CN104846411B - The method and its product of flower-like nanometer metal cobalt are prepared using anodic oxidation aluminium formwork - Google Patents
The method and its product of flower-like nanometer metal cobalt are prepared using anodic oxidation aluminium formwork Download PDFInfo
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- CN104846411B CN104846411B CN201510204698.3A CN201510204698A CN104846411B CN 104846411 B CN104846411 B CN 104846411B CN 201510204698 A CN201510204698 A CN 201510204698A CN 104846411 B CN104846411 B CN 104846411B
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Abstract
The present invention provides a kind of method for preparing flower-like nanometer metal cobalt using electro-conductive glass FTO, anodic oxidation aluminium formwork (AAO) and aqueous high molecular bonding agent for combination electrode, includes the preparation of step (1) working electrode：Aqueous adhesive polyvinyl alcohol (PVA) solution is spin-coated on electro-conductive glass, bonding anodic oxidation aluminium formwork obtains FTO/PVA/AAO combination electrodes, the preparation of (2) electrolyte：Cobaltous sulfate and boric acid solution are prepared respectively, are mixed, (3) electrodeposit reaction：Using three-electrode system, constant voltage electro-deposition is carried out on compound working electrode；(4) post-process：Working electrode after electro-deposition is immersed in sodium hydroxide, anodic oxidation aluminium formwork is removed.The metallic cobalt of the invention for being prepared for new flower-like nanostructure by constant voltage deposition using FTO/PVA/AAO as compound working electrode, this method simple and fast, compared with conventional method, reaction condition is gentle, time short efficiency high, it is not necessary to high-temperature and high-pressure conditions.
Description
Technical field
The invention belongs to metal material field, and in particular to a kind of side for electrochemically preparing nanoscale metal material
Method.
Background technology
Metallic cobalt is all widely used due to its special performance in many fields, such as hard metal, ceramic chemical industry,
In terms of catalysis, battery and magnetic material.The magnetic recording material being made of cobalt alloy, it is big with packing density height, coercivity,
Signal to noise ratio is good, many advantages, such as antioxygenic property is good；Cobalt is added in Ni-MH battery, specific discharge capacity and large current density can be improved
Electric cyclical stability.The property of the structures shape material of material, the microstructure and size of metallic cobalt have decisive to its property
Effect, it is possible to change its property by changing the microstructure and size of metallic cobalt.Therefore, it is prepared by various methods
The micro/nano material of various different-shape sizes turns into the focus of research.
At present, existing many document reports have synthesized the metallic cobalt of diverse microcosmic appearance, and such as chemical preparation process is obtained
Metal cobalt nanowire (patent CN101698234A) such as chain, nanometre metal cobalt powder (patent is prepared with liquid phase chemical reduction
CN102873336A) and laminated metal cobalt, metallic cobalt and other metals compound etc..In the preparation method of metallic cobalt, such as
Gas phase hydrogen reduction method, x ray irradiation x method, microemulsion method, oxalates thermal decomposition method, the hot method of hydrothermal/solvent etc., most complex operation,
The reaction conditions such as HTHP are needed, are unfavorable for large-scale production.Metal nano material is prepared with AAO templates, it usually needs
The face metal sprayings of AAO mono-, powder body material is obtained after template removing, and cost is also high.
Electrochemical method is the method for making metal ion form sedimentary in cathodic reduction under applied voltage, can be with
Carried out using two electrode systems or three-electrode system.During electrochemistry prepares nano metal material, by selecting work
The technological parameters such as electrode, electric current, voltage, control the generation of nucleus and the growth of nucleus, can obtain the deposition of crystal grain even compact
Layer, and be expected to that the nano metal material with particular geometric pattern is made.
The content of the invention
The problem of existing for this area, flower-like nanometer is prepared the purpose of the present invention is to propose to one kind using alumina formwork
The method of metallic cobalt.
It is another object of the present invention to propose material that the preparation method is prepared.
The technical scheme for realizing the object of the invention is：
A kind of method that utilization alumina formwork prepares flower-like nanometer metal cobalt, comprises the following steps：
(1) preparation of working electrode：Poly-vinyl alcohol solution is spin-coated on electro-conductive glass, one layer of anode is bonded on its surface
Alumina formwork, is put into vacuum drying oven and is handled 0.5-5 hours at 120-180 DEG C, regard gained combination electrode as working electrode；
(2) preparation of electrolyte：Compound concentration is respectively 0.05-0.2 Cobaltous sulfate and boric acid solution, and is mixed
Close；
(3) electrodeposition process：Using three-electrode system, constant voltage is deposited on working electrode made from step (1)；Three electricity
It is platinized platinum to electrode, reference electrode is saturated calomel electrode, and electrolysis time is 5-60min in polar body system；
(4) post-process：Working electrode after electro-deposition is immersed in sodium hydroxide solution, anodic oxidation aluminum dipping form is removed
Plate, is finally cleaned working electrode 2-6 times with ultra-pure water.
Wherein, the mass fraction of poly-vinyl alcohol solution described in step (1) is 6-7%.
The poly-vinyl alcohol solution concentration of the spin coating on electro-conductive glass is prepared on material direct influence.PVA concentration is too high,
Such as 8%, cause PVA insulating barriers on FTO too thick, cobalt ions is difficult to reach FTO surfaces through PVA layers, and can not occur electricity also
It is former；PVA concentration is too low, can not effectively be bonded AAO layers, such as 5% poly-vinyl alcohol solution, it is impossible to obtains FTO/PVA/AAO and answers
Composite electrode.
Wherein, the aperture of anodic oxidation aluminium formwork described in step (1) is 40-200nm.Specific optional 80-100nm holes
One kind is made in footpath, 40-70nm apertures, 100-120nm apertures, 160-200nm apertures, realizes the control to pattern.
Inventor cannot get flower-like structure with the FTO/PVA template electric-sedimentations without AAO (mechanism is unclear).
Preferably, compound concentration is respectively 0.1mol/L Cobaltous sulfate and boric acid solution in step (2), and is mixed
Close.
Preferably, the voltage of electrolysis is -1.5V in step (3), and electrodeposition time is 10-60min.
The material obtained by the method for the present invention for preparing flower-like nanometer metal cobalt.
The beneficial effects of the present invention are：
The present invention is prepared for a kind of metallic cobalt of new flower-like nanostructure with anodic oxidation aluminium formwork by electro-deposition,
This method simple and fast, compared with conventional method, reaction condition is gentle, it is not necessary to high-temperature and high-pressure conditions.
Nano level metal cobalt made from the method for the present invention, has well-regulated geometrical morphology.The present invention is by changing AAO moulds
Board size and electrochemical parameter regulate and control the pattern of nano level metal cobalt, so as to obtain the material of different magnetic properties.
Brief description of the drawings
Fig. 1 is the product XRD spectrum that the embodiment of the present invention 1 is prepared.
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
Detailed description below is used to illustrate the present invention, but should not be construed as limiting the invention.In embodiment, such as
Without special instruction, technological means used is this area conventional technology.
Embodiment Anodic Oxidation aluminum alloy pattern plate is purchased from Hefei Pu Yuan Science and Technology Ltd.s.Electro-conductive glass is FTO purchased in market (doping
The SnO of fluorine2Transparent conducting glass).
Embodiment 1：
By 1 × 2cm2Poly-vinyl alcohol solution (the spin coating rotating speed of electro-conductive glass FTO one layer 6% of half position spin coating
2000rpm), anodised aluminium (AAO) layer that adhesion aperture is 80-100nm afterwards, (size is 1cm × 1cm, i.e. participate in electricity
The electrode area of chemical reaction is 1cm2), it is put into vacuum drying oven 150 DEG C and handles 2 hours, obtains working electrode.Prepare respectively
0.1mol/L Cobaltous sulfate and boric acid aqueous solution, is used as the electrolyte of three-electrode system after mixing.
It is platinum plate electrode to electrode, reference electrode is saturated calomel electrode using three-electrode system, selects current-vs-time
Method, voltage is -1.5V, electro-deposition is carried out on the working electrode (s, sedimentation time is 60min.After electro-deposition terminates, with 1mol/L's
Sodium hydroxide solution removes anodic oxidation aluminium formwork, is finally cleaned working electrode three times with ultra-pure water.
Obtained material powder diffraction XRD spectrum such as Fig. 1 (on), in order to contrast, substrate FTO (in) and FTO/PVA
(under) XRD spectra also list in Fig. 1.The bright obtained material of the chart is metallic cobalt.The SEM photograph of the material such as Fig. 2, card
Large area lamella flower-shaped metallic cobalt is obtained in fact.
Embodiment 2
Choosing applies one layer 6% of poly-vinyl alcohol solution on electro-conductive glass FTO, and the anode that aperture is 40-70nm is adhered to afterwards
Aluminum oxide (AAO) layer, is put into vacuum drying oven 150 DEG C and handles 2 hours, obtains working electrode (size is 1cm × 1cm).Respectively
0.1mol/L Cobaltous sulfate and boric acid aqueous solution is prepared, the electrolyte of three-electrode system is used as after mixing.
It is platinum plate electrode to electrode, reference electrode is saturated calomel electrode using three-electrode system, selects current-vs-time
Method, voltage is -1.5V, electro-deposition is carried out on the working electrode (s, sedimentation time is 60min.After electro-deposition terminates, with 1mol/L's
Sodium hydroxide solution removes anodic oxidation aluminium formwork, is finally cleaned working electrode three times with ultra-pure water.
The SEM spectrum of obtained material such as Fig. 3.
Embodiment 3
The poly-vinyl alcohol solution (spin coating rotating speed 2000rpm) of one layer 6% of the spin coating on electro-conductive glass FTO, afterwards adhesive hole
Footpath is 160-200nm anodised aluminium (AAO) layer, is put into vacuum drying oven 150 DEG C and handles 2 hours, obtains working electrode.Point
Not Pei Zhi 0.1mol/L Cobaltous sulfate and boric acid aqueous solution, the electrolyte of three-electrode system is used as after mixing.
It is platinum plate electrode to electrode, reference electrode is saturated calomel electrode using three-electrode system, selects current-vs-time
Method, voltage is -1.5V, electro-deposition is carried out on the working electrode (s, sedimentation time is 60min.After electro-deposition terminates, with 1mol/L's
Sodium hydroxide solution removes anodic oxidation aluminium formwork, is finally cleaned working electrode three times with ultra-pure water.
The SEM spectrum of obtained material such as Fig. 4.
Embodiment 4
The poly-vinyl alcohol solution of one layer 6% of spin coating on electro-conductive glass FTO, adheres to the anode that aperture is 80-100nm afterwards
Aluminum oxide (AAO) layer, is put into vacuum drying oven 150 DEG C and handles 2 hours, obtain working electrode.Prepare 0.1mol/L's respectively
Cobaltous sulfate and boric acid aqueous solution, are used as the electrolyte of three-electrode system after mixing.
It is platinum plate electrode to electrode, reference electrode is saturated calomel electrode using three-electrode system, selects current-vs-time
Method, voltage is -1.5V, electro-deposition is carried out on the working electrode (s, sedimentation time is 30min.After electro-deposition terminates, with 1mol/L's
Sodium hydroxide solution removes anodic oxidation aluminium formwork, is finally cleaned working electrode three times with ultra-pure water.
The SEM photograph of obtained material such as Fig. 5.Relative to Fig. 2, lamella petal is more sparse and small in the figure.
Compared from the SEM photograph of embodiment 1-4 materials, the present processes, by select AAO pore size of template or
The time of electro-deposition, obtained material has different density and shape characteristic.
Embodiment above is only that the embodiment of the present invention is described, and not the scope of the present invention is entered
Row is limited, and those skilled in the art can also do numerous modifications and variations, be set not departing from the present invention on the basis of existing technology
On the premise of meter spirit, all variations and modifications that this area ordinary skill technical staff makes to technical scheme,
In the protection domain that claims of the present invention determination all should be fallen into.
Claims (2)
1. a kind of method that utilization anodic oxidation aluminium formwork prepares flower-like nanometer metal cobalt, it is characterised in that：Comprise the following steps：
(1) preparation of working electrode：Poly-vinyl alcohol solution is spin-coated on electro-conductive glass, one layer of anodic oxidation is bonded on its surface
Aluminum alloy pattern plate, is put into vacuum drying oven and is handled 0.5-5 hours at 120-180 DEG C, regard gained combination electrode as working electrode；
The mass fraction of wherein described poly-vinyl alcohol solution is 6-7%, and the aperture of the anodic oxidation aluminium formwork is 40-200nm；
(2) preparation of electrolyte：Compound concentration is respectively 0.1mol/L Cobaltous sulfate and boric acid solution, and is mixed；
(3) electrodeposition process：Using three-electrode system, constant voltage is deposited on working electrode made from step (1)；Three electrode bodies
It is platinized platinum to electrode in system, reference electrode is saturated calomel electrode, and the voltage of electrolysis is -1.5V, and electrolysis time is 15-
60min；
(4) post-process：Working electrode after electro-deposition is immersed in sodium hydroxide solution, anodic oxidation aluminium formwork is removed, most
Working electrode is cleaned 2-6 times with ultra-pure water afterwards.
2. the material prepared as the method for preparing flower-like nanometer metal cobalt described in claim 1.
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| CN105057694B (en) * | 2015-08-26 | 2017-06-27 | 南京理工大学 | A kind of method for quickly preparing nm of gold using electricity displacement reaction on electro-conductive glass |
| 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 |
| CN110158127B (en) * | 2019-05-15 | 2021-02-02 | 重庆大学 | Method for strengthening critical heat flux density of heat transfer surface liquid film drying |
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