CN104911643A - Method for electrodepositing nano-iron from iron oxide in choline chloride ionic liquid - Google Patents
Method for electrodepositing nano-iron from iron oxide in choline chloride ionic liquid Download PDFInfo
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- CN104911643A CN104911643A CN201510189705.7A CN201510189705A CN104911643A CN 104911643 A CN104911643 A CN 104911643A CN 201510189705 A CN201510189705 A CN 201510189705A CN 104911643 A CN104911643 A CN 104911643A
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- choline chloride
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- ferric oxide
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Abstract
The invention relates to a method for electrodepositing nano-iron from iron oxide in a choline chloride ionic liquid, and belongs to the technical filed of green electroplating technologies. The method adopts (chemically analytically pure) ferric oxide powder as a raw material, the choline chloride ionic liquid as an electrolyte, a platinum wire as an anode, and a copper sheet or rod metal matrix to be plated as a cathode, and mainly comprises the following steps: placing an excess amount of ferric oxide powder in the choline chloride ionic liquid, and stirring to obtain a saturated solution; electrodepositing at 60-120DEG C under an applied constant voltage of 1.2-1.9V for 1-20h to generate nano-iron on the cathode and discharge oxygen on the anode in the electrodepositing process; and taking out the cathode after the electrodeposition, washing by using water, and drying to obtain a nano-iron coating.
Description
Technical field
The present invention relates to a kind of method by ferric oxide galvanic deposit Nanoscale Iron in choline chloride 60 class ionic liquid, belong to green electrodeposition technology technical field.
Background technology
Metallic iron, as a kind of base mateiral in modern industrial society, is widely used in various field.Under cryogenic, the pure iron coating obtained by the method for galvanic deposit has the excellent properties such as the high and good wear resistance of hardness.Therefore the main application fields of the electro-deposition techniques of iron is the wearing and tearing aspects such as the reparation of device and the electroforming of mechanical component.Meanwhile, the technology of Electrodeposition Bath of Iron, also for extending the printed circuit board life-span, improves the mechanical property printing version.Because the electro-deposition techniques cost of iron is lower, be therefore adapted at extensively being promoted in large-scale industrial production.People conduct in-depth research the galvanic deposit of metallic iron in the aqueous solution, but due to the electrochemical window of the aqueous solution narrower, the hydrogen produced in electrodeposition process can produce hydrogen embrittlement harm to matrix, and the plating solution of Electrodeposition Bath of Iron the reason such as to be easily oxidized and to limit its application.Compared with the aqueous solution, ionic liquid has very wide electrochemical window, excellent electroconductibility, does not almost have vapour pressure, higher thermostability, and ionic liquid environmental protection, the excellent characteristics such as repeatedly can to reuse.Have above advantage based on ionic liquid, it is subject to people's attention just day by day, is applied to gradually in various electrodeposition.
But a large amount of existing research work around ionic liquid electrodeposition research is all (as FeCl with the halogen compounds containing certain metal ion species
2or FeCl
3) be starting material.Compared with taking halogen compounds as raw material, metal oxide more easily obtains and operational condition is more easy.Therefore, to explore with metal oxide (as ferric oxide) as raw material, find cheap ion liquid system, carry out Direct Electroplating and obtain nanometer metallic iron, just there is well reality and scientific meaning.
Summary of the invention
The object of the invention is the defect existed for existing electrodeposit metals iron technology, a kind of method being prepared metal nano iron plating under low temperature by the direct galvanic deposit of ferric oxide is provided.The method ingredient requirement is simple, service temperature is low, process control, and the environmental protection of choline chloride 60 class ionic liquid, repeatedly recirculation can utilize, have important practical significance.
For achieving the above object, the present invention adopts following technical scheme:
By a method for ferric oxide galvanic deposit Nanoscale Iron in choline chloride 60 class ionic liquid, it is characterized in that there is following process and step:
1. in choline chloride 60 class ionic liquid by a method for ferric oxide galvanic deposit Nanoscale Iron, there are following steps:
A. the preparation of ionic liquid electrolyte: be first 1:2 by choline chloride 60 and ethylene glycol according to mol ratio or be that 1:2 mix with urea according to mol ratio by choline chloride 60, then stir 4-15 hours under 50 ° of C-80 ° of C constant temperatures, form water white transparency shape choline chloride 60 class ionic liquid;
B. the preparation of plating solution: analytically pure for excess chemical ferric oxide powder is added in the ionic liquid prepared in step a, stir 40-80 hours under 25 ° of C-80 ° of C constant temperature, obtain the choline chloride 60 class ionic liquid solution that ferric oxide is saturated;
C. cell system is formed: the present invention adopts polytetrafluoroethylene beaker as reaction vessel, adopt the ferric oxide saturated choline chloride 60 class ionic liquid configured in above-mentioned steps b as ionogen, adopt the plating metal matrixes such as the copper sheet after polishing, activation or copper rod as negative electrode, platinum filament is anode, to form electro-deposition system;
D. electrodeposition process controls: in electrodeposition process, the temperature of cell system controls at 60 ° of C-120 ° of C by constant-temperature temperature-control instrument and electric mantle, and the voltage applied is 1.2 V-1.9 V, and electrodeposition time is 1-20 hour;
E. galvanic deposit complete after taking-up cathode sheets, clean with distilled water flushing, then clean with dehydrated alcohol, can nano iron plating be obtained after oven dry.
Principle of the present invention is, making electrolysis occurs, making the ferric oxide in ionic liquid generate metallic iron at cathode electrodeposition, anode generation oxygen evolution reaction by applying constant voltage or continuous current between a cathode and an anode.
Compared with prior art, the present invention has following outstanding substantive distinguishing features and significant advantage:
Present invention process flow process is short, service temperature is low, process is simple and easy to control and environmental protection.Obtained the metal iron layer of nanometer-size die by direct electrolytic oxidation iron, raw material is pure croci, and source does not simply need other process and cost is low, does not have other additives, does not produce other side reactions.Electrolytic solution environmental protection, repeatedly recirculation can use, and effectively can avoid the defect of the aqueous solution and the electrolysis of chloride.
Accompanying drawing explanation
The short route schematic diagram of Fig. 1 electrodeposited nanocrystalline metal of the present invention iron layer.
Fig. 2 time current curve figure of the inventive method electrodeposited nanocrystalline metal iron layer at different conditions.
Energy spectrogram (EDS) of Fig. 3 the inventive method electrodeposited nanocrystalline metal iron layer in embodiment three.
Fig. 4 the inventive method is the shape appearance figure of nano metal iron layer for preparing of galvanic deposit at different conditions.
The time current curve figure of Fig. 5 the inventive method electrodeposited nanocrystalline metal iron layer in embodiment five.
Fig. 6 the inventive method is electrodeposited nanocrystalline metal iron layer shape appearance figure under an optical microscope in embodiment five and embodiment six.
Embodiment
Below in conjunction with accompanying drawing, specific embodiments of the invention are further described.
embodiment one
1. embodiment one is carried out according to the short route figure shown in Fig. 1.First 70 grams of choline chloride 60s and 62 grams of ethylene glycol are placed in the polytetrafluoroethylene beaker of 250 milliliters, under 50 ° of C, constant temperature stirs 6 hours, and choline chloride 60 is fully mixed with ethylene glycol, forms water white transparency shape liquid;
2. analytically pure for excess chemical ferric oxide powder is placed in choline chloride 60 and ethylene glycol ionic liquid, stirs 50 hours under 50 ° of C constant temperature, obtain ferric oxide saturated solution.Square copper sheet (1 cm x 1 centimetre) after polishing also activation and platinum filament are fixed in the electrolytic solution as negative electrode and anode.
3. be 60 ° of C by the temperature that constant-temperature temperature-control instrument and electric mantle control electrolytic solution, apply constant voltage 1.8 V galvanic deposit 3 hours, current versus time curve as shown in Figure 2.Take out negative electrode distilled water flushing after galvanic deposit clean, then with raw spirit cleaning, dry and preserve.
The microscopic appearance of gained metal iron layer is observed, as shown in Figure 4 (a) by scanning electron microscope.Cathode sheets in the plating solution galvanic deposit, after 3 hours, galvanic deposit can obtain the thin metallic iron settled layer of one deck.
embodiment two
1. first 100 grams of choline chloride 60s and 88.913 grams of ethylene glycol are placed in the polytetrafluoroethylene beaker of 300 milliliters, under 50 ° of C, constant temperature stirs 10 hours, and choline chloride 60 is fully mixed with ethylene glycol, forms water white transparency shape liquid;
2. analytically pure for excess chemical ferric oxide powder is placed in choline chloride 60 and ethylene glycol ionic liquid, stirs 60 hours under 50 ° of C constant temperature, obtain ferric oxide saturated solution.Square copper sheet (1 cm x 1 centimetre) after polishing also activation and platinum filament are fixed in the electrolytic solution as negative electrode and anode.
3. be 80 ° of C by the temperature that constant-temperature temperature-control instrument and electric mantle control electrolytic solution, apply constant voltage 1.8 V galvanic deposit 3 hours, current versus time curve as shown in Figure 2.Take out negative electrode distilled water flushing after galvanic deposit clean, then with raw spirit cleaning, dry and preserve.
The microscopic appearance of gained metal iron layer is observed, as shown in Figure 4 (b) by scanning electron microscope.Galvanic deposit is after 3 hours in the plating solution for cathode sheets, and galvanic deposit can obtain the more uniform metallic iron settled layer of one deck, its particle size is about 100 nanometers.
embodiment three
1. first 50 grams of choline chloride 60s and 40.456 grams of ethylene glycol are placed in the polytetrafluoroethylene beaker of 200 milliliters, under 50 ° of C, constant temperature stirs 5 hours, and choline chloride 60 is fully mixed with ethylene glycol, forms water white transparency shape liquid;
2. analytically pure for excess chemical ferric oxide powder is placed in choline chloride 60 and ethylene glycol ionic liquid, stirs 48 hours under 50 ° of C constant temperature, obtain ferric oxide saturated solution.Square copper sheet (1 cm x 1 centimetre) after polishing also activation and platinum filament are fixed in the electrolytic solution as negative electrode and anode.
3. be 100 ° of C by the temperature that constant-temperature temperature-control instrument and electric mantle control electrolytic solution, apply constant voltage 1.8 V galvanic deposit 3 hours, current versus time curve as shown in Figure 2.Take out negative electrode distilled water flushing after galvanic deposit clean, then with raw spirit cleaning, dry and preserve.
As can be seen from Fig. 4 (c), by the galvanic deposit of 3 hours, can obtain the metallic iron settled layer of one deck densification at cathode sheets substrates, its particle size is about 100 nanometers.As can be seen from the energy spectrogram in Fig. 3, the now nano metal iron layer of cathode sheets surface for depositing.Along with temperature is raise, and the metal iron layer that galvanic deposit obtains is more obvious.
embodiment four
1. first 80 grams of choline chloride 60s and 70.130 grams of ethylene glycol are placed in the polytetrafluoroethylene beaker of 250 milliliters, under 50 ° of C, constant temperature stirs 8 hours, and choline chloride 60 is fully mixed with ethylene glycol, forms water white transparency shape liquid;
2. analytically pure for excess chemical ferric oxide powder is placed in choline chloride 60 and ethylene glycol ionic liquid, stirs 50 hours under 50 ° of C constant temperature, obtain ferric oxide saturated solution.Square copper sheet (1 cm x 1 centimetre) after polishing also activation and platinum filament are fixed in the electrolytic solution as negative electrode and anode.
3. be 120 ° of C by the temperature that constant-temperature temperature-control instrument and electric mantle control electrolytic solution, apply constant voltage 1.8 V galvanic deposit 3 hours.Take out negative electrode distilled water flushing after galvanic deposit clean, then with raw spirit cleaning, dry and preserve.
By the galvanic deposit of 3 hours, the metallic iron settled layer of one deck densification can be obtained at cathode sheets substrates, as shown in Fig. 4 (d).As can be seen from the time current curve of the electrodeposition process in Fig. 2, along with the rising of electrodeposition temperature, current density increases, thus the chemical reaction velocity occurred in cathode sheets in electrodeposition process is accelerated.Therefore under identical electrodeposition time, along with the rising of electrodeposition temperature, the finer and close and thickness of the metal iron layer obtained in cathode sheets increases.
embodiment five
1. first 150 grams of choline chloride 60s and 64.286 grams of urea are placed in the polytetrafluoroethylene beaker of 300 milliliters, under 80 ° of C, constant temperature stirs 15 hours, and choline chloride 60 is fully mixed with urea, forms water white transparency shape liquid;
2. analytically pure for excess chemical ferric oxide powder is placed in choline chloride 60 and urea ionic liquid, stirs 80 hours under 80 ° of C constant temperature, obtain ferric oxide saturated solution.Copper rod (f=6 mm) after polishing also activation and platinum filament are fixed in the electrolytic solution as negative electrode and anode.
3. be 100 ° of C by the temperature that constant-temperature temperature-control instrument and electric mantle control electrolytic solution, apply constant voltage 1.8 V galvanic deposit 3 hours.Take out negative electrode distilled water flushing after galvanic deposit clean, then with raw spirit cleaning, dry and preserve.
Fig. 5 is electric current curve over time in cathode sheets electrodeposition process in this embodiment, by the macrograph of observation by light microscope gained metal iron layer as shown in Figure 6 (a), as seen from the figure, cathode sheets in the plating solution galvanic deposit can obtain certain thickness metallic iron settled layer at cathode sheets substrates after 3 hours.
embodiment six
1. first 70 grams of choline chloride 60s and 30 grams of urea are placed in the polytetrafluoroethylene beaker of 200 milliliters, under 80 ° of C, constant temperature stirs 10 hours, and choline chloride 60 is fully mixed with urea, forms water white transparency shape liquid;
2. analytically pure for excess chemical ferric oxide powder is placed in choline chloride 60 and urea ionic liquid, stirs 72 hours under 80 ° of C constant temperature, obtain ferric oxide saturated solution.Copper rod (f=6 mm) after polishing also activation and platinum filament are fixed in the electrolytic solution as negative electrode and anode.
3. be 80 ° of C by the temperature that constant-temperature temperature-control instrument and electric mantle control electrolytic solution, apply constant voltage 1.8 V galvanic deposit 3 hours.Take out negative electrode distilled water flushing after galvanic deposit clean, then with raw spirit cleaning, dry and preserve.
By the macro morphology of observation by light microscope gained metal iron layer, as shown in Figure 6 (b).Cathode sheets in the plating solution galvanic deposit, after 3 hours, galvanic deposit can obtain the thin metallic iron settled layer of one deck.
Claims (1)
1. in choline chloride 60 class ionic liquid by a method for ferric oxide galvanic deposit Nanoscale Iron, it is characterized in that there is following process and step:
A. the preparation of ionic liquid electrolyte: be first 1:2 by choline chloride 60 and ethylene glycol according to mol ratio or be that 1:2 mix with urea according to mol ratio by choline chloride 60; Then stir 4-15 hours under 50 ° of C-80 ° of C constant temperatures, form water white transparency shape choline chloride 60 class ionic liquid;
B. the preparation of plating solution: analytically pure for excess chemical ferric oxide powder is added in the ionic liquid prepared in step a, stir 40-80 hours under 25 ° of C-80 ° of C constant temperature, obtain the choline chloride 60 class ionic liquid solution that ferric oxide is saturated;
C. cell system is formed: the present invention adopts polytetrafluoroethylene beaker as reaction vessel, adopt the ferric oxide saturated choline chloride 60 class ionic liquid configured in above-mentioned steps b as ionogen, adopt the plating metal matrixes such as the copper sheet after polishing, activation or copper rod as negative electrode, platinum filament is anode, to form electro-deposition system;
D. electrodeposition process controls: in electrodeposition process, the temperature of cell system controls at 60 ° of C-120 ° of C by constant-temperature temperature-control instrument and electric mantle, and the voltage applied is 1.2 V-1.9 V, and electrodeposition time is 1-20 hour;
E. galvanic deposit complete after taking-up cathode sheets, clean with distilled water flushing, then clean with dehydrated alcohol, can nano iron plating be obtained after oven dry.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104233361A (en) * | 2014-09-05 | 2014-12-24 | 昆明理工大学 | Method for electrolyzing ferric oxide by using deep eutectic solvent to prepare ferroferric oxide |
| CN107761142A (en) * | 2017-11-10 | 2018-03-06 | 昆明理工大学 | A kind of method of eutectic solvent Electrodeposition Bath of Iron evanohm coating |
| CN108754556A (en) * | 2018-06-28 | 2018-11-06 | 南京信息工程大学 | A kind of method of simple system electrodepositing zinc coating |
| CN110205651A (en) * | 2019-07-11 | 2019-09-06 | 昆明理工大学 | A kind of method that low temperature electrochemical reduction barium oxide prepares vanadium metal |
| CN110246685A (en) * | 2019-07-17 | 2019-09-17 | 徐靖才 | A kind of preparation method of samarium ferromagnetic phase |
-
2015
- 2015-04-21 CN CN201510189705.7A patent/CN104911643A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| HAOXING YANG: "Electrochemical deposition of zinc from zinc oxide in 2:1 urea/cholinechloride ionic liquid", 《ELECTROCHIMICA ACTA》 * |
| MOHAMMAD HARATI: "Preparation ofcrystallinezincoxidefilmsbyone-stepelectrodeposition in Reline", 《MATERIALS LETTERS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104233361A (en) * | 2014-09-05 | 2014-12-24 | 昆明理工大学 | Method for electrolyzing ferric oxide by using deep eutectic solvent to prepare ferroferric oxide |
| CN107761142A (en) * | 2017-11-10 | 2018-03-06 | 昆明理工大学 | A kind of method of eutectic solvent Electrodeposition Bath of Iron evanohm coating |
| CN108754556A (en) * | 2018-06-28 | 2018-11-06 | 南京信息工程大学 | A kind of method of simple system electrodepositing zinc coating |
| CN110205651A (en) * | 2019-07-11 | 2019-09-06 | 昆明理工大学 | A kind of method that low temperature electrochemical reduction barium oxide prepares vanadium metal |
| CN110246685A (en) * | 2019-07-17 | 2019-09-17 | 徐靖才 | A kind of preparation method of samarium ferromagnetic phase |
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Application publication date: 20150916 |