl of 0.1mol/L2Solution 4min, takes out sample deionized water and cleans and after drying up by sample
The ultrasound 18h in ethanol solution, you can collect one side for plane, be simultaneously petal-like nickel Janus particles.By autoreduction copper
Alumina foil sample dissolved with the sodium hydroxide solution of mass fraction 20%, it is spherical that can obtain half, and second half is petal-shaped
Copper Janus particles.
Claims (6)
1. a kind of method that autoreduction on alumina formwork prepares various metals Janus particles, it is characterised in that including as follows
Step：
1）The step of one anodised aluminium, aluminium foil is cleaned by ultrasonic at ambient temperature, and deionized water is rinsed, by aluminium foil
Alkaline etching in sodium hydroxide solution is placed on, then deionized water is rinsed, and acid etching in salpeter solution is subsequently placed in, by above-mentioned cleaning
Aluminium foil, with stereotype as negative electrode, is electrolysed, electrolyte constant temperature so as to one layer of aluminum oxide of Surface Creation as anode in phosphoric acid solution
Film；
2）The step of one aluminum oxide reaming, reacted aluminium foil is immersed in phosphoric acid solution；
3）The step of one deposited metal, the alumina foil after above-mentioned process is inserted in the salting liquid of metal, described metal
For nickel, cobalt, copper, tin, palladium, gold or platinum, the anion in described salting liquid is chlorion, is taken out after reaction；
4）It is the step of one collection Janus particle, the sample after above-mentioned deposited metal is ultrasonic again, metal Janus particles are collected,
Or dissolve the sample after deposited metal in sodium hydroxide solution, metal Janus particles are collected after washing.
2. the method that a kind of autoreduction on alumina formwork according to claim 1 prepares various metals Janus particles,
It is characterized in that：Step 1）The concentration of middle phosphoric acid solution is 2.5-4mol/L；0 ~ 5 DEG C of reaction temperature；Reaction time is 5min-24h,
Voltage is 30-60V.
3. the method that a kind of autoreduction on alumina formwork according to claim 1 prepares various metals Janus particles,
It is characterized in that：Step 2）The mass fraction 3 ~ 8% of middle phosphoric acid solution, reaction time 5-25min, reaction temperature is 25 ~ 35 DEG C.
4. the method that a kind of autoreduction on alumina formwork according to claim 1 prepares various metals Janus particles,
It is characterized in that：In step 3）Reaction temperature is normal temperature, and the example reaction time is 10s-30min.
5. the method that a kind of autoreduction on alumina formwork according to claim 1 prepares various metals Janus particles,
It is characterized in that：Step 4）The time of ultrasound is in 10-24h；The mass fraction of sodium hydroxide solution is 20%, dissolves alumina formwork
Time is in more than 2h.
6. the method that a kind of autoreduction on alumina formwork according to claim 1 prepares various metals Janus particles,
It is characterized in that：Step 1）In, it is cleaned by ultrasonic with acetone and ethanol successively.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510746413.9A CN105420761B (en) | 2015-11-05 | 2015-11-05 | Method for preparing various metal Janus particles by self-reducing on aluminum oxide template |
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| CN109502630A (en) * | 2018-12-21 | 2019-03-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of zinc oxide nanowire and products thereof and application |
| CN109834292B (en) * | 2019-04-11 | 2021-11-23 | 中国科学院宁波材料技术与工程研究所 | Macroscopic large-area two-dimensional Janus nano gold film and preparation method and application thereof |
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| FR2969508B1 (en) * | 2010-12-22 | 2015-11-13 | Univ Bordeaux 1 | DISSYMETRIC PARTICLES (JANUS PARTICLES) AND THEIR BIPOLAR ELECTROCHEMISTRY SYNTHESIS METHOD. |
| CN102191528B (en) * | 2011-04-02 | 2012-12-19 | 河北师范大学 | Preparation method of Co nanotube and alumina composite film with bright colors and different patterns |
| CN103373733B (en) * | 2012-04-12 | 2015-08-19 | 中国科学院化学研究所 | Surface has club-shaped material of multiple character and preparation method thereof |
| CN104451813A (en) * | 2014-12-01 | 2015-03-25 | 中国科学院合肥物质科学研究院 | Preparation method of gold nanometer tubes embedded in aluminum oxide template |
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