CN104876450B - Porous CoFe2O4 nano-rod array thin film material and preparation method thereof - Google Patents
Porous CoFe2O4 nano-rod array thin film material and preparation method thereof Download PDFInfo
- Publication number
- CN104876450B CN104876450B CN201510168807.0A CN201510168807A CN104876450B CN 104876450 B CN104876450 B CN 104876450B CN 201510168807 A CN201510168807 A CN 201510168807A CN 104876450 B CN104876450 B CN 104876450B
- Authority
- CN
- China
- Prior art keywords
- nano
- preparation
- thin film
- porous
- film material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention relates to a porous CoFe2O4 nano-rod array thin film material and a preparation method thereof, and belongs to the field of material preparation processes. The preparation method comprises the following steps: preparing a mixed solution by taking cobalt nitrate, deionized water, ammonium fluoride and urea as raw materials, transferring a pretreated substrate and the prepared solution to a reaction kettle, performing hydrothermal reaction, finally repeatedly washing an obtained sample by using the deionized water, drying, performing liquid phase reaction on a dried nano-rod template and a ferric nitrate solution, and drying and calcining to obtain a CoFe2O4 nano-rod array thin film material, wherein the material is prepared from porous CoFe2O4 nano-rod arrays which are arranged neatly and orderly, the length of each rod is 1.5-3 mu m, and the diameter of each rod is 70-130nm. The porous CoFe2O4 nano-rod array thin film material disclosed by the invention is prepared from cheap and easily-available raw materials, and is simple and easy to operate; the preparation method disclosed by the invention is simple, is easy to control and low in equipment requirement, and is an environment-friendly preparation method; and a prepared CoFe2O4 nano-rod array thin film can be applied to the fields of lithium batteries and photo-electro-catalysis.
Description
Technical field
The present invention relates to a kind of porous C oFe2O4Nano-stick array thin film material and preparation method thereof, belong to catalysis material and
Technical field of nanometer material preparation, is related specifically to the CoFe with loose structure2O4The preparation side of nano-stick array thin film material
Method.
Background technology
Due to the anisotropy of its shape, with higher specific surface area, more preferable space charge divides monodimension nanometer material
From efficiency, there is high power of influence and critical role at aspects such as various sensors, microelectrode, device integrated connecting lines, with
To the focus for becoming nano materials research in recent years.Spinel type composite metal oxide is the important composition metal of a class
Oxide, wherein CoFe2O4With high-coercive force and photocatalytic activity, many researchers are had at present and utilizes collosol and gel
Method, template and hydro-thermal method prepare CoFe2O4The structure such as nano wire or nanotube.Ji(GuangbinJi,Shaolong
Tang,Baolong Xu,Benxi Gu,Youwei Du,Chemical Physics Letters,2003,379,484–489)
Nano wire, Keller (N Keller, C Pham-Huu, T Shiga, C Estournes, J.- are prepared for using sol-gal process
M Grenèche,M.J Ledoux,Journal of Magnetism and Magnetic Materials,2004,272–
276,1642-1644) it is prepared for CoFe for template using multilayer carbon nanotube2O4Nano wire, Xu (Yan Xu, Jie Wei,
Jinli Yao, Junli Fu, DeshengXue, Materials Letters, 2008,62,1403-1405) utilize anodic oxygen
Change aluminum and be prepared for CoFe for template2O4Nanotube simultaneously discusses its ferromagnetism.But template is passed through as template using cobalt/cobalt oxide
Synthesizing porous CoFe2O4The one-dimensional material of nanometer rods is rarely reported.
The content of the invention
The technical problem to be solved in the present invention is that one kind prepares porous C oFe2O4The method of nano-stick array thin film.Specifically
Using hydro-thermal reaction and liquid phase reactor, the calcining after template and liquid phase reactor obtains porous C oFe2O4Nanometer stick array, group
Nanorod length into array is about 1.5～3 μm.Raw materials are cheap and easy to get, and operation is simple, and preparation method is simple, it is easy to
Control, equipment requirements are low, are a kind of preparation methoies of environmental protection.
A kind of porous C oFe2O4Nano-stick array thin film material, including CoFe2O4Nanometer rods and substrate；CoFe2O4Nanometer rods
For loose structure, it is closely grown in substrate, CoFe2O4A diameter of 70～130nm of nanometer rods, length is 1.5～3 μm；
Substrate material is the conductive or electrically non-conductive material of the laminated structure with support function, including sheet glass, the SnO of doping fluorine2Thoroughly
Bright electro-conductive glass or sheet metal.
Technical scheme is as follows：
1) pretreatment of substrate：Acetone soln and aqueous isopropanol mixed solution are prepared, substrate is placed wherein, at ultrasound
Reason, dries, standby；Described substrate is the conductive or electrically non-conductive material of the laminated structure with support function；
2) hydro-thermal reaction and liquid phase reactor：Hydro-thermal reaction first, the mixing for preparing cabaltous nitrate hexahydrate, ammonium fluoride and urea is molten
Liquid, molar concentration rate is 1:2:5, by step 1) substrate handled well is placed in above-mentioned mixed solution, hydro-thermal reaction 5- at 120 DEG C
12h；Then liquid phase reactor, is washed with deionized to be placed in 0.05-0.15M iron nitrate solutions after drying and stands 6-24h；
3) it is dried and calcining：By step 2) material that obtains is dried, calcines under the conditions of being subsequently placed in 400-500 DEG C
2h。
When adopting sheet metal for substrate, hydro-thermal reaction must be added to ammonium fluoride, and concentration is 0.2mol L-1。
Step 2) in the hydro-thermal reaction time be 6h；Step 2) in liquid reactive iron nitrate solution solubility be 0.1M, liquid phase
Response time is 12h.
Step 2) in drying temperature be 60 DEG C, the time is 15min.
Step 3) in calcining heat be 450 DEG C.
The present invention proposes that one kind prepares porous C oFe2O4The array film method of nanometer rods, it is anti-using template and liquid phase
Should, the nano-stick array thin film obtained after calcining is by porous C oFe2O4Nanometer rods are constituted, and are easy to be applied in lithium battery, thin film
The aspects such as solaode, are a kind of easy to operate, the flexible environmentally friendly preparation methoies of method.
Description of the drawings
Fig. 1 is porous C oFe for preparing2O4The X-ray diffractogram that nano-stick array thin film material is contrasted with FTO substrates
(XRD).Abscissa is the twice angle of diffraction (2 θ), and vertical coordinate is diffraction peak intensity (a.u.).
Fig. 2 is the scanning electron microscope (SEM) photograph (SEM) of the templating nanoparticles rod array film material for preparing.
Fig. 3 a are porous Cs oFe for preparing2O4The scanning electron microscope (SEM) photograph (SEM) of nano-stick array thin film material.
Fig. 3 b are porous Cs oFe for preparing2O4The scanning electron microscope (SEM) photograph (SEM) of nano-stick array thin film material.
Fig. 3 c are porous Cs oFe for preparing2O4The scanning electron microscope (SEM) photograph (SEM) of nano-stick array thin film material.
Fig. 4 a are porous Cs oFe for preparing2O4The transmission electron microscope picture (TEM) of nano-stick array thin film material.
Fig. 4 b are porous Cs oFe for preparing2O4The transmission electron microscope picture (TEM) of nano-stick array thin film material.
Fig. 4 c are porous Cs oFe for preparing2O4The transmission electron microscope picture (TEM) of nano-stick array thin film material.
Fig. 5 is porous C oFe for preparing2O4The corresponding SEAD figure of sample of nano-stick array thin film material.
Specific embodiment
The specific embodiment of the present invention is described in detail below in conjunction with technical scheme and accompanying drawing.
Embodiment 1
Pretreatment FTO electro-conductive glass first, 10ml deionized waters, 10ml acetone solns and the 10ml for preparing equal-volume ratio is different
The mixed solution of propanol solution, stirs 10min, is transferred to beaker, is put into dimension (8cm2) FTO glass, shake in ultrasound
Supersound process 10min under 100W power is swung in pond, nature is then taken out and is dried, conducting surface is downwardly inclined and is positioned over 25ml poly- four
Fluorothene reactor inwall is standby；0.55g cabaltous nitrate hexahydrates are taken, 0.15g ammonium fluorides, 0.6g ureas are dissolved in the deionization of 20ml
In water, 5min, in settled solution being transferred to the reactor of the 25ml for filling the good FTO electro-conductive glass of pretreatment, 120 DEG C are stirred
Lower hydro-thermal reaction 6h；It is washed with deionized to be placed in 20ml 0.1M iron nitrate solutions after drying and stands 12h.Liquid phase reactor it
Afterwards, take out FTO glass, in being placed in beaker, in 60 DEG C of baking oven 15min is dried, then take out be placed in Muffle furnace with 2 DEG C/
Min speed is from room temperature temperature programming to 450 DEG C and calcines 2h.
Embodiment 2
Consumption according to cabaltous nitrate hexahydrate during hydro-thermal reaction in the present invention of embodiment 1 is reduced to 0.5g, other raw materials
Consumption and experimental procedure keep constant, and porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 3
Consumption according to cabaltous nitrate hexahydrate during hydro-thermal reaction in the present invention of embodiment 1 increases to 0.6g, other raw materials
Consumption and experimental procedure keep constant, and porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 4
Consumption according to ammonium fluoride during hydro-thermal reaction in the present invention of embodiment 1 is reduced to 0.12g, other raw material dosages with
And experimental procedure keeps constant, and porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 5
Consumption according to ammonium fluoride during hydro-thermal reaction in the present invention of embodiment 1 increases to 0.2g, other raw material dosages with
And experimental procedure keeps constant, and porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 6
Consumption according to urea during hydro-thermal reaction in the present invention of embodiment 1 is reduced to 0.4g, other raw material dosages and reality
Test step and keep constant, porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 7
Consumption according to urea during hydro-thermal reaction in the present invention of embodiment 1 increases to 0.6g, other raw material dosages and reality
Test step and keep constant, porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 8
It is 2cm according to the FTO dimensions chosen in the present invention of embodiment 12, other raw material dosages and experimental procedure are protected
Hold constant, porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 9
It is 25cm according to the FTO dimensions chosen in the present invention of embodiment 12, other raw material dosages and experimental procedure
Keep constant, porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 10
8cm is changed to according to substrate is chosen in the present invention of embodiment 12Titanium sheet, other raw material dosages and experimental procedure are protected
Hold constant, porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 11
2cm is changed to according to substrate is chosen in the present invention of embodiment 12Titanium sheet, other raw material dosages and experimental procedure are protected
Hold constant, porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 12
8cm is changed to according to substrate is chosen in the present invention of embodiment 12Sheet glass, other raw material dosages and experimental procedure
Keep constant, porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 13
2cm is changed to according to substrate is chosen in the present invention of embodiment 12Sheet glass, other raw material dosages and experimental procedure
Keep constant, porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 14
According to the preparation method in the present invention of embodiment 1, the hydro-thermal reaction time is reduced to 5h, and reaction temperature is constant, other
Raw material dosage and experimental procedure keep constant, and porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 15
According to the preparation method in the present invention of embodiment 1, the hydro-thermal reaction time increases to 12h, and reaction temperature is constant, other
Raw material dosage and experimental procedure keep constant, and porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 16
Concentration according to iron nitrate solution during liquid phase reactor in the present invention of embodiment 1 is reduced to 0.05M, and other raw materials are used
Amount and experimental procedure keep constant, and porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 17
Concentration according to iron nitrate solution during liquid phase reactor in the present invention of embodiment 1 increases to 0.15M, and other raw materials are used
Amount and experimental procedure keep constant, and porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 18
According to the preparation method in the present invention of embodiment 1, the liquid phase reactor time is reduced to 6h, other raw material dosages and reality
Test step and keep constant, porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 19
According to the preparation method in the present invention of embodiment 1, the liquid phase reactor time increases to 24h, other raw material dosages and
Experimental procedure keeps constant, and porous C oFe is obtained2O4Nano-stick array thin film material.
Embodiment 20
According to the preparation method in the present invention of embodiment 1, Muffle furnace calcining heat is reduced to 400 DEG C after liquid phase reactor, its
His raw material dosage and experimental procedure keep constant, and porous C oFe is obtained2O4Nano-stick array thin film material.
Claims (10)
1. a kind of porous C oFe2O4Nano-stick array thin film material, it is characterised in that porous C oFe2O4Nano-stick array thin film
Material includes CoFe2O4Nanometer rods and substrate；CoFe2O4Nanometer rods are loose structure, and it is closely grown in substrate,
CoFe2O4A diameter of 70～130nm of nanometer rods, length is 1.5～3 μm；Substrate material is the laminated structure with support function
Conductive or electrically non-conductive material.
2. porous C oFe according to claim 12O4Nano-stick array thin film material, it is characterised in that described substrate is
Sheet glass or sheet metal.
3. porous C oFe described in claim 1 or 22O4The preparation method of nano-stick array thin film material, it is characterised in that
1) pretreatment of substrate：Acetone soln and aqueous isopropanol mixed solution are prepared, substrate are placed wherein, supersound process,
Dry, it is standby；Described substrate is the conductive or electrically non-conductive material of the laminated structure with support function；
2) hydro-thermal reaction and liquid phase reactor：First hydro-thermal reaction, prepares the mixed solution of cabaltous nitrate hexahydrate, ammonium fluoride and urea,
Molar concentration rate is 1:2:5, by step 1) substrate handled well is placed in above-mentioned mixed solution, hydro-thermal reaction 5- at 120 DEG C
12h；Then liquid phase reactor, is washed with deionized drying, is placed in 0.05-0.15M iron nitrate solutions and stands 6-24h；
3) it is dried and calcining：By step 2) material that obtains is dried, and 2h is calcined under the conditions of being subsequently placed in 400-500 DEG C.
4. preparation method according to claim 3, it is characterised in that when adopting sheet metal for substrate, hydro-thermal reaction is added
Concentration is 0.2mol L-1Ammonium fluoride.
5. preparation method according to claim 3, it is characterised in that：Step 2) in the hydro-thermal reaction time be 6h；Step 2)
In liquid reactive iron nitrate solution solubility be 0.1M, the liquid phase reactor time be 12h.
6. preparation method according to claim 4, it is characterised in that：Step 2) in the hydro-thermal reaction time be 6h；Step 2)
In liquid reactive iron nitrate solution solubility be 0.1M, the liquid phase reactor time be 12h.
7. the preparation method according to claim 4,5 or 6, it is characterised in that：Step 2) in drying temperature be 60 DEG C, the time
For 15min.
8. preparation method according to claim 3, it is characterised in that：Step 2) in drying temperature be 60 DEG C, the time is
15min。
9. the preparation method according to claim 4,5,6 or 8, it is characterised in that：Step 3) in calcining heat be 450 DEG C.
10. preparation method according to claim 7, it is characterised in that：Step 3) in calcining heat be 450 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510168807.0A CN104876450B (en) | 2015-04-08 | 2015-04-08 | Porous CoFe2O4 nano-rod array thin film material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510168807.0A CN104876450B (en) | 2015-04-08 | 2015-04-08 | Porous CoFe2O4 nano-rod array thin film material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104876450A CN104876450A (en) | 2015-09-02 |
| CN104876450B true CN104876450B (en) | 2017-05-03 |
Family
ID=53944173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510168807.0A Expired - Fee Related CN104876450B (en) | 2015-04-08 | 2015-04-08 | Porous CoFe2O4 nano-rod array thin film material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104876450B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508468A (en) * | 2009-04-03 | 2009-08-19 | 华中师范大学 | Nano-superstructure polyporous material of ferrite and method of preparing the same |
| CN101747046A (en) * | 2009-10-15 | 2010-06-23 | 南京航空航天大学 | Method for preparing crystalline-state mesoporous CoFe204 with large specific surface area |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104475313B (en) * | 2010-09-14 | 2017-05-17 | 应用奈米结构公司 | Glass substrates having carbon nanotubes grown thereon and methods for production thereof |
-
2015
- 2015-04-08 CN CN201510168807.0A patent/CN104876450B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508468A (en) * | 2009-04-03 | 2009-08-19 | 华中师范大学 | Nano-superstructure polyporous material of ferrite and method of preparing the same |
| CN101747046A (en) * | 2009-10-15 | 2010-06-23 | 南京航空航天大学 | Method for preparing crystalline-state mesoporous CoFe204 with large specific surface area |
Non-Patent Citations (2)
| Title |
|---|
| 《Highly ordered CoFe2O4 nanowires array prepared via a modified sol–gel templated approach and its optical and magnetic properties》;Jingyi Chen等;《Journal of Alloys and Compounds》;20121025;第552卷;第65-69页 * |
| 《Ordered CoFe2O4 nanowire arrays with preferred crystal orientation and magnetic anisotropy》;Y. Xua等;《Electrochimica Acta》;20090313;第56卷;第5684–5687页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104876450A (en) | 2015-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | Excellent catalytic performance of molten-salt-synthesized Bi0. 5Na0. 5TiO3 nanorods by the piezo-phototronic coupling effect | |
| Wang et al. | Solvent-controlled synthesis and electrochemical lithium storage of one-dimensional TiO2 nanostructures | |
| CN104058461B (en) | A kind of delafossite structure CuFeO2The low temperature preparation method of crystalline material | |
| CN105803580B (en) | A kind of preparation method of phosphatization cobalt hollow Nano fiber in use material | |
| Droepenu et al. | Zinc oxide nanoparticles synthesis methods and its effect on morphology: A review | |
| CN104311142B (en) | A kind of vertical-growth TiO2nanometer sheet and preparation method thereof | |
| CN101985367B (en) | Method for preparing multilayer alpha-Ni(OH)2 or NiO nanocrystal by microwave solvothermal method | |
| CN102824884B (en) | A kind of TiO 2/ Fe 2o 3compound hollow microballoon and preparation method thereof | |
| CN104192900B (en) | A kind of TiO2Nanocrystalline synthetic method | |
| CN106540673A (en) | A kind of three-dimensional TiO2The synthetic method of/ZnO heterojunction array | |
| CN106745231B (en) | A kind of taper titanium dioxide nano-rod and preparation method thereof | |
| CN104752071A (en) | Cobaltosic oxide and cobalt molybdate core-shell heterostructure nanowire array, preparation method and application thereof | |
| Kim et al. | Facile synthesis and capacitive properties of nickel–cobalt binary metal oxide nanoaggregates via oxalate route | |
| CN103466703B (en) | Bismuth titanate nanoneedle and preparation method thereof | |
| Guo et al. | Synthesis of novel Mn3O4 microsphere and its distinctive capacitance change during electrochemical cycling | |
| CN106064829B (en) | A kind of preparation method of the flower-shaped magnesia of carrying tin oxide | |
| CN104198560A (en) | Preparation method of graphene modified porous titanium dioxide composite film | |
| CN106564950B (en) | A kind of magnesium molybdate/graphene nano chip arrays and preparation method thereof | |
| CN107803170A (en) | A kind of preparation method of titanium dioxide/nickel oxide bivalve hollow ball | |
| CN106882845A (en) | A kind of mesoporous sea urchin shape NiCo2O4The preparation method of meter Sized Materials | |
| CN101863451B (en) | Method for preparing zinc oxide in three-dimensional nanostructure with cryogenic fluid method | |
| CN108346517B (en) | Nanometer Nb2O5The preparation method of/carbon cloth combination electrode material | |
| CN104876450B (en) | Porous CoFe2O4 nano-rod array thin film material and preparation method thereof | |
| CN107369824A (en) | The preparation method of lithium ion battery NiO/MgO/C composite negative pole materials | |
| CN103882558A (en) | Perovskite structure AgNbO3 fiber and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170503 Termination date: 20200408 |