CN104846411A - Method for preparing flowerlike nanometer cobalt by using anodised aluminum template, and product of same - Google Patents
Method for preparing flowerlike nanometer cobalt by using anodised aluminum template, and product of same Download PDFInfo
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Abstract
The invention provides a method for preparing flowerlike nanometer cobalt by using electro-conductive glass FTO, an anodised aluminum template (AAO) and an aqueous high-molecular adhesive as a combined electrode. The method comprises the following steps: (1) preparation of a working electrode: a step of coating the electro-conductive glass with a solution of the aqueous high-molecular adhesive--polyvinyl alcohol (PVA) through spin coating and bonding the anodised aluminum template so as to obtain the FTO/PVA/AAO combined electrode; (2) preparation of an electrolyte: separately preparing cobaltous sulfate and a boric acid solution and mixing the cobaltous sulfate with the boric acid solution; (3) electrodeposition reaction: a step of carrying out constant-voltage electrodeposition on the combined working electrode; and (4) post-treatment: a step of soaking the working electrode having undergone electrodeposition in sodium hydroxide to remove the anodised aluminum template. According to the invention, FTO/PVA/AAO is used as the combined working electrode and constant-voltage electrodeposition is carried out so as to prepare the novel flowerlike nanostructured cobalt; and the method is simple and fast and has the advantages of mild reaction conditions, short time, high efficiency and no need for high temperature and high pressure conditions compared with conventional methods.
Description
Technical field
The invention belongs to metal material field, be specifically related to a kind of method electrochemically preparing nanoscale metal material.
Background technology
Cobalt metal, due to its special performance, is all widely used in a lot of fields, as hard metal, and ceramic chemical industry, catalysis, the aspect such as battery and magneticsubstance.With the magnetic recording material that cobalt-base alloy is made, have that recording density is high, coercive force is large, the plurality of advantages such as signal to noise ratio is good, and antioxidant property is good; Add cobalt in nickel metal hydride battery, specific discharge capacity and high current charge-discharge cyclical stability can be improved.The character of the structures shape material of material, the microtexture of cobalt metal and size have decisive role to its character, so can change its character by the microtexture and size changing cobalt metal.Therefore, the micro/nano material preparing various different-shape size by various method has become the focus of research.
At present, existing many bibliographical informations have synthesized the cobalt metal of diverse microcosmic appearance, and such as chemical preparation process obtains metal cobalt nanowire (patent CN101698234A) as chain, the mixture etc. preparing nanometre metal cobalt powder (patent CN102873336A) and laminated metal cobalt, cobalt metal and other metals with liquid phase chemical reduction.In the preparation method of cobalt metal, as gas phase hydrogen reduction method, x ray irradiation x method, microemulsion method, oxalate thermal decomposition method, the hot method of hydrothermal/solvent etc., most complicated operation, needs the reaction conditionss such as High Temperature High Pressure, is unfavorable for scale operation.With AAO Template preparation metal nano material, usually need at AAO metal spraying, after template removes, obtain powder body material, and cost is also high.
Electrochemical method is under impressed voltage, makes metal ion form the method for settled layer in cathodic reduction, and two electrode systems or three-electrode system can be adopted to carry out.Prepare in nano metal material process in electrochemistry, by selecting the processing parameters such as working electrode, electric current, voltage, control the generation of nucleus and the growth of nucleus, the settled layer of uniform crystal particles densification can be obtained, and be expected to the obtained nano metal material with particular geometric pattern.
Summary of the invention
For this area Problems existing, the object of the invention is to propose a kind of method utilizing alumina formwork to prepare flower-like nanometer metal cobalt.
Another object of the present invention is the material that the described preparation method of proposition prepares.
The technical scheme realizing the object of the invention is:
Utilize alumina formwork to prepare a method for flower-like nanometer metal cobalt, comprise the following steps:
(1) preparation of working electrode: be spin-coated on by polyvinyl alcohol solution on conductive glass, at its surface bonding one deck anodic oxidation aluminium formwork, puts into vacuum drying oven at 120-180 DEG C of process 0.5-5 hour, using gained combined electrode as working electrode;
(2) preparation of electrolytic solution: compound concentration is respectively Cobaltous sulfate and the boric acid solution of 0.05-0.2, and is mixed;
(3) electrodeposition process: adopt three-electrode system, constant voltage deposition on the working electrode that step (1) is obtained; In three-electrode system, be platinized platinum to electrode, reference electrode is saturated calomel electrode, and electrolysis time is 5-60min;
(4) aftertreatment: be immersed in sodium hydroxide solution by the working electrode after galvanic deposit, removing anodic oxidation aluminium formwork, finally cleans 2-6 time with ultrapure water by working electrode.
Wherein, described in step (1), the massfraction of polyvinyl alcohol solution is 6-7%.
The polyvinyl alcohol solution concentration of spin coating on conductive glass has direct impact to material preparation.PVA concentration is too high, and such as 8%, cause PVA insulation layer on FTO too thick, cobalt ion is difficult to arrive FTO surface through PVA layer, and electroreduction can not occur; PVA concentration is too low then cannot effective bonding AAO layer, and the polyvinyl alcohol solution of such as 5%, cannot obtain FTO/PVA/AAO combined electrode.
Wherein, described in step (1), the aperture of anodic oxidation aluminium formwork is 40-200nm.Concrete optional 80-100nm aperture, 40-70nm aperture, 100-120nm aperture, the obtained one in 160-200nm aperture, realize the control to pattern.
Contriver, with the FTO/PVA template electric-sedimentation not having AAO, can not get flower-like structure (mechanism it be unclear that).
Preferably, in step (2), compound concentration is respectively Cobaltous sulfate and the boric acid solution of 0.1mol/L, and is mixed.
Preferably, in step (3), the voltage of electrolysis is-1.5V, and electrodeposition time is 10-60min.
The material obtained by the method preparing flower-like nanometer metal cobalt of the present invention.
Beneficial effect of the present invention is:
The present invention, by galvanic deposit, has prepared a kind of cobalt metal of novel flower-like nanostructure with anodic oxidation aluminium formwork, the method simple and fast, and compared with traditional method, reaction conditions is gentle, does not need high-temperature and high-pressure conditions.
The nano level metal cobalt that method of the present invention is obtained, the well-regulated geometrical morphology of tool.The present invention regulates and controls the pattern of nano level metal cobalt by change AAO template size and electrochemical parameter, thus can obtain the material of different magnetic property.
Accompanying drawing explanation
Fig. 1 is the product XRD figure spectrum that the embodiment of the present invention 1 prepares.
Fig. 2 is product scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 1.
Fig. 3 is product scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 2.
Fig. 4 is product scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 3.
Fig. 5 is product scanning electron microscope (SEM) photograph prepared by the embodiment of the present invention 4.
Embodiment
Following embodiment for illustration of the present invention, but should not be construed as limitation of the present invention.In embodiment, if no special instructions, technique means used is the technique means of this area routine.
Embodiment Anodic Oxidation aluminum alloy pattern plate is purchased from Hefei Pu Yuan Science and Technology Ltd..Conductive glass is the commercial FTO (SnO of doped with fluorine
2transparent conducting glass).
Embodiment 1:
By 1 × 2cm
2the polyvinyl alcohol solution (spin coating rotating speed 2000rpm) of half position spin coating one deck 6% of conductive glass FTO, adhere to anodised aluminium (AAO) layer that aperture is 80-100nm afterwards, (be of a size of 1cm × 1cm, that is, the electrode area participating in electrochemical reaction is 1cm
2), put into vacuum drying oven 150 DEG C process 2 hours, obtain working electrode.Prepare Cobaltous sulfate and the boric acid aqueous solution of 0.1mol/L respectively, as the electrolytic solution of three-electrode system after mixing.
Adopt three-electrode system, be platinum plate electrode to electrode, reference electrode is saturated calomel electrode, and select current-vs-time method, voltage is-1.5V, carries out galvanic deposit on the working electrode (s, and depositing time is 60min.After galvanic deposit terminates, with the sodium hydroxide solution removing anodic oxidation aluminium formwork of 1mol/L, finally with ultrapure water, working electrode is cleaned three times.
The material obtained powdery diffractometry XRD figure spectrum as Fig. 1 (on), in order to contrast, substrate FTO (in) and FTO/PVA (under) XRD spectra also list in FIG.This figure shows that the material obtained is cobalt metal.The SEM photo of this material, as Fig. 2, confirms to obtain big area lamella flower-shaped metallic cobalt.
Embodiment 2
On conductive glass FTO, choosing is coated with the polyvinyl alcohol solution of one deck 6%, adheres to anodised aluminium (AAO) layer that aperture is 40-70nm afterwards, puts into vacuum drying oven 150 DEG C process 2 hours, obtains working electrode (being of a size of 1cm × 1cm).Respectively prepare 0.1mol/L Cobaltous sulfate and boric acid aqueous solution, as the electrolytic solution of three-electrode system after mixing.
Adopt three-electrode system, be platinum plate electrode to electrode, reference electrode is saturated calomel electrode, and select current-vs-time method, voltage is-1.5V, carries out galvanic deposit on the working electrode (s, and depositing time is 60min.After galvanic deposit terminates, with the sodium hydroxide solution removing anodic oxidation aluminium formwork of 1mol/L, finally with ultrapure water, working electrode is cleaned three times.
The SEM collection of illustrative plates of the material obtained is as Fig. 3.
Embodiment 3
The polyvinyl alcohol solution (spin coating rotating speed 2000rpm) of spin coating one deck 6% on conductive glass FTO, adhere to anodised aluminium (AAO) layer that aperture is 160-200nm afterwards, put into vacuum drying oven 150 DEG C process 2 hours, obtain working electrode.Respectively prepare 0.1mol/L Cobaltous sulfate and boric acid aqueous solution, as the electrolytic solution of three-electrode system after mixing.
Adopt three-electrode system, be platinum plate electrode to electrode, reference electrode is saturated calomel electrode, and select current-vs-time method, voltage is-1.5V, carries out galvanic deposit on the working electrode (s, and depositing time is 60min.After galvanic deposit terminates, with the sodium hydroxide solution removing anodic oxidation aluminium formwork of 1mol/L, finally with ultrapure water, working electrode is cleaned three times.
The SEM collection of illustrative plates of the material obtained is as Fig. 4.
Embodiment 4
The polyvinyl alcohol solution of spin coating one deck 6% on conductive glass FTO, adheres to anodised aluminium (AAO) layer that aperture is 80-100nm afterwards, puts into vacuum drying oven 150 DEG C process 2 hours, obtains working electrode.Respectively prepare 0.1mol/L Cobaltous sulfate and boric acid aqueous solution, as the electrolytic solution of three-electrode system after mixing.
Adopt three-electrode system, be platinum plate electrode to electrode, reference electrode is saturated calomel electrode, and select current-vs-time method, voltage is-1.5V, carries out galvanic deposit on the working electrode (s, and depositing time is 30min.After galvanic deposit terminates, with the sodium hydroxide solution removing anodic oxidation aluminium formwork of 1mol/L, finally with ultrapure water, working electrode is cleaned three times.
The SEM photo of the material obtained is as Fig. 5.Relative to Fig. 2, in this figure, lamella petal is comparatively sparse and little.
From embodiment 1-4 material SEM photo relatively, the method for the application, by selecting the time of AAO pore size of template or galvanic deposit, obtained material has different density and shape characteristic.
Above embodiment is only be described the specific embodiment of the present invention; not scope of the present invention is limited; those skilled in the art also can do numerous modifications and variations on the basis of existing technology; under not departing from the present invention and designing the prerequisite of spirit; the various modification that the common engineering technical personnel in this area make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determine.
Claims (6)
1. utilize anodic oxidation aluminium formwork to prepare a method for flower-like nanometer metal cobalt, it is characterized in that: comprise the following steps:
(1) preparation of working electrode: be spin-coated on by polyvinyl alcohol solution on conductive glass, at its surface bonding one deck anodic oxidation aluminium formwork, puts into vacuum drying oven at 120-180 DEG C of process 0.5-5 hour, using gained combined electrode as working electrode;
(2) preparation of electrolytic solution: compound concentration is respectively Cobaltous sulfate and the boric acid solution of 0.05-0.2mol/L, and is mixed;
(3) electrodeposition process: adopt three-electrode system, constant voltage deposition on the working electrode that step (1) is obtained; In three-electrode system, be platinized platinum to electrode, reference electrode is saturated calomel electrode, and electrolysis time is 5-60min;
(4) aftertreatment: be immersed in sodium hydroxide solution by the working electrode after galvanic deposit, removing anodic oxidation aluminium formwork, finally cleans 2-6 time with ultrapure water by working electrode.
2. the method preparing flower-like nanometer metal cobalt according to claim 1, is characterized in that: described in step (1), the massfraction of polyvinyl alcohol solution is 6-7%.
3. the method preparing flower-like nanometer metal cobalt according to claim 1 and 2, is characterized in that: described in step (1), the aperture of anodic oxidation aluminium formwork is 40-200nm.
4. the method preparing flower-like nanometer metal cobalt according to claim 1 and 2, is characterized in that: in step (2), compound concentration is Cobaltous sulfate and the boric acid solution of 0.1mol/L respectively, and is mixed.
5. the method preparing flower-like nanometer metal cobalt according to claim 1 and 2, is characterized in that: in step (3), the voltage of electrolysis is-1.5V, and electrolysis time is 15-60min.
6. the material prepared by the arbitrary described method preparing flower-like nanometer metal cobalt of claim 1-5.
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Cited By (3)
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| CN105057694A (en) * | 2015-08-26 | 2015-11-18 | 南京理工大学 | Method for quickly preparing nanogold on conducting glass through electric replacement reaction |
| CN107620100A (en) * | 2017-08-22 | 2018-01-23 | 滁州玛特智能新材料科技有限公司 | A kind of preparation method of thin film thermoelectric materials |
| CN110158127A (en) * | 2019-05-15 | 2019-08-23 | 重庆大学 | A kind of method for the critical heat flux density that enhanced heat transfer surfaces liquid film dryouies |
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| CN110158127A (en) * | 2019-05-15 | 2019-08-23 | 重庆大学 | A kind of method for the critical heat flux density that enhanced heat transfer surfaces liquid film dryouies |
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