CN108441886A - A method of preparing metal using ionic liquid electrolytic metal oxide - Google Patents
A method of preparing metal using ionic liquid electrolytic metal oxide Download PDFInfo
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- CN108441886A CN108441886A CN201810439196.2A CN201810439196A CN108441886A CN 108441886 A CN108441886 A CN 108441886A CN 201810439196 A CN201810439196 A CN 201810439196A CN 108441886 A CN108441886 A CN 108441886A
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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
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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
- C25C1/02—Electrolytic production, recovery or refining of metals by electrolysis of solutions of light metals
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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
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
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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
- C25C1/18—Electrolytic production, recovery or refining of metals by electrolysis of solutions of lead
Abstract
The present invention relates to a kind of method preparing metal using ionic liquid electrolytic metal oxide, this method is using a substituted imidazole ion liquid dissolving metal oxide as electrolyte；Using copper sheet or stainless steel as cathode, inert electrode prepares metal as anode, direct electrolytic oxidation object；Copper sheet or stainless steel substrates are taken out after electrolysis, obtain the metal for being deposited on surface.The present invention uses medium of the substituted imidazole ionic liquid as electrolytic preparation metal, and electrolytic process can be made to carry out at a lower temperature, corrosion of the electrolyte to equipment is alleviated while energy saving, and the yield of metal is made to reach 99%；The ionic liquid price of use is relatively cheap, fusing point is low, can reduce production cost；The metal ion source used is oxide, and what is be precipitated on inert anode is oxygen, and there are no pollution to the environment.In addition, the method for the present invention process is simple, it is easy to operate.
Description
Technical field
The present invention relates to a kind of methods preparing metal using ionic liquid electrolytic metal oxide, belong to metallurgical technology neck
Domain.
Background technology
Solubility property (solubility and solution rate) of the metal oxide usually in cryogenic media is poor, thus current metal
The electrolysis of oxide mainly carries out in high-temperature molten salt.It, should although high temperature fused salt electrolysis can realize the large-scale production of metal
Method there are electrolysis temperatures it is high, energy consumption is big, complicated for operation, discharge amount of exhaust gas is more a series of problems, such as.Add in energy shortage, pollution
Under acute severe situation, how to realize that the energy-saving and emission-reduction of metal electrodeposition and green production are a problem to be solved.Therefore, it looks for
Just show particularly important to a kind of pollution-free low temperature green solvent of metal oxide that can dissolve.
Ionic liquid, refer to room temperature or close at room temperature present liquid, completely by organic cation and inorganic the moon
From molecular liquid substance, also referred to as room temperature molten salt.Ionic liquid is lower melting-point main as ionic compound
The reason is that because the asymmetry of certain substituent groups in its structure prevent ion from being regularly piled into crystal caused by.Common sun from
Son has quaternary ammonium salt ion, quaternary phosphine salt ion, imidazolium ion and pyrroles's salt ion etc., and anion has halide ion, tetrafluoro boric acid
Radical ion, hexafluorophosphoricacid acid ions etc..Ionic liquid is a kind of ideal room temperature fused salt, with high-temperature molten salt and organic solvent
Advantage can be obtained ability electro-deposition obtains in high-temperature molten salt metal and its alloy, but also only adopts at present at room temperature
With based on anhydrous AlCl3It is electrolysed AlCl in the ionic liquid being mixed to prepare with chlorination 1- butyl -3- methylimidazoles3Prepare gold
Belong to aluminium, also there are other metal chlorides based on AlCl3Respectively with chlorinated butyl pyridine, chlorination 1- ethyl-3-methylimidazoles, chlorine
The mixed liquor electro-deposition for changing the compositions such as 1- butyl -3- methylimidazoles obtains the alloy of metal or metal and aluminium, but is utilizing chlorination
Electrodeposition process of the zinc on gold, platinum, tungsten and glass-carbon electrode, as a result, it has been found that have undercurrent potential phenomenon on metal electrode, and in glass
There was only ternary nucleation process on carbon electrode；What is obtained under overvoltage is the alloy of zinc and aluminium, can not prepare pure gold
Belong to zinc.Organic salt and AlCl in the reaction3Relative mole content need stringent control, because of AlCl3In acidity when excessive；It is organic
In alkalinity when salt excess；And the variation of acid-base property will cause metal ion to generate different substances.Such as Ag+Under acidic environment
It is bare ion, and under alkaline environment then and Cl-In conjunction with, therefore usually need to make buffer with NaCl.The electrochemistry of this class I liquid I
Window ranges are generally 2~4V, but due to AlCl3Easily water suction thus can only use in dry conditions.When based on AlCl3's
When ionic liquid is in neutrality, since alkyl imidazolium cation is weakly acidic, and paired anion is in then alkalescent, this kind of liquid
The electrochemical window of body be usually above 4V, but shortcoming be its anion be easy and AlCl3Equal highly acids substance reacts,
For example, PF6 -Meet AlCl3Generate PF5Gas and fluorine chloro-aluminate, and meet water and partial hydrolysis then occurs and generates a certain amount of
HF has certain harmfulness to body, also pollutes environment.
Invention content
(1) technical problems to be solved
In order to solve the above problem of the prior art, present invention offer is a kind of to utilize ionic liquid electrolytic metal oxide system
The method of standby metal, and carrying out at a lower temperature, it is energy saving, alleviate equipment corrosion and easily operated, while in anode
Upper precipitation is oxygen, environmentally safe.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include：
A method of metal being prepared using ionic liquid electrolytic metal oxide, method includes the following steps：
The preparation of S1, electrolyte：Metal oxide is added in the ionic liquid of heating, is uniformly mixed to form ion
Liquid electrolyte；
S2, electrolytic preparation metal：Using copper sheet or stainless steel as cathode, inert electrode as anode, in constant potential or
Under constant current, electro-deposition is carried out to il electrolyte described in step S1；
The copper sheet or stainless steel substrates are taken out after S3, electrolysis, obtain the metal for being deposited on its surface.
Method as described above, it is preferable that in step sl, the ionic liquid is a substituted imidazole ionic liquid,
Wherein, cation can be selected from：1- methylimidazoles, 1- ethyl imidazol(e)s, 1- propyl imidazoles, 1- butyl imidazoles, 1- amyls imidazoles, 1- oneself
The mixing of one or more of base imidazoles, 1- heptyl imidazoles, 1- octylimidazoles, 1- nonyls imidazoles or 1- decyl imidazoles etc.；
Or at least one of the derivative of aforementioned substituted imidazole cationoid；
It can be selected from anion：F-、Cl-、Br-、I-、BF4 -、PF6 -、NO3 -、N(CN)2 -、CF3SO3 -、N(CF3SO2)2 -In
It is at least one.
Method as described above, it is preferable that in step sl, the metal oxide that the present invention is applicable in is Al2O3、
MgO、TiO2、ZnO、PbO、CuO、Cu2O、MnO、FeO、Fe2O3, CoO or NiO.
Method as described above, it is preferable that in step sl, the temperature of the heating is 90~100 DEG C, the stirring
Speed is 300~700r/min.
Method as described above, it is preferable that in step sl, the metal oxide is a concentration of in ionic liquid
0.5~3mol/L.
Method as described above, it is preferable that in step s 2, current potential is -0.4~-1.0V, institute to the constant potential in order to control
Stating constant current, cathode-current density is 0.01~0.04A/cm in order to control2。
Method as described above, it is preferable that in step s 2, the temperature for controlling electrolysis is 90~120 DEG C.
When electrolysis temperature is controlled at 90~120 DEG C, metal oxide can be made to be dissolved completely in ionic liquid, make reaction
Fully.
Method as described above, it is preferable that in step s 2, the inert electrode is nickel, titanium, platinum, gold or other inertia
Metal electrode.
Method as described above, it is preferable that in step s 2, the time of the electro-deposition is 1~4h.
Method as described above, it is preferable that in step s3, the copper sheet or stainless steel substrates are cleaned simultaneously with second alcohol and water
The metal for being deposited on its surface is obtained after drying.
Method as described above, it is preferable that in step s 2, the copper sheet or stainless steel need to carry out pre-treatment：Using
Sand paper polishes to the surface of copper sheet or stainless steel, keeps copper sheet and stainless steel surface smooth, then cleaned with EtOH Sonicate ripple, so
It is cleaned with deionized water, is used after finally drying afterwards.
(3) advantageous effect
The beneficial effects of the invention are as follows：
The substituted imidazole ionic liquid that the present invention uses is to metal oxide electrolytic preparation metal, a substituted imidazole
Ionic liquid can be such that electrolytic process carries out at a lower temperature, and corruption of the electrolyte to equipment is alleviated while energy saving
Erosion, and the yield of metal is made to reach 99%；The ionic liquid price of use is relatively cheap, fusing point is low, can reduce production cost.
The metal ion source used in the present invention is oxide, and what is be precipitated on inert anode is oxygen, and there are no pollution to the environment.This
Outside, the method for the present invention process is simple, easy to operate.
Description of the drawings
Fig. 1 is the SEM figures of the metallic zinc prepared in the embodiment of the present invention 4；
Fig. 2 is the EDS figures of the metallic zinc prepared in the embodiment of the present invention 4；
Fig. 3 is the XRD diagram of the metallic zinc prepared in the embodiment of the present invention 4；
Fig. 4 is the SEM figures of the metallic lead prepared in the embodiment of the present invention 5；
Fig. 5 is the EDS figures of the metallic lead prepared in the embodiment of the present invention 5；
Fig. 6 is the XRD diagram of the metallic lead prepared in the embodiment of the present invention 5.
Specific implementation mode
The present invention, which is directed to while how improving metal quality, eliminates harm of the electrodeposit liquid to environment, in ionic liquid
Numerous studies are carried out, discovery is worked as can at certain lower temperature to metal oxide using a substituted imidazole ionic liquid
Dissolving, pure metal can be prepared by carrying out electro-deposition, and principle is to contain one in a substituted imidazole compound structure used
A amino (- NH) not replaced by alkyl, with certain activity, thus can react with metal oxide and make gold
Belong to oxide to be dissolved in ionic liquid.Ionic liquid dissolved with metal oxide is electrolysed as electrolyte, preferably
As cathode, inert electrode is determined by a large number of experiments under certain current potential, metal ion as anode for copper sheet or stainless steel
It can be reduced and be enriched on cathode, and the precipitated oxygen on inert anode, to prepare pure metal, and not have to environment
Pollution, electrolyte is also reusable, to cost-effective.Solves metal oxide solubility in cryogenic media simultaneously
It is low, it is difficult to the problems such as electrolytic metal oxide obtains metal at low temperature, and existing method pollutes environment.
Ionic liquid used in the present invention is a substituted imidazole ionic liquid, wherein cation uses：1- methyl miaows
Azoles, 1- ethyl imidazol(e)s, 1- propyl imidazoles, 1- butyl imidazoles, 1- amyls imidazoles, 1- hexyl imidazoliums, 1- heptyl imidazoles, 1- octyl miaows
Any one or a few in azoles, 1- nonyls imidazoles, 1- decyl imidazoles etc., which mixes, or a substituted imidazole noted earlier is cationic spreads out
Any one or a few in biology；It is with anion：F-、Cl-、Br-、I-、BF4 -、PF6 -、NO3 -、N(CN)2 -、CF3SO3 -、N
(CF3SO2)2 -In any one or a few mixing when, temperature be 90~100 DEG C when, be used equally for dissolving metal oxide,
For the pure metal of electrolytic preparation.Wherein, applicable metal oxide has Al2O3、MgO、TiO2、ZnO、PbO、CuO、Cu2O、
MnO、FeO、Fe2O3, CoO or NiO, can prepare corresponding pure metal, an above-mentioned substituted imidazole ionic liquid can lead to
Market purchase is crossed to obtain.
In order to preferably explain the present invention, in order to understand, below in conjunction with the accompanying drawings, by specific implementation mode, to this hair
It is bright to be described in detail.
Embodiment 1
The method for preparing metallic aluminium using ionic liquid low-temperature electrolysis of aluminum oxide is carried out according to following processing step：
(1) preparation of electrolyte：The 1- methylimidazole villiaumite ionic liquids of appropriate mass are weighed, cation therein is 1-
Methylimidazole, anion F-, control heating temperature is 100 DEG C, and mixing speed 300r/min is then slowly added to Al2O3,
It is uniformly mixed to form il electrolyte, and makes metal oxide dense in 1- methylimidazole villiaumite ionic liquids
Degree is 0.5mol/L；
(2) electrolytic preparation metal：Using copper sheet as cathode, for nickel sheet as anode, control electrolysis temperature is 120 DEG C, is adopted
With constant potential mode, controlling potential is -1.0V, the electro-deposition 1h in the electrolyte of step (1)；
(3) copper sheet is taken out after being electrolysed, cleaned with second alcohol and water and obtains the metallic aluminium for being deposited on its surface after drying.
Embodiment 2
The method for preparing magnesium metal using ionic liquid low-temperature electrolytic magnesia is carried out according to following processing step：
(1) preparation of electrolyte：The 1- ethyl imidazol(e) chloride salt ions liquid of appropriate mass is weighed, cation therein is 1-
Ethyl imidazol(e), anion Cl-, control heating temperature is 90 DEG C, and mixing speed 400r/min is then slowly added to MgO, stirs
It mixes to be uniformly mixed and forms il electrolyte, wherein making a concentration of 1.0mol/L of metal oxide MgO；
(2) electrolytic preparation metal：Using stainless steel as cathode, titanium sheet is 110 DEG C as anode, control electrolysis temperature,
Using constant current mode, control current density is 0.01A/cm2, the electro-deposition 2h in the electrolyte of step (1)；
(3) stainless steel substrates are taken out after being electrolysed, cleaned with second alcohol and water and obtain the gold for being deposited on its surface after drying
Belong to magnesium.
Embodiment 3
The method for preparing Titanium using ionic liquid low-temperature electrolytic titanium oxide is carried out according to following processing step：
(1) preparation of electrolyte：The 1- propyl imidazole bromide ionic liquids of appropriate mass are weighed, cation therein is 1-
Propyl imidazole, anion Br-, control heating temperature is 100 DEG C, and mixing speed 500r/min is then slowly added to TiO2,
It is uniformly mixed to form il electrolyte, wherein metal oxide TiO2A concentration of 1.5mol/L；
(2) electrolytic preparation metal：Using copper sheet as cathode, for platinized platinum as anode, control electrolysis temperature is 100 DEG C, is adopted
With constant potential mode, controlling potential is -0.9V, the electro-deposition 3h in the electrolyte of step (1)；
(3) copper sheet is taken out after being electrolysed, cleaned with second alcohol and water and obtains the Titanium for being deposited on its surface after drying.
Embodiment 4
The method for preparing metallic zinc using ionic liquid low-temperature electrolytic zinc oxide is carried out according to following processing step：
(1) preparation of electrolyte：The 1- butyl imidazole metal iodide ions liquid of appropriate mass is weighed, cation therein is 1-
Butyl imidazole, anion I-, control heating temperature is 100 DEG C, and mixing speed 600r/min is then slowly added to ZnO, stirs
It mixes to be uniformly mixed and forms il electrolyte, the wherein a concentration of 2.0mol/L of metal oxide ZnO；
(2) electrolytic preparation metal：Using copper sheet as cathode, platinized platinum is 90 DEG C as anode, control electrolysis temperature, is used
Constant potential mode, controlling potential are -0.8V, the electro-deposition 2h in the electrolyte of step (1)；
(3) copper sheet is taken out after being electrolysed, cleaned with second alcohol and water and obtains the metallic zinc for being deposited on its surface after drying.
Embodiment 5
The method for preparing metallic lead using ionic liquid low-temperature electrolytic lead oxide is carried out according to following processing step：
(1) preparation of electrolyte：Weigh the 1- amyl tetrafluoroborate ionic liquids of appropriate mass, sun therein from
Son is 1- amyl imidazoles, anion BF4 -, control heating temperature is 100 DEG C, mixing speed 700r/min, is then slowly added
Enter PbO, be uniformly mixed to form il electrolyte, wherein a concentration of 2.0mol/L of metal oxide PbO；
(2) electrolytic preparation metal：Using copper sheet as cathode, platinized platinum is 90 DEG C as anode, control electrolysis temperature, is used
Constant potential mode, controlling potential are -0.4V, the electro-deposition 2h in the electrolyte of step (1)；
(3) copper sheet is taken out after being electrolysed, cleaned with second alcohol and water and obtains the metallic lead for being deposited on its surface after drying.
In the above-described embodiments, ionic liquid purity >=99% of use, metal oxide >=99%, cathode copper sheet purity
>=99.99%, when the copper sheet of cathode is replaced with stainless steel, can prepare corresponding metal, wherein the copper sheet of use and
Stainless steel is needed before use by following processing procedure：It is polished copper sheet and stainless steel surface using different model sand paper, makes copper
Piece and stainless steel surface are smooth, then are cleaned with EtOH Sonicate ripple, are then cleaned with deionized water, last drying for standby.
In in embodiments the step of (1), ZNCL-BS type intelligent digital magnetic force heating plates can be used and heated,
In step (2), 30 type potentiostats of AUTOLAB PGSTAT can be used and be electrolysed.And the metal to being prepared in each embodiment
The pattern and ingredient that metal is analyzed using Japanese Shimadzu SSX-550 types scanning electron microscope (SEM), using the subsidiary energy of SEM
Chromatic dispersion quantity X-ray spectrum (EDS) analyzes the chemical composition of metal, using Dutch Panaco MPDDY2094 type X-ray diffractometers
(XRD) product object phase composition is analyzed.By taking metallic lead zinc and metallic lead prepared by embodiment 4 and 5 as an example, to illustrate preparation of the present invention
The pattern and ingredient and purity of metal.It is the SEM figures of prepared metallic zinc, the zinc prepared as can be seen from Figure as shown in Figure 1
The smooth densification of layer, is illustrated in figure 2 EDS (energy dispersion X-ray spectrum) figure of prepared metallic zinc, the results showed that preparation
Zinc Deposit ingredient is mainly Zn elements, and does not contain other impurity peaks；Illustrate that obtained Coating composition is single, purity ratio
It is higher.It is illustrated in figure 3 the XRD diagram of prepared metallic zinc, as a result illustrates that the coating prepared is that metallic zinc purity is high, it is reachable
99%.
SEM figures, the Fig. 5 for being illustrated in figure 4 prepared metallic lead show the EDS figures and Fig. 6 of prepared metallic lead
It is shown the XRD diagram of prepared metallic lead, illustrates the smooth densification of lead layer, the lead-coat surface composition of preparation is mainly Pb members
Element, and do not contain other impurity peaks；Illustrate that obtained Coating composition is single, metallic lead purity is high, up to 99%.
The above described is only a preferred embodiment of the present invention, being not the limitation for doing other forms to the present invention, appoint
What those skilled in the art can be changed or be modified as the equivalence enforcement of equivalent variations using technology contents disclosed above
Example.But it is every without departing from technical solution of the present invention content, according to the technical essence of the invention to appointing made by above example
What simple modification, equivalent variations and remodeling, still falls within the protection domain of technical solution of the present invention.
Claims (10)
1. a kind of method preparing metal using ionic liquid electrolytic metal oxide, which is characterized in that its method includes as follows
Step：
The preparation of S1, electrolyte：Metal oxide is added in the ionic liquid of heating, is uniformly mixed to form ionic liquid
Electrolyte；
S2, electrolytic preparation metal：Using copper sheet or stainless steel as cathode, inert electrode is as anode, in constant potential or permanent electricity
It flows down, electro-deposition is carried out to il electrolyte described in step S1；
The copper sheet or stainless steel substrates are taken out after S3, electrolysis, obtain the metal for being deposited on its surface.
2. the method as described in claim 1, which is characterized in that in step sl, the ionic liquid is a substituted imidazole
Ionic liquid, wherein cation is selected from：1- methylimidazoles, 1- ethyl imidazol(e)s, 1- propyl imidazoles, 1- butyl imidazoles, 1- amyl miaows
At least one of azoles, 1- hexyl imidazoliums, 1- heptyl imidazoles, 1- octylimidazoles, 1- nonyls imidazoles or 1- decyl imidazoles；Or it is aforementioned
At least one of the derivative of one substituted imidazole cationoid；
It is selected from anion：F-、Cl-、Br-、I-、BF4 -、PF6 -、NO3 -、N(CN)2 -、CF3SO3 -Or N (CF3SO2)2 -In at least one
Kind.
3. the method as described in claim 1, which is characterized in that in step sl, the metal oxide is Al2O3、MgO、
TiO2、ZnO、PbO、CuO、Cu2O、MnO、FeO、Fe2O3, CoO or NiO.
4. the method as described in claim 1, which is characterized in that in step sl, the temperature of the heating is 90~100 DEG C,
The speed of the stirring is 300~700r/min.
5. the method as described in claim 1, which is characterized in that in step sl, the metal oxide is in ionic liquid
A concentration of 0.5~3mol/L.
6. the method as described in claim 1, which is characterized in that in step s 2, current potential is -0.4 to the constant potential in order to control
~-1.0V, cathode-current density is 0.01~0.04A/cm to the constant current in order to control2。
7. the method as described in claim 1, which is characterized in that in step s 2, the temperature for controlling electrolysis is 90~120 DEG C.
8. the method as described in claim 1, which is characterized in that in step s 2, the inert electrode is nickel, titanium, platinum or gold.
9. the method as described in claim 1, which is characterized in that in step s 2, the time of the electro-deposition is 1~4h,
In step S3, the copper sheet or stainless steel substrates are cleaned with second alcohol and water and obtain the metal for being deposited on its surface after drying.
10. method as claimed in any one of claims 1-9 wherein, which is characterized in that in step s 2, the copper sheet or stainless steel
It needs to carry out pre-treatment：It is polished the surface of copper sheet or stainless steel using sand paper, keeps copper sheet and stainless steel surface smooth, then
It is cleaned with EtOH Sonicate ripple, is then cleaned with deionized water, used after finally drying.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109536994A (en) * | 2019-01-23 | 2019-03-29 | 东北大学 | A kind of method that electrodeposition process prepares metallic lead |
| CN109536993A (en) * | 2019-01-23 | 2019-03-29 | 东北大学 | A kind of method of electrodeposit metals zinc in eutectic solvent |
| CN110415969A (en) * | 2019-09-02 | 2019-11-05 | 江西理工大学 | A kind of method that Low-temperature electro-deposition prepares Dy-Ni alloy film |
| CN110860294A (en) * | 2019-11-27 | 2020-03-06 | 河北科技大学 | Preparation method of copper-lead composite metal catalyst and application of copper-lead composite metal catalyst |
| CN112342607A (en) * | 2020-08-31 | 2021-02-09 | 黄勇 | Method for purifying metal complex single crystal by using ionic liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109536994A (en) * | 2019-01-23 | 2019-03-29 | 东北大学 | A kind of method that electrodeposition process prepares metallic lead |
| CN109536993A (en) * | 2019-01-23 | 2019-03-29 | 东北大学 | A kind of method of electrodeposit metals zinc in eutectic solvent |
| CN110415969A (en) * | 2019-09-02 | 2019-11-05 | 江西理工大学 | A kind of method that Low-temperature electro-deposition prepares Dy-Ni alloy film |
| CN110860294A (en) * | 2019-11-27 | 2020-03-06 | 河北科技大学 | Preparation method of copper-lead composite metal catalyst and application of copper-lead composite metal catalyst |
| CN110860294B (en) * | 2019-11-27 | 2022-10-25 | 河北科技大学 | Method for preparing formic acid by electrochemical reduction reaction of carbon dioxide by using copper-lead composite metal as electrode |
| CN112342607A (en) * | 2020-08-31 | 2021-02-09 | 黄勇 | Method for purifying metal complex single crystal by using ionic liquid |
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Application publication date: 20180824 |