CN106835356B - A method of preparing cobalt protoxide hollow nano fiber - Google Patents
A method of preparing cobalt protoxide hollow nano fiber Download PDFInfo
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- CN106835356B CN106835356B CN201710088960.1A CN201710088960A CN106835356B CN 106835356 B CN106835356 B CN 106835356B CN 201710088960 A CN201710088960 A CN 201710088960A CN 106835356 B CN106835356 B CN 106835356B
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 12
- 239000010941 cobalt Substances 0.000 title claims abstract description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 24
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000009987 spinning Methods 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 19
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 17
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 12
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 25
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 229910002651 NO3 Inorganic materials 0.000 claims description 16
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims 1
- 229920002521 macromolecule Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 8
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 17
- 239000000835 fiber Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 238000001523 electrospinning Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229910002230 La2Zr2O7 Inorganic materials 0.000 description 1
- 229910002333 LaMO3 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt(II) nitrate Inorganic materials [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000005492 condensed matter physics Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000005315 stained glass Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- -1 template Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Fibers (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The present invention relates to a kind of methods for preparing cobalt protoxide hollow nano fiber, belong to technical field of nanometer material preparation.The present invention prepares CoO hollow nano fiber with the method that ammonia thermal reduction combines using electrostatic spinning technique.The present invention includes four steps: (1) preparing spinning solution；(2) PVP/Co (NO is prepared3)2Composite nano fiber is prepared using electrostatic spinning technique；(3) Co is prepared3O4Hollow nano fiber, by being heat-treated PVP/Co (NO3)2It is prepared by composite nano fiber；(4) CoO hollow nano fiber is prepared, by Co3O4Hollow nano fiber is heat-treated with ammonia, obtains CoO hollow nano fiber, has good crystallinity, belongs to cubic system, and diameter is 81.17 ± 0.71nm, and length is greater than 50 μm.Of the invention preparation method is simple, can produce in batches, have broad application prospects.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, in particular relate to a kind of prepare cobalt protoxide hollow nano fiber
Method.
Background technique
The preparation and property research of inorganic matter nanofiber and hollow nano fiber, are material science, Condensed Matter Physics, change
One of etc. forward position focus research field of subjects.Nanofiber refers to that having bidimensional to be on the three-dimensional space scale of material receives
The filamentary material of metrical scale, generally radially scale is nanometer scale, and length is then larger.Since the radial dimension of nanofiber is small
To nanometer scale, series of characteristics is shown, most outstanding is large specific surface area, so that its surface can increase with activity, in turn
Small-size effect, surface or interfacial effect, quantum size effect, macro quanta tunnel effect etc. are generated, and therefore shows one
The specificity of sequence of chemical, physics such as heat, light, sound, electricity, magnetic etc..Hollow nano fiber is due to having bigger specific surface
Product, will have wider application.In the prior art, there is the method for much preparing nanofiber, such as method of reeling off raw silk from cocoons, template are closed
Cheng Fa, split-phase method and self-assembly method etc..In addition, there are also arc evaporation, laser high temperature inustion, compound pyrolysis.This
Three kinds of methods are essentially all after at high temperature evaporating compound or simple substance, through the obtained nanofiber of pyrolysis or directly condensation or
Nanotube essentially belongs to compound vapor deposition.
Cobalt protoxide CoO makes it in gas sensor, lithium ion battery, ni-mh electricity due to its special structure and performance
Pond, nickel-cadmium cell, ceramic glaze, coloured glass, the paint fields such as colorant and Co catalysts, have broad application prospects.Mesh
Preceding researcher has used hydro-thermal method, and solvent-thermal method, the compound high temperature thermal decomposition method of cobalt, pyrosol heat are divided under reducing atmosphere
The methods of solution has successfully prepared CoO ball shaped nano crystalline substance, nanometer octahedron, nanocube, nano-hollow ball, nanometer
The nanometer material of the different-shapes such as flower, nanotube, nano wire, monocrystalline porous C oO nanometer stick array and class A foam A CoO nano material
Material.Currently, having no the relevant report of CoO hollow nano fiber preparation.
One related electrospinning process (electrospinning) of the U.S. Patent Publication of Patent No. 1975504
Technical solution, this method is a kind of effective ways for preparing continuous micro nanometer fiber with macro length, by
Formhals was proposed first in 1934.This method is mainly used to prepare high polymer nanometer fiber, it is characterized in that making electrification
Polymer solution or melt is sprayed by the traction of electrostatic force by nozzle in electrostatic field, invests the receiving screen on opposite, thus real
Existing wire drawing, then solvent evaporation or melt are cooled to room temperature and solidify at normal temperature, obtain micro nanometer fiber.In the past 10 years,
Occur preparing inorganic compound such as oxide nanofiber using electrospinning process in inorfil preparation technical field
Technical solution, the oxide include TiO2、ZrO2、Y2O3、Y2O3:RE3+(RE3+=Eu3+、Tb3+、Er3+、Yb3+/Er3+)、
NiO、Co3O4、Mn2O3、Mn3O4、CuO、SiO2、Al2O3、ZnO、Nb2O5、MoO3、CeO2、LaMO3(M=Fe、Cr、Mn、Co、Ni、
Al)、Y3Al5O12、La2Zr2O7Equal metal oxides and composite oxide of metal.By adjusting the composition of spinning solution, Dong Xiangting etc.
CeO is directly prepared for using electrostatic spinning technique2Hollow nano fiber [Journal of Rare Earths, 2008,26
(5), 664-669]；Wang Jinxian etc. is directly prepared for LaCoO using electrostatic spinning technique3Porous hollow nano fiber
[Applied Physics Research, 2009, 1(1), 8-14].It is had no at present using electrostatic spinning technique and ammonia heat
Restore the report that the method combined prepares CoO hollow nano fiber.
When preparing nano material using electrostatic spinning technique, the type of raw material, the molecular weight of high polymer templates, spinning solution
Composition, spinning process parameters and heat treatment process all has a major impact the morphology and size of final products.The present invention uses
Electrostatic spinning technique and ammonia NH3Heat-treat the method preparation CoO hollow nano fiber combined.With cabaltous nitrate hexahydrate Co
(NO3)2·6H2O is raw material, and solvent is addedN,NDimethylformamide DMF and ethyl alcohol C2H5It is poly- to add high polymer templates by OH
Vinylpyrrolidone PVP carries out electrostatic spinning after obtaining spinning solution, under the best experimental conditions, prepares PVP/Co
(NO3)2 It is heat-treated in air, obtains Co by composite nano fiber3O4Hollow nano fiber, using the ammonia of flowing
By Co3O4Hollow nano fiber is heat-treated, and the CoO hollow nano fiber of pure phase has been prepared.
Summary of the invention
Preparation CoO ball shaped nano crystalline substance, nanometer octahedron, nanocube, nano-hollow ball, nanometer in the background technology
The nanometer material of the different-shapes such as flower, nanotube, nano wire, monocrystalline porous C oO nanometer stick array and class A foam A CoO nano material
Material uses hydro-thermal method, solvent-thermal method, under reducing atmosphere the compound high temperature thermal decomposition method of cobalt, pyrosol thermal decomposition method
The methods of.Co is prepared for using electrostatic spinning technique in background technique3O4Nanofiber and CeO2Equal metal oxide hollows are received
Rice fiber.Used raw material, template, solvent and reducing agent and method of the invention are different.In order in CoO nanometers of materials
Material field provides a kind of novel hollow nano fiber material, and we have invented the Co for preparing electrostatic spinning technique3O4It is hollow to receive
Rice fiber is carried out ammonia and heat-treats the method for preparing CoO hollow nano fiber as presoma.
The invention is realized in this way preparing the spinning solution with certain viscosity for electrostatic spinning first, apply
Electrostatic spinning technique carries out electrostatic spinning and prepares PVP/Co (NO under the best experimental conditions3)2Composite nano fiber, will
It is heat-treated in air, obtains Co3O4Hollow nano fiber, then heat-treated with the ammonia of flowing, it prepares and finishes
The CoO hollow nano fiber of structure novelty pure phase.It the steps include:
(1) spinning solution is prepared
Cobalt source uses cabaltous nitrate hexahydrate Co (NO3)2·6H2O, high polymer templates use polyvinylpyrrolidone
PVP, molecular weight 90000 useN,NDimethylformamide DMF and ethyl alcohol C2H5OH is solvent, by 1.0052 g Co
(NO3)2·6H2O is added in 5.0022 g DMF and the mixed solution of 5.0022 g ethyl alcohol, is added after magnetic agitation dissolution
1.0031 g PVP continue 10 h of stirring and obtain transparent spinning solution；
(2) PVP/Co (NO is prepared3)2 Composite nano fiber
Spinning solution is injected in a 10 mL syringes with 1 mL plastic spray gun head, graphite rod is inserted into spinning solution
In, with the positive terminal of copper wire connection graphite rod and high-voltage DC power supply, by the earth terminal of high-voltage DC power supply and hang down
The wire netting directly placed copper wire connect and ground, reception device of the wire netting as composite nano fiber, lance head and level
The angle in face is 15o, and the spacing of lance head and receiving screen wire netting is 17 cm, and spinning voltage is 14 kV, room temperature 20-
30 °C, relative humidity is 20 % -50 %, carries out electrostatic spinning and obtains PVP/Co (NO3)2Composite nano fiber；
(3) Co is prepared3O4Hollow nano fiber
By the PVP/Co (NO3)2Composite nano fiber is put into temperature programmed control Muffle furnace and is heat-treated, with 1 °C/
The heating rate of min rises to 380 °C and keeps the temperature 2 h, 200 °C is down to later with the rate of temperature fall of 1 °C/min, then with furnace
Body cooled to room temperature, obtains Co3O4Hollow nano fiber；
(4) CoO hollow nano fiber is prepared
By the Co3O4Hollow nano fiber is placed in quartz boat, is placed into vacuum tube furnace, and vacuum pumping is first used
Furnace air out then passes to ammonia, with the heating rate of 1 °C/min rise to 310 °C and keep the temperature 6 h, later with 1 °C/
The rate of temperature fall of min is down to 100 °C, then with furnace body cooled to room temperature, obtains CoO hollow nano fiber, diameter is
81.17 ± 0.71 nm, length are greater than 50 μm.
The CoO hollow nano fiber has good crystallinity in above process, belongs to cubic system, diameter is
81.17 ± 0.71 nm, length are greater than 50 μm, realize goal of the invention.
Detailed description of the invention
Fig. 1 is PVP/Co (NO3)2 The SEM photograph of composite nano fiber；
Fig. 2 is PVP/Co (NO3)2 The diameter distribution histogram of composite nano fiber；
Fig. 3 is Co3O4The XRD spectra of hollow nano fiber；
Fig. 4 is Co3O4The SEM photograph of hollow nano fiber；
Fig. 5 is Co3O4The diameter distribution histogram of hollow nano fiber；
Fig. 6 is Co3O4The EDS spectrogram of hollow nano fiber；
Fig. 7 is Co3O4The TEM photo of hollow nano fiber；
Fig. 8 is the XRD spectra of CoO hollow nano fiber；
Fig. 9 is the SEM photograph of CoO hollow nano fiber, which doubles as Figure of abstract；
Figure 10 is the diameter distribution histogram of CoO hollow nano fiber；
Figure 11 is the EDS spectrogram of CoO hollow nano fiber；
Figure 12 is the TEM photo of CoO hollow nano fiber.
Specific embodiment
Cabaltous nitrate hexahydrate Co (NO selected by the present invention3)2·6H2O, the polyvinylpyrrolidone that molecular weight is 90000
PVP, ammonia,N,NDimethylformamide DMF and ethyl alcohol are commercially available analysis net product；It glass apparatus used, crucible and sets
Standby is common instrument and equipment in laboratory.
Embodiment: by 1.0052 g Co (NO3)2·6H2O is added to the mixed of 5.0022 g DMF and 5.0022 g ethyl alcohol
It closes in solution, adds 1.0031 g PVP after magnetic agitation dissolution, continue 10 h of stirring and obtain transparent spinning solution；By spinning
Liquid injects in a 10 mL syringes with 1 mL plastic spray gun head, and graphite rod is inserted into spinning solution, connects stone with copper wire
The positive terminal of inker and high-voltage DC power supply uses the earth terminal of high-voltage DC power supply with the wire netting being disposed vertically
The angle of copper wire connect and ground, reception device of the wire netting as composite nano fiber, lance head and horizontal plane is 15o, spray
Pipette tips and the spacing of receiving screen wire netting are 17 cm, and spinning voltage is 14 kV, and room temperature is 20-30 °C, and relative humidity is
20 % -50 % carry out electrostatic spinning and obtain PVP/Co (NO3)2Composite nano fiber；By the PVP/Co (NO3)2It is compound
Nanofiber is put into temperature programmed control Muffle furnace and is heat-treated, and rises to 380 °C with the heating rate of 1 °C/min and keeps the temperature 2
H is down to 200 °C later with the rate of temperature fall of 1 °C/min, then with furnace body cooled to room temperature, obtains Co3O4It is hollow to receive
Rice fiber；By the Co3O4Hollow nano fiber is placed in quartz boat, is placed into vacuum tube furnace, is first extracted out with vacuum pump
Furnace air then passes to ammonia, rises to 310 °C with the heating rate of 1 °C/min and keeps the temperature 6 h, later with 1 °C/min
Rate of temperature fall be down to 100 °C, then with furnace body cooled to room temperature, obtain CoO hollow nano fiber.The PVP/
Co(NO3)2Composite nano fiber has good fiber morphology, and fiber surface is smooth, and diameter is evenly distributed, as shown in Figure 1；With
Shapiro-Wilk method is to PVP/Co (NO3)2The diameter of composite nano fiber carries out normal distribution-test, in the confidence of 95 %
Under degree, diameter distribution belongs to normal distribution, and diameter is 213.14 ± 1.20 nm, as shown in Figure 2；The Co3O4Hollow Nano
Fiber has good crystallinity, the d value and relative intensity and Co of diffraction maximum3O4PDF standard card (65-3103) it is listed
D value it is consistent with relative intensity, belong to a cube prismatic crystal system, as shown in Figure 3；The Co3O4Hollow nano fiber has good
Hollow nano fiber pattern, diameter are evenly distributed, and length is greater than 50 μm, as shown in Figure 4；With Shapiro-Wilk method pair
Co3O4The diameter of hollow nano fiber carries out normal distribution-test, and under the confidence level of 95 %, diameter distribution belongs to normal distribution,
Diameter is 83.09 ± 0.49 nm, as shown in Figure 5；The Co3O4Hollow nano fiber is made of Co and O element, and Pt is derived from
The Pt conductive layer of sample surfaces plating, a small amount of C derive from double-sided adhesive used when SEM is tested, as shown in Figure 6；The Co3O4
Hollow nano fiber has apparent hollow structure, as shown in Figure 7；The CoO hollow nano fiber has good crystallization
Property, the d value and relative intensity of diffraction maximum are consistent with d value listed by the PDF standard card (70-2856) of CoO and relative intensity,
Belong to cubic system, as shown in Figure 8；The CoO hollow nano fiber has good hollow nano fiber pattern, diameter point
Cloth is uniform, and length is greater than 50 μm, as shown in Figure 9；It is carried out with diameter of the Shapiro-Wilk method to CoO hollow nano fiber
Normal distribution-test, under the confidence level of 95 %, diameter distribution belongs to normal distribution, and diameter is 81.17 ± 0.71 nm, sees figure
Shown in 10；The CoO hollow nano fiber is made of Co and O element, and the Pt of sample surfaces plating is led when Pt is tested from SEM
Electric layer, a small amount of C derive from double-sided adhesive used, as shown in Figure 11；The CoO hollow nano fiber has apparent hollow
Structure, as shown in Figure 12.
Certainly, the invention may also have other embodiments, without deviating from the spirit and substance of the present invention, ripe
It knows those skilled in the art and makes various corresponding changes and modifications, but these corresponding changes and change in accordance with the present invention
Shape all should fall within the scope of protection of the appended claims of the present invention.
Claims (2)
1. a kind of method for preparing cobalt protoxide hollow nano fiber, which is characterized in that using electrostatic spinning technique and ammonia heat
The method combined is restored, the use of polyvinylpyrrolidone PVP is high polymer templates, usesN,NDimethylformamide DMF
It is solvent with ethyl alcohol, preparing product is cobalt protoxide CoO hollow nano fiber, be the steps include:
(1) spinning solution is prepared
Cobalt source uses cabaltous nitrate hexahydrate Co (NO3)2·6H2O is usedN,NDimethylformamide DMF and ethyl alcohol C2H5OH
For solvent, by 1.0052 g Co (NO3)2·6H2O is added in 5.0022 g DMF and the mixed solution of 5.0022 g ethyl alcohol,
1.0031 g PVP are added after magnetic agitation dissolution, continues 10 h of stirring and obtains transparent spinning solution；
(2) PVP/Co (NO is prepared3)2 Composite nano fiber
Spinning solution is injected in a 10 mL syringes with 1 mL plastic spray gun head, graphite rod is inserted into spinning solution, is used
Copper wire connect graphite rod and high-voltage DC power supply positive terminal, by the earth terminal of high-voltage DC power supply be disposed vertically
Wire netting copper wire connect and ground, reception device of the wire netting as composite nano fiber, the folder of lance head and horizontal plane
Angle is 15o, and the spacing of lance head and receiving screen wire netting is 17 cm, and spinning voltage is 14 kV, and room temperature is 20-30 DEG C,
Relative humidity is 20 % -50 %, carries out electrostatic spinning and obtains PVP/Co (NO3)2Composite nano fiber；
(3) Co is prepared3O4Hollow nano fiber
By the PVP/Co (NO3)2Composite nano fiber is put into temperature programmed control Muffle furnace and is heat-treated, with 1 DEG C/min
Heating rate rise to 380 DEG C and keep the temperature 2 h, 200 DEG C are down to later with the rate of temperature fall of 1 DEG C/min, then with furnace body
Cooled to room temperature obtains Co3O4Hollow nano fiber；
(4) CoO hollow nano fiber is prepared
By the Co3O4Hollow nano fiber is placed in quartz boat, is placed into vacuum tube furnace, first extracts furnace out with vacuum pump
Interior air, then passes to ammonia, rises to 310 DEG C with the heating rate of 1 °C/min and keeps the temperature 6 h, later with 1 °C/min's
Rate of temperature fall is down to 100 DEG C, then with furnace body cooled to room temperature, obtains CoO hollow nano fiber, and diameter is 81.17 ±
0.71 nm, length are greater than 50 μm.
2. a kind of method for preparing cobalt protoxide hollow nano fiber according to claim 1, which is characterized in that macromolecule
Template is the polyvinylpyrrolidone of molecular weight Mr=90000.
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