CN106391129B - Luminous four two layers of nano-fiber composite films of function of photocatalysis of electromagnetism and preparation method thereof - Google Patents
Luminous four two layers of nano-fiber composite films of function of photocatalysis of electromagnetism and preparation method thereof Download PDFInfo
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 66
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 63
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 229920000767 polyaniline Polymers 0.000 claims abstract description 62
- 238000004020 luminiscence type Methods 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 238000009987 spinning Methods 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 33
- 239000005642 Oleic acid Substances 0.000 claims abstract description 16
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 16
- 230000003760 hair shine Effects 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 107
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 80
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 9
- 229940043267 rhodamine b Drugs 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 7
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 7
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 7
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 7
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 6
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
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- 239000000725 suspension Substances 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 239000002070 nanowire Substances 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 230000005415 magnetization Effects 0.000 claims description 3
- 229910052603 melanterite Inorganic materials 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005057 refrigeration Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 12
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- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
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- 238000005507 spraying Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000001523 electrospinning Methods 0.000 abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 239000000835 fiber Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 6
- -1 nanometer rods Substances 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
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- 238000010521 absorption reaction Methods 0.000 description 2
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- 150000001875 compounds Chemical class 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000003745 diagnosis Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 229940056319 ferrosoferric oxide Drugs 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000009291 secondary effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
- 229910003454 ytterbium oxide Inorganic materials 0.000 description 1
- 229940075624 ytterbium oxide Drugs 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Luminescent Compositions (AREA)
Abstract
It shines four two layers of nano-fiber composite films of function of photocatalysis and preparation method thereof the present invention relates to electromagnetism, belongs to technical field of nanometer material preparation.The present invention includes four steps: (1) precipitation method prepare the Fe of Coated with Oleic Acid3O4It is nanocrystalline;(2) method of electrostatic spinning combination high-temperature roasting prepares Bi2WO6:Yb3+,Er3+Nanofiber;(3) spinning solution is prepared;(4) [PANI/Fe is prepared3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four functions, two layers of nano-fiber composite film, it is prepared using uniaxial electrospinning technology.Prepared nano-fiber composite film has the function of good electromagnetism up-conversion luminescence photocatalysis four simultaneously.Method of the invention is simple and easy, can produce in batches, and this novel nano structural material has broad application prospects.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, in particular relate to luminous two layers nanometer of four function of photocatalysis of electromagnetism
Composite fiber membrane and preparation method thereof.
Background technique
Simple function applications to nanostructures is limited in scope, and difunctional or multi-functional nanometer material application range is more
Extensively, this kind of material has more characteristic and attraction, therefore, highest attention of the multi-functional nanometer material by researcher.With nanometer
The development of science and technology, nano material such as have the characteristics of luminescence, photocatalysis property, electric conductivity is magnetic, towards double function by simple function
Can and multifunctional direction development, such as have magnetism-fluorescence, shine-photocatalysis, fluorescence-conduction or conduction-magnetism it is difunctional with
And-photocatalysis-four function of conduction-magnetism that shines, difunctional or four functions can be realized on a kind of nano structural material in this way,
It is of great significance to the development of nano-device, nanotechnology and relevant science and technology.For example, magnetism-fluorescent dual-function
Nanocomposite provides a kind of new platform for medical diagnosis on disease and treatment, since their difunctional property makes disease
" it was found that-detection-treatment " is integrally formed.The use of this nanocomposite is by the efficiency for being further improved diagnosis and reduces secondary
Effect, causes the highest attention of researcher.Electromagnetism dual-functional nanometer compound is in thunderstorm activity, electromagnetic shielding, antistatic
Coating and sensor etc. have broad application prospects.
Ferroso-ferric oxide Fe3O4It is a kind of important and widely applied magnetic material.People have used a variety of methods, such as
The methods of the precipitation method, sol-gel method, microemulsion method, hydro-thermal and solvent-thermal method, thermal decomposition method, method of electrostatic spinning are successfully made
It is standby gone out Fe3O4The nano materials such as nanocrystalline, nanometer rods, nano wire, nanometer film, hybrid structure, Core-shell Structure Nanoparticles, skill
Art comparative maturity.Bi2WO6:Yb3+,Er3+With good photocatalysis and Upconversion luminescence, researcher has used a variety of
Method is prepared for Bi2WO6:Yb3+,Er3+Nano material, technology also comparative maturity.Polyaniline PANI is since it is readily synthesized, conductance
The advantages that rate height and good environmental stability, has become one of the hot spot of conducting polymer area research.People have synthesized
Therefore the polyaniline PANI of the one-dimensional nano structures such as nano wire, nanometer rods, nanotube and nanofiber utilizes electrically conductive polyaniline
PANI, magnetic Fe3O4Nanocrystalline and Bi2WO6:Yb3+,Er3+Construct receiving with four functional characteristic of electromagnetism up-conversion luminescence photocatalysis
Rice material is ideal substance.
Existing research is it has been proved that work as dark colour electrically conductive polyaniline PANI and magnetic Fe3O4With mix rare earth luminous chemical combination
Object directly mixes, and can significantly reduce its illumination effect, therefore to obtain and mix the good illumination effect of rare earth compound, it is necessary to make to mix
Rare earth compound and PANI and Fe3O4Realization efficiently separates.If by conductive polymer polyanilinc PANI and Fe3O4It is nanocrystalline with
Polyacrylonitrile (PAN) is compounded to form nano fibrous membrane, then this layer film will have electromagnetism difunctional, if rare earth compound will be mixed
Bi2WO6:Yb3+,Er3+It is compounded to form nano fibrous membrane with PAN, then this layer film will have up-conversion luminescence and the double function of photocatalysis
Can, then by both Film laminateds to being formed together upper layer and lower layer composite membrane, so that it may realize polyaniline PANI and Fe3O4With mix
Rare earth compound Bi2WO6:Yb3+,Er3+It efficiently separates, to obtain four function of electromagnetism up-conversion luminescence photocatalysis of good performance
Two layers of nano-fiber composite film, this novel membrane material will be with important application prospects, has not yet to see relevant document
Report.
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, these fibers
It is stacked into and is formed micro nanometer fiber film together.People have used electrostatic spinning technique to be prepared for shining, photocatalysis, conduction
With magnetic simple function, difunctional and three-function nano tunica fibrosa.Q.Z.Yu, et al. are prepared for having using electrostatic spinning technique
There is the polyaniline PANI nano fibrous membrane [Mater.Sci.Eng.B, 2008,150,70-76] of single conducting function;W.W.Ma,
Et al. etc. is prepared for the LaOBr:Yb with up-conversion luminescence performance using electrostatic spinning technique3+/Er3+It nanofiber and receives
Rice band film [Luminescence, 2014,29 (7), 908-913];Guo Yueqiu etc. is prepared for using electrostatic spinning technique with light
The flexible TiO of catalytic property2Nanofiber [Rare Metals Materials and engineering, 2010,39 (12), 2227-2230];Wang Ce etc. is adopted
It is prepared for having magnetic polyvinylpyrrolidone/ferroso-ferric oxide composite nano-fiber film [high with method of electrostatic spinning
School chemistry journal, 2006,27 (10), 2002-2004];Qingbiao Yang, et al. are prepared for using electrostatic spinning technique
Fe2O3nanoparticles/Eu(DBM)3(Bath) compound difunctional magneto-optic nano fibrous membrane [Journal of Colloid
And Interface Science, 2010,350,396-401], Dong Xiangting etc. is prepared for Fe using electrostatic spinning technique3O4/Eu
(BA)3Phen/PVP magneto-optic double-function composite nano-fiber membrane [Journal of Nanoparticle Research, 2012,
14(10):1203-1209]、Eu(BA)3Phen/PANI/PVP photoelectricity difunctional composite nano-fiber membrane [institution of higher education's Science of Chemistry
Report, 2012,33 (8), 1657-1662] and Eu (BA)3phen/PANI/Fe3O4/ PVP photoelectromagnetic three-function nano tunica fibrosa
[Journal of Materials Science:Materials in Electronics,2014,25(3),1309-1316]。
Currently, having no the phase for preparing electromagnetism up-conversion luminescence photocatalysis four functions, two layers of nano-fiber composite film using electrostatic spinning technique
Close report.
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 parameter and spinning head structure the morphology and size of final products is all had a major impact.In the present invention,
Bi prepared by electrostatic spinning technique2WO6:Yb3+,Er3+Nanofiber and polyacrylonitrile (PAN) are added to N,N-dimethylformamide
In DMF, it is configured to the electrostatic spinning liquid with certain viscosity, referred to as spinning solution I, by the Fe of Coated with Oleic Acid3O4Nanocrystalline,
PAN, aniline, camphorsulfonic acid, ammonium persulfate, DMF mixing, constitute another spinning solution, referred to as after aniline polymerization is at polyaniline
Spinning solution II, the viscosity for controlling spinning solution are most important.Electrostatic spinning is carried out using uniaxial electrospinning technology, first uses spinning
Liquid I carries out electrostatic spinning and prepares Bi under optimal process conditions2WO6:Yb3+,Er3+/ PAN up-conversion luminescence photocatalysis is double
Then functional nano-fiber film carries out electrostatic spinning using spinning solution II on this film, obtains PANI/Fe3O4/ PAN electromagnetism
Dual-functional nanometer fiber membrane is thus successfully prepared for the [PANI/Fe of structure novel3O4/PAN]/[Bi2WO6:Yb3+,
Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four functions, two layers of nano-fiber composite film.
Summary of the invention
Up-conversion luminescence, photocatalysis, conduction and magnetic single function are prepared for using electrostatic spinning technique in the background technology
Energy, difunctional and three-function nano tunica fibrosa, used raw material, template and final target product and method of the invention
It is different.The present invention is prepared for [PANI/Fe using electrostatic spinning technique3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism
Up-conversion luminescence photocatalysis four functions, two layers of nano-fiber composite film increases a kind of with new features for nano fibrous membrane field
With the nanofiber composite film material of new construction.
The invention is realized in this way the Fe of Coated with Oleic Acid is prepared using the precipitation method first3O4It is nanocrystalline, using electrostatic
Spining technology combination high-temperature calcination process prepares Bi2WO6:Yb3+,Er3+Up-conversion luminescence photocatalysis dual-functional nanometer fiber, will
Bi2WO6:Yb3+,Er3+Nanofiber and polyacrylonitrile (PAN) are added in n,N-Dimethylformamide DMF, and being configured to one has
The electrostatic spinning liquid of certain viscosity, referred to as spinning solution I, by the Fe of Coated with Oleic Acid3O4Nanocrystalline, aniline, camphorsulfonic acid, PAN, DMF
It is mixed with ammonium persulfate and constitutes another spinning solution, wherein aniline polymerization is at polyaniline PANI, referred to as spinning solution II;Control spinning
The viscosity of liquid is most important.Electrostatic spinning is carried out using single spinning head electrostatic spinning technique, under optimal process conditions, is obtained
[PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four functions, two layers of nanofiber be multiple
Film is closed, the steps include:
(1) precipitation method prepare the Fe of Coated with Oleic Acid3O4It is nanocrystalline
By 5.4060g FeCl3·6H2O, 2.7800g FeSO4·7H2O, 4.04g NH4NO3It is with 1.9000g molecular weight
20000 polyethylene glycol is dissolved in 100mL deionized water, is heated to 50 DEG C and is passed through argon gas 30min, ammonium hydroxide is then slowly added dropwise
PH value to solution is 11, continues logical argon gas 20min and obtains black suspension, after this suspension Magneto separate, uses dehydrated alcohol
It is successively washed with deionized water three times, place the product in 12h dry in 60 DEG C of vacuum oven, and obtaining diameter is 8-10nm's
Fe3O4It is nanocrystalline;Take Fe prepared by 2.0000g3O4It is nanocrystalline to be dispersed in the 100mL deionized water for being passed through 30min argon gas
And ultrasonic disperse 20min, then solution is heated to 80 DEG C, and 1mL oleic acid is added under protection of argon gas, then proceedes to react
Obtained precipitating is carried out Magneto separate by 40min, is removed water layer and will be deposited in 60 DEG C of vacuum ovens dry 6h, obtains
The Fe of Coated with Oleic Acid3O4It is nanocrystalline;
(2) method of electrostatic spinning combination high-temperature roasting prepares Bi2WO6:Yb3+,Er3+Nanofiber
Weigh 0.0194g Yb2O3With 0.0095g Er2O3It is dissolved in suitable concentrated nitric acid simultaneously evaporative crystallization, is obtained dilute
After 5mL deionized water dissolving is added, 0.6085g (NH is added in native nitrate mixture4)10W12O41With 1.0087g citric acid, in
110 DEG C of stirring evaporations form gel, and 2.3285g Bi (NO is added after being cooled to room temperature3)3·5H2O and 23.4960g N, N- bis-
Methylformamide DMF adds the polyvinylpyrrolidone PVP that 2.9431g molecular weight is 1300000, stirs 4h and static 4h
Afterwards, the flaxen spinning solution of homogeneous transparent is formed, spinning solution is injected into the 5mL with 1mL plastic spray gun head and is injected
In device, the anode of high-voltage DC power supply is connected with copper wire electrode in syringe, and cathode is connected with reception device wire netting, lance head
It is in 15 ° of angles with horizontal direction, lance head is 15cm, spinning voltage 13kV, environment temperature 20-25 at a distance from wire netting
DEG C, relative humidity 40%-50% is collected into PVP/Bi (NO after carrying out electrostatic spinning on wire netting3)3/(NH4)10W12O41
Nanofiber, the PVP/Bi (NO that will be obtained3)3/(NH4)10W12O41Nanofiber is put into crucible, then crucible is put into program liter
In warm furnace, 300 DEG C are warming up to the heating rate of 1 DEG C/min, keeps the temperature half an hour, then be warming up to the heating rate of 2 DEG C/min
500 DEG C, after keeping the temperature 1h, Bi is obtained after natually cooled to room temperature2WO6:Yb3+,Er3+Nanofiber;
(3) spinning solution is prepared
Weigh Bi described in 0.36g2WO6:Yb3+,Er3+Nanofiber is added 6.0g DMF and ultrasound 20min, adds
The polyacrylonitrile (PAN) that 0.6g molecular weight is 86000 stirs 2h at 70 DEG C, obtains spinning solution I after cooling;By 0.6g oleic acid packet
The Fe covered3O4It is nanocrystalline to be added in 4.0g DMF solvent simultaneously ultrasound 20min, add the polypropylene that 0.6g molecular weight is 86000
Nitrile PAN stirs 2h at 70 DEG C, and aniline ANI and 0.5238g the camphorsulfonic acid CSA of 0.42g, room temperature are added after being cooled to room temperature
1.0291g ammonium persulfate APS is dissolved in 2.0g DMF, magnetic agitation 2h by lower magnetic agitation 2h, by this two parts of solution in ice water
1h is placed in bath, this two parts of solution are mixed in ice-water bath later, after magnetic agitation 3h, mixed liquor is put into 5 DEG C of refrigerator
Middle refrigeration for 24 hours, obtains spinning solution II;
(4) [PANI/Fe is prepared3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] four function of electromagnetism up-conversion luminescence photocatalysis
Two layers of nano-fiber composite film
Spinning solution I is injected in the 10mL syringe with 1mL plastic spray gun head, the anode of high-voltage DC power supply with
Copper wire electrode is connected in syringe, and cathode is connected with reception device wire netting, using perpendicular spray mode, lance head and wire netting away from
From for 15cm, spinning voltage 15kV, environment temperature is 20-25 DEG C, relative humidity 40%-50%, carries out electrostatic spinning and obtains
To Bi2WO6:Yb3+,Er3+/ PAN up-conversion luminescence photocatalysis dual-functional nanometer tunica fibrosa, after spinning solution I exhausts, by spinning solution
II is injected into syringe, continues electrostatic spinning, in Bi2WO6:Yb3+,Er3+/ PAN up-conversion luminescence photocatalysis is difunctional
[PANI/Fe is obtained on nano fibrous membrane3O4/ PAN] electromagnetism dual-functional nanometer tunica fibrosa finally obtains as the solvent evaporates
[PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four functions, two layers of nanofiber be multiple
Close film.
Prepared [PANI/Fe in above process3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetically convert hair
Light photocatalysis four functions, two layers of nano-fiber composite film, is combined by double-layer films, PANI/Fe3O4/ PAN electromagnetism is difunctional to be received
The average thickness of rice fibrous layer is 112.35 μm, Bi2WO6:Yb3+,Er3+/ PAN up-conversion luminescence photocatalysis dual-functional nanometer fiber
The average thickness of layer is 133.47 μm;Under the diode laser excitation of 980nm, [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3 +,Er3+/ PAN] side that shines in electromagnetism up-conversion luminescence photocatalysis four functions, two layers of nano-fiber composite film launches main peak position
In the Green band of 531nm and 545nm and the emitting red light band of 658nm;[PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,
Er3+/ PAN] average conductivity of conductive side is in electromagnetism up-conversion luminescence photocatalysis four functions, two layers of nano-fiber composite film
8.03×10-3S·cm-1;[PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] four function of electromagnetism up-conversion luminescence photocatalysis
The saturation magnetization of two layers of nano-fiber composite film of energy is 14.48emu/g;In the ultraviolet light that wavelength is 365nm
After 300min, [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] it receives for two layers of four functions of electromagnetism up-conversion luminescence photocatalysis
Rice composite fiber membrane reaches 88.30% to the photocatalytic activity of rhodamine B, and two layers prepared of nano-fiber composite film has
Good four function of electromagnetism up-conversion luminescence photocatalysis, realizes goal of the invention.
Detailed description of the invention
Fig. 1 is [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] four function two of electromagnetism up-conversion luminescence photocatalysis
The XRD spectra of layer nano-fiber composite film;
Fig. 2 is [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] four function two of electromagnetism up-conversion luminescence photocatalysis
The SEM photograph of layer nano-fiber composite film, the figure also serve as Figure of abstract;
Fig. 3 is [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] four function two of electromagnetism up-conversion luminescence photocatalysis
The optical microscope photograph of layer nano-fiber composite film;
Fig. 4 is [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] four function two of electromagnetism up-conversion luminescence photocatalysis
The up-conversion emission spectra of layer nano-fiber composite film;
Fig. 5 is [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] four function two of electromagnetism up-conversion luminescence photocatalysis
Change curve of the layer nano-fiber composite film to rhodamine B photocatalytic degradation absorbance;
Fig. 6 is [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] four function two of electromagnetism up-conversion luminescence photocatalysis
The degradation rate curve of layer nano-fiber composite film ultraviolet catalytic rhodamine B degradation;
Fig. 7 is [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] four function two of electromagnetism up-conversion luminescence photocatalysis
The hysteresis loop figure of layer nano-fiber composite film.
Specific embodiment
Ytterbium oxide Yb selected by the present invention2O3With erbium oxide Er2O3Purity be 99.99%, ammonium tungstate (NH4)10W12O41, citric acid, Bi (NO3)3·5H2O, n,N-Dimethylformamide DMF, Iron(III) chloride hexahydrate, seven hydrated sulfuric acids are sub-
Iron, ammonium nitrate, the polyethylene glycol that molecular weight is 20000, nitric acid, the polyvinylpyrrolidone PVP that molecular weight is 1300000, point
The polyacrylonitrile (PAN) that son amount is 86000, dehydrated alcohol, ammonium hydroxide, aniline, camphorsulfonic acid, ammonium persulfate, oleic acid, argon gas is city
Sell analysis net product;The self-control of deionized water laboratory;Glass apparatus and equipment used common instrument and is set in laboratory
It is standby.
Embodiment: by 5.4060g FeCl3·6H2O, 2.7800g FeSO4·7H2O, 4.04g NH4NO3And 1.9000g
The polyethylene glycol that molecular weight is 20000 is dissolved in 100mL deionized water, is heated to 50 DEG C and is passed through argon gas 30min, then slowly
The pH value that ammonium hydroxide is added dropwise to solution is 11, continues logical argon gas 20min and obtains black suspension, after this suspension Magneto separate, uses
Dehydrated alcohol and deionized water are successively washed three times, and place the product in 12h dry in 60 DEG C of vacuum oven, and obtaining diameter is
The Fe of 8-10nm3O4It is nanocrystalline;Take Fe prepared by 2.0000g3O4Nanocrystalline be dispersed in has been passed through the 100mL of 30min argon gas
In ionized water and ultrasonic disperse 20min, then solution is heated to 80 DEG C under protection of argon gas, and 1mL oleic acid is added, then after
Continuous reaction 40min, carries out Magneto separate for obtained precipitating, removes water layer and will be deposited in 60 DEG C of vacuum ovens dry
6h obtains the Fe of Coated with Oleic Acid3O4It is nanocrystalline;Weigh 0.0194g Yb2O3With 0.0095g Er2O3It is dissolved in suitable concentrated nitric acid
In and evaporative crystallization, obtain rare earth nitrades mixture, after 5mL deionized water dissolving is added, 0.6085g (NH be added4)10W12O41With 1.0087g citric acid, gel is formed in 110 DEG C of stirring evaporations, 2.3285g Bi is added after being cooled to room temperature
(NO3)3·5H2O and 23.4960g n,N-Dimethylformamide DMF adds the poly- second that 2.9431g molecular weight is 1300000
Alkene pyrrolidone PVP, after stirring 4h and static 4h, forms the flaxen spinning solution of homogeneous transparent, and spinning solution is injected one
With in the 5mL syringe of 1mL plastic spray gun head, the anode of high-voltage DC power supply is connected branch with copper wire electrode in syringe, bears
Pole is connected with reception device wire netting, and lance head and horizontal direction are in 15 ° of angles, and lance head is 15cm at a distance from wire netting, spins
Filament voltage is 13kV, and environment temperature is 20-25 DEG C, relative humidity 40%-50%, is received on wire netting after carrying out electrostatic spinning
Collect PVP/Bi (NO3)3/(NH4)10W12O41Nanofiber, the PVP/Bi (NO that will be obtained3)3/(NH4)10W12O41Nanofiber is put
Enter in crucible, then crucible be put into temperature programming furnace, is warming up to 300 DEG C with the heating rate of 1 DEG C/min, keeps the temperature half an hour,
500 DEG C are warming up to the heating rate of 2 DEG C/min again, after keeping the temperature 1h, is obtained after natually cooled to room temperature flaxen
Bi2WO6:Yb3+,Er3+Nanofiber;Weigh Bi described in 0.36g2WO6:Yb3+,Er3+Nanofiber is added 6.0g DMF and surpasses
Sound 20min adds the polyacrylonitrile (PAN) that 0.6g molecular weight is 86000, and 2h is stirred at 70 DEG C, obtains spinning solution after cooling
I;By the Fe of 0.6g Coated with Oleic Acid3O4It is nanocrystalline to be added in 4.0g DMF solvent simultaneously ultrasound 20min, add 0.6g molecular weight
For 86000 polyacrylonitrile (PAN), 2h is stirred at 70 DEG C, aniline ANI and the 0.5238g camphor tree of 0.42g is added after being cooled to room temperature
Brain sulfonic acid CSA, magnetic agitation 2h, 1.0291g ammonium persulfate APS is dissolved in 2.0g DMF, magnetic agitation 2h, by this at room temperature
Two parts of solution place 1h in ice-water bath, later mix this two parts of solution in ice-water bath, after magnetic agitation 3h, by mixed liquor
It is put into 5 DEG C of refrigerator and refrigerates for 24 hours, obtain spinning solution II;Spinning solution I is injected into the 10mL for having 1mL plastic spray gun head
In syringe, the anode of high-voltage DC power supply is connected with copper wire electrode in syringe, and cathode is connected with reception device wire netting, adopts
With perpendicular spray mode, lance head is 15cm at a distance from wire netting, and spinning voltage 15kV, environment temperature is 20-25 DEG C, relatively wet
Degree is 40%-50%, carries out electrostatic spinning and obtains Bi2WO6:Yb3+,Er3+/ PAN up-conversion luminescence photocatalysis dual-functional nanometer is fine
Spinning solution II is injected into syringe after spinning solution I exhausts, continues electrostatic spinning, in Bi by dimension film2WO6:Yb3+,
Er3+[PANI/Fe is obtained on/PAN up-conversion luminescence photocatalysis dual-functional nanometer tunica fibrosa3O4/ PAN] electromagnetism dual-functional nanometer fibre
Dimension film finally obtains [PANI/Fe as the solvent evaporates3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetically convert hair
Light photocatalysis four functions, two layers of nano-fiber composite film.[the PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electricity
Contain cubic phase Fe in magnetic up-conversion luminescence photocatalysis four functions, two layers of nano-fiber composite film3O4It is nanocrystalline and rhombic system
Bi2WO6:Yb3+,Er3+, as shown in Figure 1;[the PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetically convert
Shine four function of photocatalysis, two layers of nano-fiber composite film, is combined by double-layer films, PANI/Fe3O4/ PAN electromagnetism is difunctional
The average thickness of layers of nanofibers is 112.35 μm, Bi2WO6:Yb3+,Er3+/ PAN up-conversion luminescence photocatalysis dual-functional nanometer is fine
The average thickness for tieing up layer is 133.47 μm, as shown in Figure 2;[the PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/PAN]
The side of electromagnetism up-conversion luminescence photocatalysis four functions, two layers of nano-fiber composite film includes dark colour polyaniline and Fe3O4It receives
Meter Jing, other side light colour include Bi2WO6:Yb3+,Er3+, as shown in Figure 3;Under the diode laser excitation of 980nm,
[PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four functions, two layers of nanofiber be multiple
It closes the side that shines in film to launch main peak and be located at the Green band of 531nm and 545nm and the emitting red light band of 658nm, divide
It Dui Yingyu not Er3+Ion2H11/2→4I15/2With4S3/2→4I15/2And4F9/2→4I15/2Transition transmitting, as shown in Figure 4;It is described
[PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four functions, two layers of nanofiber
Composite membrane have stronger magnetism, saturation magnetization 14.48emu/g, as shown in Figure 5;It is surveyed using Hall effect tester
Obtain [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four functions, two layers of nanofiber
The average conductivity of conductive side is 8.03 × 10 in composite membrane-3S·cm-1;Rhodamine B solution has characteristic absorption at 553nm
Peak, in the case where wavelength is 365nm ultraviolet light, [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetically convert hair
Light photocatalysis four functions, two layers of nano-fiber composite film has photocatalytic Degradation to rhodamine B, with prolonging for light irradiation time
The characteristic absorption peak intensity of long rhodamine B gradually weakens, as shown in Figure 6;In the case where wavelength is 365nm ultraviolet light, [PANI/
Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four functions, two layers of nano-fiber composite film pair
Rhodamine B has good photocatalytic Degradation, when degradation time is 300min, reaches to the degradation rate of rhodamine B
88.30%, as shown in Figure 7.
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 (1)
- The preparation method of four function of photocatalysis, two layers of nano-fiber composite film 1. electromagnetism shines, which is characterized in that use single spraying silk Head electrostatic spinning technique, preparing product is [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence light It is catalyzed four functions, two layers of nano-fiber composite film, by PANI/Fe3O4/ PAN electromagnetism dual-functional nanometer fibrous layer and Bi2WO6:Yb3+, Er3+/ PAN up-conversion luminescence photocatalysis dual-functional nanometer fibrous layer is combined up and down, the steps include:(1) precipitation method prepare the Fe of Coated with Oleic Acid3O4It is nanocrystallineBy 5.4060g FeCl3·6H2O, 2.7800g FeSO4·7H2O, 4.04g NH4NO3It is with 1.9000g molecular weight 20000 polyethylene glycol is dissolved in 100mL deionized water, is heated to 50 DEG C and is passed through argon gas 30min, ammonium hydroxide is then slowly added dropwise PH value to solution is 11, continues logical argon gas 20min and obtains black suspension, after this suspension Magneto separate, uses dehydrated alcohol It is successively washed with deionized water three times, place the product in 12h dry in 60 DEG C of vacuum oven, and obtaining diameter is 8-10nm's Fe3O4It is nanocrystalline;Take Fe prepared by 2.0000g3O4It is nanocrystalline to be dispersed in the 100mL deionized water for being passed through 30min argon gas And ultrasonic disperse 20min, then solution is heated to 80 DEG C, and 1mL oleic acid is added under protection of argon gas, then proceedes to react Obtained precipitating is carried out Magneto separate by 40min, is removed water layer and will be deposited in 60 DEG C of vacuum ovens dry 6h, obtains The Fe of Coated with Oleic Acid3O4It is nanocrystalline;(2) method of electrostatic spinning combination high-temperature roasting prepares Bi2WO6:Yb3+,Er3+NanofiberWeigh 0.0194g Yb2O3With 0.0095g Er2O3It is dissolved in suitable concentrated nitric acid simultaneously evaporative crystallization, obtains rare earth nitric acid After 5mL deionized water dissolving is added, 0.6085g (NH is added in salt mixture4)10W12O41With 1.0087g citric acid, in 110 DEG C Stirring evaporation forms gel, and 2.3285g Bi (NO is added after being cooled to room temperature3)3·5H2O and 23.4960g N, N- dimethyl methyl Amide DMF adds the polyvinylpyrrolidone PVP that 2.9431g molecular weight is 1300000, after stirring 4h and static 4h, is formed The flaxen spinning solution of homogeneous transparent injects spinning solution in one 5mL syringe with 1mL plastic spray gun head, high The anode of pressure DC power supply is connected with copper wire electrode in syringe, and cathode is connected with reception device wire netting, lance head and level Direction is in 15 ° of angles, and lance head is 15cm at a distance from wire netting, and spinning voltage 13kV, environment temperature is 20-25 DEG C, relatively Humidity is 40%-50%, and PVP/Bi (NO is collected on wire netting after carrying out electrostatic spinning3)3/(NH4)10W12O41Nanowire Dimension, the PVP/Bi (NO that will be obtained3)3/(NH4)10W12O41Nanofiber is put into crucible, then crucible is put into temperature programming furnace It is interior, 300 DEG C are warming up to the heating rate of 1 DEG C/min, keeps the temperature half an hour, then be warming up to 500 with the heating rate of 2 DEG C/min DEG C, after keeping the temperature 1h, Bi is obtained after natually cooled to room temperature2WO6:Yb3+,Er3+Nanofiber;(3) spinning solution is preparedWeigh Bi described in 0.36g2WO6:Yb3+,Er3+Nanofiber is added 6.0g DMF and ultrasound 20min, adds 0.6g The polyacrylonitrile (PAN) that molecular weight is 86000 stirs 2h at 70 DEG C, obtains spinning solution I after cooling;By 0.6g Coated with Oleic Acid Fe3O4It is nanocrystalline to be added in 4.0g DMF solvent simultaneously ultrasound 20min, add the polyacrylonitrile that 0.6g molecular weight is 86000 PAN stirs 2h at 70 DEG C, aniline ANI and 0.5238g the camphorsulfonic acid CSA of 0.42g is added after being cooled to room temperature, at room temperature 1.0291g ammonium persulfate APS is dissolved in 2.0g DMF, magnetic agitation 2h by magnetic agitation 2h, by this two parts of solution in ice-water bath This two parts of solution are mixed in ice-water bath later, after magnetic agitation 3h, mixed liquor are put into 5 DEG C of refrigerator by middle placement 1h Refrigeration for 24 hours, obtains spinning solution II;(4) [PANI/Fe is prepared3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] two layers of four functions of electromagnetism up-conversion luminescence photocatalysis Nano-fiber composite filmSpinning solution I is injected in the 10mL syringe with 1mL plastic spray gun head, anode and the injection of high-voltage DC power supply Copper wire electrode is connected in device, and cathode is connected with reception device wire netting, and using perpendicular spray mode, lance head is at a distance from wire netting 15cm, spinning voltage 15kV, environment temperature are 20-25 DEG C, relative humidity 40%-50%, carry out electrostatic spinning and obtain Bi2WO6:Yb3+,Er3+/ PAN up-conversion luminescence photocatalysis dual-functional nanometer tunica fibrosa, after spinning solution I exhausts, by spinning solution II It is injected into syringe, continues electrostatic spinning, in Bi2WO6:Yb3+,Er3+/ PAN up-conversion luminescence photocatalysis is difunctional to be received [PANI/Fe is obtained on rice tunica fibrosa3O4/ PAN] electromagnetism dual-functional nanometer tunica fibrosa finally obtains as the solvent evaporates [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four functions, two layers of nanofiber be multiple Close film, PANI/Fe3O4The average thickness of/PAN electromagnetism dual-functional nanometer fibrous layer is 112.35 μm, Bi2WO6:Yb3+,Er3+/PAN The average thickness of up-conversion luminescence photocatalysis dual-functional nanometer fibrous layer is 133.47 μm;Swash in the diode laser of 980nm It gives, [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four functions, two layers of Nanowire The side that shines in dimension composite membrane launches main peak and is located at the Green band of 531nm and 545nm and the emitting red light of 658nm Band;[PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four functions, two layers of nanofiber The average conductivity of conductive side is 8.03 × 10 in composite membrane-3S·cm-1;[PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3 +/ PAN] electromagnetism up-conversion luminescence photocatalysis four functions, two layers of nano-fiber composite film saturation magnetization be 14.48emu/g; After wavelength is the ultraviolet light 300min of 365nm, [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetically It converts four function of photocatalysis, two layers of the nano-fiber composite film that shine and 88.30% is reached to the photocatalytic activity of rhodamine B, it is made Two layers standby of nano-fiber composite film has the function of good electromagnetism up-conversion luminescence photocatalysis four.
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