CN101629320A - Preparation method of one-dimensional mesoporous Co nanowire array - Google Patents
Preparation method of one-dimensional mesoporous Co nanowire array Download PDFInfo
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- CN101629320A CN101629320A CN200910183086A CN200910183086A CN101629320A CN 101629320 A CN101629320 A CN 101629320A CN 200910183086 A CN200910183086 A CN 200910183086A CN 200910183086 A CN200910183086 A CN 200910183086A CN 101629320 A CN101629320 A CN 101629320A
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Abstract
The invention discloses a preparation method of a one-dimensional mesoporous Co nanowire array, which comprising the following steps: preparing a precursor solution at room temperature by mixing 0.5-0.7g of PEP-POO-PEP (P123) which is an addition polymer of polypropylene glycol and ethylene oxide, 0.9-3g of tetraethyl orthosilicate and 0.4g of 38 wt% muriatic acid together; in an AAO (anodised aluminium) template, synthesizing SBA (mesoporous silica) nanofibers, wherein the mesoporous canals of the SBA (mesoporous silica) nanofibers are parallel to AAO canals; preparing electrodeposit liquid in the ratio of 2-4g of Co(CH3COO)2 : 1-3g of H3BO3; taking an aluminium base AAO-SBA composite mesoporous template as a working electrode and taking graphite as an auxiliary electrode, and controlling electrode density between 0.5-1.5 mA/cm2 and electrodepositing for 1.0-1.5h to obtain a Co nanowire with the width of about 200nm, wherein the Co nanowire consists of 4-6mn mesoporous Co nano rods. The invention adopts a simple electrochemical method to generate Co nano structures in AAO-SBA composite mesopores for the first time; and the growth direction of the crystals of the nano structures is controlled by the mesoporous canals. The invention has simple equipment, can be operated easily and is suitable to the industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of one-dimensional mesoporous Co nanowire array, belong to the synthetic field of inorganic nano material.
Background technology
Along with the continuous development of new technology, more and more higher to nano material's structure and performance requriements.One-dimensional mesoporous material is owing to have features such as pore size distribution is narrow, the duct shape is various, high-specific surface area, high pore volume, and is studied personnel's extensive concern.Adopt electrochemical deposition method at one-dimensional mesoporous SiO
2The relative solid nano line of the meso-porous nano wire material of synthetic novel structure is compared and had a lot of obvious characteristics in the duct: (1) has higher specific surface area; (2) the adjustable pattern of periodicity, metallic surface pattern can have influence on metallic surface cytogene resonance, have expanded the application of metal in field of spectroscopy; (3) at electronics and phonon transmission field huge application potential is arranged.One-dimensional mesoporous magneticsubstance is a kind of up-and-coming new adsorbent, adsorbing agent carrier, has application prospect in the magnetic resolution field.Europe Elsevier " investigation of materials communique " (Materials ResearchBulletin 2004 the 39th phase 811 pages) report adopts three electrode dc electrodeposition methods to synthesize the Co nano-wire array that is of a size of 45nm in anodised AAO of two steps; The U.S. " physical chemistry C " (TheJournal of Physical Chemistry C 2008 112 the 5th phase 1468 pages) is reported in the AAO template, adopt the pulse electrodeposition method synthesize different orientation monocrystalline Co nano wire, when pulsed voltage is 1.5V, time is 5ms, can be oriented to the Co nano wire of [1010] HCP structure, when being 3.0V when pulsed voltage, the time is 7.5ms, can be oriented to the Co nano wire of [220] FCC structure.Although there is bibliographical information electrochemical deposition in the AAO template to prepare the Co nano-wire array, adopt this method can't obtain having the one-dimensional magnetic Co nanostructure of meso-hole structure.Britain's " nature " (Nature 2004 the 3rd phase 816 pages) and U.S.'s " nanometer wall bulletin " (Nano Letter 2004 the 4th phase 2337 pages) have reported employing collosol and gel (Sol-Gel) method, the SiO that obtains having hexagonal mesoporous structure in macropore AAO respectively
2Fiber (SBA) can obtain the SiO of spiral, laminate structure by the adding proportion in control surface promoting agent, structure directing agent, silicon source
2Fiber, and can't obtain being parallel to the SBA structure of AAO template hole wall.So adopt this AAO-SBA composite shuttering electrochemical deposition, can only obtain the point-like size distribution in the SBA mesopore orbit, can't prepare and have one-dimension oriented meso-porous nano structure.
Summary of the invention
The present invention proposes the novel SBA structure that in AAO synthesising mesoporous duct is parallel to the AAO duct, and galvanic deposit obtains having one-dimension oriented mesoporous Co nanowire array in this composite mesopore template.
The preparation method of the one-dimensional mesoporous Co nanowire array that the present invention proposes is characterized in that may further comprise the steps:
1), adopt a step anonizing to prepare porous alumina formwork;
2), parallel aluminum oxide (AAO)-silicon-dioxide (SBA) the composite mesopore template in Prepared by Sol Gel Method duct: under the room temperature, addition polymer PEO-PPO-PEO (P123) 0.5-0.7g of polypropylene glycol and oxyethane, positive tetraethyl orthosilicate 0.93g, 38wt% hydrochloric acid 0.4g are mixed with pioneer's solution, porous alumina formwork is immersed in 20-24h in pioneer's solution, take out afterwards under 50-70 ℃ of condition and carry out dry 12-15h, at 400-500 ℃ of following thermal treatment 4-6h, obtain the AAO-SBA composite mesopore template of the parallel alumina formwork of mesopore orbit then;
3), remove composite mesopore template surface SiO
2Zone of oxidation;
4), preparation electroplate liquid: press Co (CH
3COO)
22-4g: H
3BO
3The 1-3g wiring solution-forming, regulate behind the constant volume pH value to 4-6 as electrodeposit liquid;
5), the preparation of mesoporous Co nanowire array: as working electrode, is supporting electrode with graphite with above-mentioned aluminium substrate AAO-SBA composite mesopore template, and control electrode density is at 0.5-1.5mA/cm
2, galvanic deposit 1.0-1.5 hour, promptly obtain mesoporous Co nanowire.
Mesoporous Co nano-array of the present invention is characterized in that: nanowire size is 200nm, is made up of the mesoporous Co nanofiber of 4-6nm, and crystal growth direction is parallel to mesopore orbit.
Key point of the present invention is to obtain being parallel to the SBA meso-hole structure in AAO hole in the AAO template, and is that template electrochemical deposition obtains one-dimensional mesoporous Co nanowire with this complex mesoporous material.
(1) by adjustment sheet surface-active agent P123, silicon source, hydrochloric acid additional proportion, under appropriate postprocessing technology, can obtain being parallel to the mesoporous SBA structure in AAO duct;
(2) mesoporous Co nano-array preparation method materials of the present invention are simple, and preparation technology is easy and simple to handle, need not complicated synthesis device, greatly reduce preparation cost;
(3) the present invention adopts the grown mesoporous Co nano-array of guiding at AAO-SBA composite mesopore template hole, because diameter, the adjustable length of AAO pattern hole, the mesoporous size of mesoporous SBA, controllable specific surface area, and the area of alumina formwork can be regulated by simple technology.So the inventive method can be used for preparing the mesoporous Co nanowire array of big area, mesoporous size adjustable, the Co nano-wire array of traditional relatively AAO template preparation, it is big that the Co nano wire of the present invention preparation has less mesoporous size, a specific surface, has potential application foreground at magnetic separation, absorption, catalytic field.
Description of drawings
Fig. 1 is parallel to transmission electron microscope figure (a: the embodiment 1 of the AAO-SBA composite mesopore template in AAO duct for the SBA mesopore orbit; B: embodiment 2; C: embodiment 3).
Fig. 2 is FE-SEM figure (a: the embodiment 1 of the mesoporous Co nano-array of growing in AAO-SBA composite mesopore template; B: embodiment 2; C: embodiment 3).
Fig. 3 is the TEM figure with the different amplification of the prepared mesoporous Co nano-array of the embodiment 1 of JEOL JEM 2100 high resolution transmission electron microscopies observation.
Fig. 4 is for by adopting the x-ray diffraction pattern of the mesoporous Co nano-array that embodiment 1 technology grows in AAO-SBA composite mesopore template, X-coordinate is a diffraction angle.
Fig. 5 schemes for the magnetic hysteresis loop (M-H) of the prepared mesoporous Co nano-array of the embodiment that records under 300K with VersaLab 1.
Embodiment:
It below is specific embodiment of the present invention.
Embodiment 1:
1) adopt a step anonizing to prepare porous alumina formwork
The aluminium flake of annealed processing is packed in the electrolyzer, and adopting 0.36mol/mL phosphoric acid is electrolytic solution, and under 0-5 ℃ of condition, the oxidation voltage that adds 120V carries out oxidation, and oxidization time is 60 hours.Then the alumina formwork for preparing is immersed in the 0.36mol/mL phosphoric acid solution 2-3 hour, this step is used for enlarging the porous alumina formwork aperture.
2) the preparation mesopore orbit is parallel to the AAO-SBA composite mesopore template in AAO duct
At room temperature, 0.6g P123 and 40ml ethanol are mixed.Drip positive tetraethyl orthosilicate and the 0.4g hydrochloric acid (38wt%) of 0.93g then respectively, continue stirring solution is mixed, obtain pioneer's solution.At ambient temperature, the porous alumina formwork for preparing is immersed in 24h in pioneer's solution.Afterwards with alumina formwork taking-up and the Gel Treatment on alumina formwork surface is clean.Carry out dry 12h then under 60 ℃ of conditions, the back is at 450 ℃ of insulation 4h.Obtain AAO/SBA composite mesopore template.
3) remove composite mesopore template surface SiO
2Zone of oxidation
The NaOH solution of preparation 1mol/mL drips small amount of N aOH solution at AAO-SBA composite mesopore template surface with dropper, soaks 3-6 time continuously 1-3 minute.This step is in order to remove the SiO that AAO-SBA composite mesopore template surface exists
2Zone of oxidation.
4) preparation electroplate liquid
In this example: accurately take by weighing the 2.47g cobaltous acetate and 1g boric acid is dissolved in the distilled water of 100mL, be stirred to cobaltous acetate and boric acid and all dissolve and mix.Obtain the electroplate liquid of 0.1mol/mL.
5) preparation of one-dimensional mesoporous Co nanowire
Adopt two electrode galvanostatic methods to prepare mesoporous Co nanowire in this example, wherein current density is controlled by universal meter:
The AAO-SBA composite mesopore template of handling well is put into electrolyzer, pour the electric degree liquid of electrolyzer volume 70% into, connect electrode, at room temperature coming control current density by change voltage is 0.5mA/cm
2Electrodeposition time is 1.2h, closes AC power after reaction finishes.Template is taken out, clean with distilled water flushing then.
5) handle having deposited mesoporous Co nanowire AAO-SBA composite shuttering before the sign
The NaOH solution that utilizes 1mol/mL can carry out TEM, FE-SEM, HR-TEM test to after having deposited mesoporous Co nanowire AAO-SBA composite shuttering and carrying out in various degree corrosion.
Embodiment 2:
1) adopt a step anonizing to prepare porous alumina formwork (with embodiment 1)
2) the preparation mesopore orbit is parallel to the AAO-SBA composite mesopore template in AAO duct
At room temperature, 0.5g P123 and 40ml ethanol are mixed.Drip positive tetraethyl orthosilicate and the 0.4g hydrochloric acid (38wt%) of 0.93g then respectively, continue stirring solution is mixed, the AAO template for preparing is immersed in 20h in pioneer's solution.Afterwards alumina formwork is taken out the drying of carrying out 13h under 50 ℃ of conditions, the back is at 400 ℃ of insulation 5h.
3) remove composite mesopore template surface SiO
2Zone of oxidation (with embodiment 1)
4) preparation of one-dimensional mesoporous Co nanowire
Take by weighing the 2g cobaltous acetate and 2g boric acid is dissolved in the distilled water of 100mL, be stirred to cobaltous acetate and boric acid and all dissolve and mix.Control current density 1.0mA/cm
2Carry out electrochemical deposition.Electrodeposition time is 1.0h.
Embodiment 3:
1) adopt a step anonizing to prepare porous alumina formwork (with embodiment 1)
2) the preparation mesopore orbit is parallel to the AAO-SBA composite mesopore template in AAO duct
At room temperature, 0.7g P123 and 40ml ethanol are mixed.Drip positive tetraethyl orthosilicate and the 0.4g hydrochloric acid (38wt%) of 0.93g then respectively, continue stirring solution is mixed, the AAO template for preparing is immersed in 22h in pioneer's solution.Carry out the drying of 15h then under 70 ℃ of conditions, the back is at 500 ℃ of insulation 6h.
3) remove composite mesopore template surface SiO
2Zone of oxidation (with embodiment 1)
4) preparation of one-dimensional mesoporous Co nanowire
Take by weighing the 2g cobaltous acetate and 3g boric acid is dissolved in the distilled water of 100mL, be stirred to cobaltous acetate and boric acid and all dissolve and mix.Control current density 1.5mA/cm
2Carry out electrochemical deposition.Electrodeposition time is 1.5h.
(a, b c) are respectively embodiment 1 to Fig. 1, the TEM figure of 2,3 prepared AAO-SBA composite mesopore templates, can embodiment from figure the 1 prepared about 200nm of mesoporous SBA Fibre diameter, meso-hole structure is perfect (mesopore orbit is parallel to the AAO duct, mesoporous aperture 5-7nm) relatively; And the mesoporous order of AAO duct middle portion is poor among the embodiment 2; Homogeneity mesoporous among the embodiment 3 is relatively poor, and the prepared AAO-SBA composite mesopore structure of possible embodiments 1 is best thus.
Fig. 2 (a, b c) are respectively embodiment 1,2, the FE-SEM figure of 3 prepared mesoporous Co nanowires, and as can be seen from the figure, the mesoporous Co nanowire of embodiment 1 growth is the most perfect, and has the Part of Co nanometer rod to be generated as nanometer sheet among the embodiment 3.
This embodiment 1 prepared mesoporous Co nanowire of Fig. 3 is placed on the HR-TEM figure of multiple in difference, as can be seen from the figure, mesoporous Co nanowire is piled up by some undersized Co nanometer rod and is formed, and the diameter of Co nanometer rod probably is that the mesoporous aperture of 4-6nm and composite mesopore template is suitable.
Fig. 4 is the x-ray diffraction pattern of the prepared mesoporous Co nanowire of embodiment 1.Can see the diffraction peak (311) of Co from the XRD diffractogram, comparison card is the crystalline structure of FCC as can be known.
Fig. 5 is the magnetic hysteresis loop figure (probe temperature: 300K) of the prepared mesoporous Co nano-array of embodiment 1.As can be seen from the figure, the coercive force that records when outfield parallel nanowires long axis direction magnetizes is about 250Oe (Fig. 5 a), remanence ratic is 0.5; It is 0.1 that the coercive force that records when outfield vertical nano-wire long axis direction magnetizes is about 330Oe (Fig. 5 b) remanence ratic.This mesoporous Co nano-array of analysis revealed has stronger shape anisotropy.
Claims (1)
1, a kind of preparation method of one-dimensional mesoporous Co nanowire array is characterized in that may further comprise the steps:
1), adopt a step anonizing to prepare porous alumina formwork;
2), parallel aluminum oxide (AAO)-silicon-dioxide (SBA) the composite mesopore template in Prepared by Sol Gel Method duct: under the room temperature, addition polymer PEO-PPO-PEO (P123) 0.5-0.7g of polypropylene glycol and oxyethane, positive tetraethyl orthosilicate 0.93g, 38wt% hydrochloric acid 0.4g are mixed with pioneer's solution, porous alumina formwork is immersed in 20-24h in pioneer's solution, take out afterwards under 50-70 ℃ of condition and carry out dry 12-15h, at 400-500 ℃ of following thermal treatment 4-6h, obtain the AAO-SBA composite mesopore template of the parallel alumina formwork of mesopore orbit then;
3), remove composite mesopore template surface SiO
2Zone of oxidation;
4), preparation electroplate liquid: press Co (CH
3COO)
22-4g: H
3BO
3The 1-3g wiring solution-forming, regulate behind the constant volume pH value to 4-6 as electrodeposit liquid;
5), the preparation of mesoporous Co nanowire array: as working electrode, is supporting electrode with graphite with above-mentioned aluminium substrate AAO-SBA composite mesopore template, and control electrode density is at 0.5-1.5mA/cm
2, galvanic deposit 1.0-1.5 hour, promptly obtain mesoporous Co nanowire.
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CN102751487A (en) * | 2011-04-18 | 2012-10-24 | 夏普株式会社 | Method for producing positive electrode active substance, and use of said active substance |
CN102897851A (en) * | 2012-06-01 | 2013-01-30 | 长春理工大学 | Method for preparing nickel, cobalt and their oxide nanostructures based on diffusion-limited aggregation (DLA) principle |
CN109921042A (en) * | 2017-12-13 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of anion-exchange membrane fuel cells metal array Catalytic Layer and preparation method thereof |
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2009
- 2009-07-30 CN CN200910183086A patent/CN101629320A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102751487A (en) * | 2011-04-18 | 2012-10-24 | 夏普株式会社 | Method for producing positive electrode active substance, and use of said active substance |
CN102751487B (en) * | 2011-04-18 | 2015-10-28 | 夏普株式会社 | Manufacture the method for positive electrode active materials and the purposes of described active material |
CN102897851A (en) * | 2012-06-01 | 2013-01-30 | 长春理工大学 | Method for preparing nickel, cobalt and their oxide nanostructures based on diffusion-limited aggregation (DLA) principle |
CN102897851B (en) * | 2012-06-01 | 2015-11-25 | 长春理工大学 | A kind of method preparing nickel, cobalt and oxide nano structure thereof based on diffusional limitation cohesion (DLA) principle |
CN109921042A (en) * | 2017-12-13 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of anion-exchange membrane fuel cells metal array Catalytic Layer and preparation method thereof |
CN115475614A (en) * | 2021-06-16 | 2022-12-16 | 中国石油化工股份有限公司 | Catalyst for synthesizing acrolein by propylene oxidation and preparation method and application thereof |
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