CN105965032B - The method that electrochemistry prepares Ag-Pd Nanoalloys in quaternary ion liquid microemulsion - Google Patents
The method that electrochemistry prepares Ag-Pd Nanoalloys in quaternary ion liquid microemulsion Download PDFInfo
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- CN105965032B CN105965032B CN201610595950.2A CN201610595950A CN105965032B CN 105965032 B CN105965032 B CN 105965032B CN 201610595950 A CN201610595950 A CN 201610595950A CN 105965032 B CN105965032 B CN 105965032B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/24—Alloys obtained by cathodic reduction of all their ions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses the methods that electrochemistry in a kind of quaternary ion liquid microemulsion prepares Ag Pd Nanoalloys, for this method in the quaternary ion liquid microemulsion system with high electrical conductivity that bimetal salt aqueous solution, 1 butyl of chlorination, 3 methylimidazole ionic liquid, n-butanol, cetyl trimethylammonium bromide are constituted, Direct Electrochemistry is prepared into the Ag Pd Nanoalloys that grain size is 2~13nm.The method of the present invention has the advantages that equipment is cheap, easy to operate, and the size of gained Ag Pd Nanoalloys and distribution can be regulated and controled by different electrochemistry preparation conditions.
Description
Technical field
The present invention relates to one kind using quaternary ion liquid microemulsion as in electrolyte solution, is directly existed by electrochemical reduction
The method that Ag-Pd Nanoalloys are prepared in electrolyte solution.
Background technology
Nano metal material be in recent years by new material of people's attention, therefore, the preparation of nano metal material
It is a very active research field.Nano metal material because its grain size is small, large specific surface area due to have it is unusual, excellent
Physics more and chemical characteristic.Nano metal material illustrates good application prospect in each field, such as：Electro-catalysis,
Bio-sensing microelectronic component and photocatalysis etc..Currently, having much for the method for preparing nano metal material, wherein micro-
Emulsion method is one of the method for very promising synthesis nano metal material.
Microemulsion be by two or more immiscible liquid, under the action of surfactant molecule interfacial film, shape
At a kind of Thermodynamically stable and isotropic dispersed system.The liquid-drop diameter of microemulsion dispersed phase is usually 1~
100nm is a kind of solution system with special construction and performance.In this system, " the nanometer stablized by surfactant
Pond " can be used as microreactor, can limit nucleation, growth and the reunion of particle.Therefore, in this medium, pass through
Regulation and control synthesis condition can obtain granular size and composition it is controllable, the good nano material of particle diameter distribution.Currently, it largely receives
Rice size material is prepared by chemical method in microemulsion, often by the way that reducing agent or oxidant are added into microemulsion
Corresponding nano material is obtained using electronation or chemical oxidation.It is difficult since the electric conductivity of general microemulsion system is very poor
For electrochemical research, so, the method for preparing nano metal material in microemulsion currently with electrochemical method obtains
Extensive concern.
Ionic liquid is since its thermal stability is good, conductivity is high, vapour pressure is extremely low, nonflammable, suitable polarity, wide electricity
Chemical window and cyclicity wait well excellent properties, thus receive researcher and widely pay attention to.In addition, ionic liquid can also lead to
It crosses and changes the structure and composition of zwitterion to adjust its physics, chemical property.Ionic liquid is determined because of its unique structure
Its unique physical and chemical performance, this also becomes a kind of novel solvent or material and is widely used.Currently, ionic liquid
Body also plays an important role as a kind of novel medium and material in the preparation of nano material.Ionic liquid due to
Its wide electrochemical window and relatively high conductivity, are widely used in electrochemical research.
Invention content
The technical problems to be solved by the invention are a kind of easy to operate in offer, molten by electrolyte of ion liquid microemulsion
Liquid, the method that the Ag-Pd Nanoalloys of size tunable are directly prepared in ion liquid microemulsion.
Technical solution is made of following step used by solving above-mentioned technical problem:
1, quaternary ion liquid microemulsion is prepared
The raw material of following percent mass proportionings is mixed, quaternary ion liquid microemulsion is formed；
2, using glass-carbon electrode as cathode, it is micro- to be placed in the quaternary ionic liquid that step (1) obtains as anode for platinum plate electrode
It is 0.5~4.5mA/cm in current density in lotion2Lower room temperature reaction 10~25 minutes, centrifuges, is washed with deionized water
It washs, obtains Ag-Pd Nanoalloys.
In above-mentioned steps 1, preferably the raw material of following percent mass proportionings is mixed, forms quaternary ion liquid microemulsion：
In the above-mentioned aqueous solution containing palladium salt and silver salt, a concentration of 0.005~0.05mol/L of palladium salt and silver salt, and
Palladium salt and the molar ratio of silver salt are 3:7~7:3, the silver salt is silver nitrate, and the palladium salt is potassium chloropalladite.
Preferably it is 2~3mA/cm in current density in above-mentioned steps 22Lower room temperature reaction 15 minutes.
The present invention using chlorination 1- butyl -3- methylimidazoles ionic liquid, n-butanol, cetyl trimethylammonium bromide with
The quaternary ion liquid microemulsion with high electrical conductivity that the aqueous solutions of Ag-Pd bimetal salts is constituted as electrolyte solution,
Itself and glass-carbon electrode are built into three-electrode system, coupled ion liquid microemulsion and the respective advantage of electrochemical reduction, utilized
" nanometer pond " in ion liquid microemulsion is used as microreactor, is realized in electrolyte solution by the method for electrochemical reduction
In directly obtain that granular size is consistent, Ag-Pd Nanoalloy of the grain size between 2~13nm.Wherein chlorination 1- butyl -3- methyl miaows
The cosurfactant that oxazolinium ion liquid acts not only as soft template and micro- reaction is formed, but also it is molten to improve electrolyte
Electron-transport between the conductivity and promotion drop of liquid.The size of Ag-Pd Nanoalloys and distribution can pass through different electricity
Sedimentary condition regulates and controls, and various patterns are obtained in electrolyte solution for difference that finally can be according to demand and the Ag-Pd of function receives
Meter He Jin.
The present invention uses quaternary ion liquid microemulsion system, can be direct by electrochemical reduction using three-electrode system
Obtain the metal that largely cannot or be difficult to deposit in substrate media in microemulsion electrolyte, and the method do not need to by
The metal simple-substance or Nanoalloy particle that any medium can be obtained by size tunable, be evenly distributed, operating method is simple, can profit
High with rate, cost is small.Ag-Pd Nanoalloys prepared by the present invention are a kind of good catalyst of effect, are aoxidized with oxygen also in alcohol
High catalytic activity and stability have all been embodied in former two catalyst system and catalyzings, has been had potential application.
The method of the present invention has the advantage that：(1) ionic liquid and water are all green solvents；(2) ionic liquid and water-soluble
Liquid all has electric conductivity so that microemulsion has better conductive capability；(3) ion liquid microemulsion has preferably molten compared with ionic liquid
Xie Xing；(4) electrochemical reduction is carried out in ion liquid microemulsion system preparing size controllably and particle diameter distribution one as a kind of
The effective ways of the nano metal material of cause, this method are not necessarily to special installation and special process flow, not only economical but also conveniently.
Description of the drawings
Fig. 1 is the XPS figures of Ag in Ag-Pd Nanoalloys prepared by embodiment 1.
Fig. 2 is the XPS figures of Pd in Ag-Pd Nanoalloys prepared by embodiment 1.
Fig. 3 is the transmission electron microscope photo of Ag-Pd Nanoalloys prepared by embodiment 1.
Fig. 4 is the transmission electron microscope photo of Ag-Pd Nanoalloys prepared by embodiment 2.
Fig. 5 is the transmission electron microscope photo of Ag-Pd Nanoalloys prepared by embodiment 3.
Fig. 6 is the transmission electron microscope photo of Ag-Pd Nanoalloys prepared by embodiment 4.
Fig. 7 is the transmission electron microscope photo of Ag-Pd Nanoalloys prepared by embodiment 5.
Fig. 8 is the transmission electron microscope photo of Ag-Pd Nanoalloys prepared by embodiment 6.
Specific implementation mode
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
1,0.4g 0.02mol/L silver nitrate aqueous solutions and 0.4g 0.02mol/L palladium bichloride acid aqueous solutions of potassium are mixed equal
It is even, 6.8g n-butanols, 1.3g cetyl trimethylammonium bromides, 1.1g chlorination 1- butyl -3- methylimidazole ions is then added
Liquid makes it be mixed thoroughly, obtains ion liquid microemulsion by fully shaking.
2, it is 0.07cm by surface area2Glass-carbon electrode distilled water by surface clean it is clean after, be sequentially placed into anhydrous second
It is dry each ultrasonic 5 minutes in alcohol and distilled water, the glass-carbon electrode cleaned up.Using the glass-carbon electrode cleaned up as
Working electrode connects power cathode, reference electrode and be platinum plate electrode to electrode, and positive pole is connect to electrode, micro- with ionic liquid
Lotion is electrolyte, is 2.5mA/cm in current density2Lower room temperature reaction 15 minutes, centrifuges, lower sediment distilled water
It is centrifuged again after washing, obtains Ag-Pd Nanoalloys.
Products therefrom is aobvious using AXIS ULTRAX type Multifunctional imagings photoelectron spectrograph, JEM-2100 type transmitted electrons
Micro mirror is characterized respectively, the result is shown in Figure 1~3.By Fig. 1 and 2 as it can be seen that products therefrom is nanometer Ag-Pd alloys.As seen from Figure 3,
The even particle distribution and grain size of gained Ag-Pd Nanoalloys are 3.5~6.5nm.
Embodiment 2
It is 1.0mA/cm in current density in the step 2 of embodiment 12Lower room temperature reaction 15 minutes, other steps and reality
It is identical to apply example 1, obtains Ag-Pd Nanoalloys.From fig. 4, it can be seen that the grain size of gained Ag-Pd Nanoalloys is 2.0~4.0nm.
Embodiment 3
It is 4.0mA/cm in current density in the step 2 of embodiment 12Lower room temperature reaction 15 minutes, other steps and reality
It is identical to apply example 1, obtains Ag-Pd Nanoalloys.As seen from Figure 5, the grain size of gained Ag-Pd Nanoalloys is 6.0~13.0nm.
Embodiment 4
In the step 1 of the present embodiment, by 0.45g 0.02mol/L silver nitrate aqueous solutions and 0.45g 0.02mol/L chlorinations
Palladium acid aqueous solutions of potassium is uniformly mixed, and 6.8g n-butanols, 1.6g cetyl trimethylammonium bromides, 0.8g chlorination 1- fourths is then added
Base -3- methylimidazole ionic liquids, make it be mixed thoroughly, obtain ion liquid microemulsion by fully shaking.This implementation
It is 3.0mA/cm in current density in the step 2 of example2Lower room temperature reaction 15 minutes, other steps are same as Example 1, obtain
Ag-Pd Nanoalloys.As seen from Figure 6, the grain size of gained Ag-Pd Nanoalloys is 5.5~11.5nm.
Embodiment 5
In the step 1 of the present embodiment, by 0.45g 0.02mol/L silver nitrate aqueous solutions and 0.45g 0.02mol/L chlorinations
Palladium acid aqueous solutions of potassium is uniformly mixed, and 6.4g n-butanols, 1.6g cetyl trimethylammonium bromides, 1.1g chlorination 1- fourths is then added
Base -3- methylimidazole ionic liquids, make it be mixed thoroughly, obtain ion liquid microemulsion by fully shaking.This implementation
It is 3.0mA/cm in current density in the step 2 of example2Lower room temperature reaction 15 minutes, other steps are same as Example 1, obtain
Ag-Pd Nanoalloys.As seen from Figure 7, the grain size of gained Ag-Pd Nanoalloys is 3.5~6.5nm.
Embodiment 6
In the step 1 of the present embodiment, by 0.45g 0.02mol/L silver nitrate aqueous solutions and 0.45g 0.02mol/L chlorinations
Palladium acid aqueous solutions of potassium is uniformly mixed, and 5.8g n-butanols, 1.6g cetyl trimethylammonium bromides, 1.7g chlorination 1- fourths is then added
Base -3- methylimidazole ionic liquids, make it be mixed thoroughly, obtain ion liquid microemulsion by fully shaking.This implementation
It is 3.0mA/cm in current density in the step 2 of example2Lower room temperature reaction 15 minutes, other steps are same as Example 1, obtain
Ag-Pd Nanoalloys.As seen from Figure 8, the grain size of gained Ag-Pd Nanoalloys is 2.0~4.5nm.
Claims (4)
1. a kind of method that electrochemistry prepares Ag-Pd Nanoalloys in quaternary ion liquid microemulsion, it is characterised in that it is under
State step composition:
（1）Prepare quaternary ion liquid microemulsion
The raw material of following percent mass proportionings is mixed, quaternary ion liquid microemulsion is formed；
Aqueous solution 2.5%~13% containing palladium salt and silver salt
N-butanol 57%~72%
Chlorination 1- butyl -3- methylimidazoles ionic liquid 6.5%~18%
Cetyl trimethylammonium bromide 7%~19%
（2）Using glass-carbon electrode as cathode, platinum plate electrode is placed in step as anode（1）Obtained quaternary ionic liquid micro emulsion
It is 0.5~4.5 mA/cm in current density in liquid2Lower room temperature reaction 10~25 minutes, centrifuges, is washed with deionized,
Obtain Ag-Pd Nanoalloys.
2. the method that electrochemistry prepares Ag-Pd Nanoalloys in quaternary ion liquid microemulsion according to claim 1,
It is characterized in that：In step（1）In, the raw material of following percent mass proportionings is mixed, quaternary ion liquid microemulsion is formed；
Aqueous solution 7%~10% containing palladium salt and silver salt
N-butanol 65%~69%
Chlorination 1- butyl -3- methylimidazoles ionic liquid 12%~16%
Cetyl trimethylammonium bromide 11%~17%.
3. electrochemistry prepares the side of Ag-Pd Nanoalloys in quaternary ion liquid microemulsion according to claim 1 or 2
Method, it is characterised in that：The silver salt is silver nitrate, and the palladium salt is potassium chloropalladite.
4. the method that electrochemistry prepares Ag-Pd Nanoalloys in quaternary ion liquid microemulsion according to claim 1,
It is characterized in that：The step（2）In, it is 2~3 mA/cm in current density2Lower room temperature reaction 15 minutes.
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| CN111203545B (en) * | 2020-01-16 | 2022-09-13 | 河南科技大学 | Preparation method of chrysanthemum-shaped Pd nanoparticles regulated and controlled by ionic liquid |
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