CN106391129A - Electromagnetism, luminescence, and photocatalysis four-function two-layer nanofiber composite film as well as preparation method thereof - Google Patents
Electromagnetism, luminescence, and photocatalysis four-function two-layer nanofiber composite film as well as preparation method thereof Download PDFInfo
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- CN106391129A CN106391129A CN201610765905.7A CN201610765905A CN106391129A CN 106391129 A CN106391129 A CN 106391129A CN 201610765905 A CN201610765905 A CN 201610765905A CN 106391129 A CN106391129 A CN 106391129A
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 68
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 67
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 66
- 238000004020 luminiscence type Methods 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229920000767 polyaniline Polymers 0.000 claims abstract description 63
- 238000009987 spinning Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 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
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 109
- 238000006243 chemical reaction Methods 0.000 claims description 56
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 239000012528 membrane Substances 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 16
- 229910052786 argon Inorganic materials 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 12
- -1 rare earth nitric acid Salt Chemical class 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
- 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
- 241000209094 Oryza Species 0.000 claims description 6
- 235000007164 Oryza sativa Nutrition 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
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 235000009566 rice Nutrition 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 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
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 239000002070 nanowire Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 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
- 238000009413 insulation Methods 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
- 238000004321 preservation Methods 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
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000011833 salt mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 239000000835 fiber Substances 0.000 abstract description 12
- 239000002086 nanomaterial Substances 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000010923 batch production Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 37
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 229910002651 NO3 Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 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
- 238000001523 electrospinning Methods 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
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010409 thin film 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
- 230000015572 biosynthetic process Effects 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
- 230000007613 environmental effect Effects 0.000 description 1
- ZXGIFJXRQHZCGJ-UHFFFAOYSA-N erbium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Er+3].[Er+3] ZXGIFJXRQHZCGJ-UHFFFAOYSA-N 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
- 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
- 238000000048 melt cooling Methods 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
- 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
- 150000002910 rare earth metals Chemical class 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
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 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
-
- 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)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to an electromagnetism, luminescence, and photocatalysis four-function two-layer nanofiber composite film as well as a preparation method thereof, and belongs to the technical field of nano-material preparation. The preparation method comprises four steps: (1) Fe3O4 nanocrystalline coated by oleic acid is prepared by a precipitation method; (2) Bi2WO6:Yb3+,Er3+ nanometer fiber is prepared by combination of an electrostatic spinning method and high temperature roasting; (3) spinning liquid is prepared; (4) the [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/PAN] electromagnetism, luminescence, and photocatalysis four-function two-layer nanofiber composite film is prepared, and a single shaft electrostatic spinning technology is used for preparation. The nanometer composite film has four good functions containing electromagnetism, upconversion luminescence, and photocatalysis. The method is easy to operate and used for large-batch production, and the novel material with the nanostructure has wide application prospects.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, in particular relate to the luminous photocatalysis four function two-layer nanometer of electromagnetism
Composite fiber membrane and preparation method thereof.
Background technology
Simple function applications to nanostructures is limited in scope, and the range of application of difunctional or multi-functional nanometer material is more
Extensively, this kind of material has more characteristic and captivation, and therefore, multi-functional nanometer material is paid high attention to by researcher.With nanometer
The development of science and technology, nano material, by simple function, such as has the characteristics of luminescence, photocatalysis property, electric conductivity, magnetic, towards double work(
Can and multifunctional direction development, such as have magnetic-fluorescence, luminous-photocatalysis, fluorescence-conduction or conduction-magnetic difunctional with
And-photocatalysis-conduction-magnetic four function that lights, so difunctional or four functions can be realized on a kind of nano structural material,
Development to the science and technology of nano-device, nanotechnology and correlation is significant.For example, magnetic-fluorescent dual-function
Nano composite material is medical diagnosis on disease and treatment provides a kind of new platform, and the difunctional property due to them makes disease
" finding-detection-treatment " is integrally formed.The use of this nano composite material is improved the efficiency of diagnosis further and is reduced secondary
Effect, causes the highest attention of researcher.Electromagnetism dual-functional nanometer complex is in thunderstorm activity, electromagnetic shielding, antistatic
The aspect such as coating and sensor has broad application prospects.
Ferroso-ferric oxide Fe3O4It is a kind of important and wide variety of magnetic material.People have adopted multiple methods, such as
The method such as the sedimentation method, sol-gel process, microemulsion method, hydro-thermal and solvent-thermal method, thermal decomposition method, method of electrostatic spinning is successfully made
Standby gone out Fe3O4The nanocrystalline, nano material such as nanometer rods, nano wire, nanometer film, hybrid structure, Core-shell Structure Nanoparticles, skill
Art comparative maturity.Bi2WO6:Yb3+,Er3+There is good photocatalysis and Upconversion luminescence, researcher has adopted multiple
Method is prepared for Bi2WO6:Yb3+,Er3+Nano material, technology also comparative maturity.Polyaniline PANI is readily synthesized due to it, conductance
The advantages of rate is high good with environmental stability, has become as one of focus of conducting polymer area research.People have synthesized
The polyaniline PANI of the one-dimensional nano structures such as nano wire, nanometer rods, nanotube and nanofiber, therefore, using electrically conductive polyaniline
PANI, magnetic Fe3O4Nanocrystalline and Bi2WO6:Yb3+,Er3+Construct and there is receiving of electromagnetism up-conversion luminescence photocatalysis four functional characteristic
Rice material is preferable material.
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
Thing directly mixes, and can significantly reduce its illumination effect, therefore will 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 Fe3O4Nanocrystalline with
Polyacrylonitrile (PAN) is compounded to form nano fibrous membrane, then will to have electromagnetism difunctional, if rare earth compound will be mixed for this layer film
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 work(of photocatalysis
Can, then by both Film laminateds to forming upper and lower two-layer composite membrane together it is possible to realize polyaniline PANI and Fe3O4With mix
Rare earth compound Bi2WO6:Yb3+,Er3+Efficiently separate, thus obtaining electromagnetism up-conversion luminescence photocatalysis four function of good performance
Two-layer nano-fiber composite film, this new membrane material will have important application prospect, have not yet to see the document of correlation
Report.
The United States Patent (USP) of Patent No. 1975504 discloses a relevant electrospinning process (electrospinning)
Technical scheme, the method is to prepare a kind of effective ways of micro nanometer fiber that is continuous, having macro length, by
Formhals proposed first in 1934.This method is mainly used to prepare high polymer nanometer fiber, it is characterized in that making powered
Macromolecular solution or melt are sprayed by nozzle by the traction of electrostatic force in electrostatic field, invest the receiving screen on opposite, thus real
Existing wire drawing, then, solvent evaporation, or melt cooling at normal temperatures solidifies to room temperature, obtains micro nanometer fiber, these fibers
It is stacked into and be the formation of micro nanometer fiber film together.People are prepared for lighting using electrostatic spinning technique, photocatalysis, conduction
With magnetic simple function, difunctional and three-function nano fibrous membrane.Q.Z.Yu, et al. is prepared for using electrostatic spinning technique to be had
There is 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 with up-conversion luminescence performance using electrostatic spinning technique:Yb3+/Er3+Nanofiber and receiving
Rice band film [Luminescence, 2014,29 (7), 908-913]；Guo Yueqiu etc. is prepared for light using electrostatic spinning technique
The flexible TiO of catalytic property2Nanofiber [Rare Metals Materials and engineering, 2010,39 (12), 2227-2230]；Wang Ce etc. adopts
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. is prepared for using electrostatic spinning technique
Fe2O3nanoparticles/Eu(DBM)3(Bath) it is combined 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 fibrous membrane
[Journal of Materials Science:Materials in Electronics,2014,25(3),1309-1316].
At present, have no the phase preparing electromagnetism up-conversion luminescence photocatalysis four function two-layer nano-fiber composite film using electrostatic spinning technique
Close report.
During using electrostatic spinning technique preparation nano material, the species of raw material, the molecular weight of high polymer templates, spinning liquid
The structure of composition, spinning process parameter and spinning head the pattern of final products and size are 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 an electrostatic spinning liquid with certain viscosity, referred to as spinning liquid I, by the Fe of Coated with Oleic Acid3O4Nanocrystalline,
PAN, aniline, camphorsulfonic acid, Ammonium persulfate., DMF mixing, become to constitute another kind of spinning liquid after polyaniline after aniline polymerization, referred to as
Spinning liquid II, controls the viscosity of spinning liquid most important.Electrostatic spinning is carried out using single shaft electrostatic spinning technique, first using spinning
Liquid I carries out electrostatic spinning, under optimal process conditions, prepares Bi2WO6:Yb3+,Er3+/ PAN up-conversion luminescence photocatalysis are double
Functional nano-fiber thin film, then carries out electrostatic spinning using spinning liquid II on this thin film, obtains PANI/Fe3O4/ PAN electromagnetism
Dual-functional nanometer fiber membrane, is thus successfully prepared for the novel [PANI/Fe of structure3O4/PAN]/[Bi2WO6:Yb3+,
Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two-layer nano-fiber composite film.
Content of the invention
In the introduction up-conversion luminescence, photocatalysis, conduction and the single work(of magnetic are prepared for using electrostatic spinning technique
Energy, difunctional and three-function nano fibrous membrane, the raw material being used, template and final target product and the method for the present invention
Different.The present invention is prepared for [PANI/Fe using electrostatic spinning technique3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism
Up-conversion luminescence photocatalysis four function two-layer nano-fiber composite film, is that nano fibrous membrane field increased one kind and has new features
Nanofiber composite film material with new construction.
The present invention is achieved in that the Fe preparing Coated with Oleic Acid initially with the sedimentation method3O4Nanocrystalline, using electrostatic
Spining technology prepares Bi with reference to high-temperature calcination process2WO6:Yb3+,Er3+Up-conversion luminescence photocatalysis dual-functional nanometer fiber, will
Bi2WO6:Yb3+,Er3+Nanofiber and polyacrylonitrile (PAN) are added in DMF DMF, are configured to one and have
The electrostatic spinning liquid of certain viscosity, referred to as spinning liquid I, by the Fe of Coated with Oleic Acid3O4Nanocrystalline, aniline, camphorsulfonic acid, PAN, DMF
Mix with Ammonium persulfate. and constitute another spinning liquid, wherein aniline polymerization becomes polyaniline PANI, referred to as spinning liquid 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, obtains
[PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two-layer nanofiber is again
Close film, its step is：
(1) sedimentation method prepare the Fe of Coated with Oleic Acid3O4Nanocrystalline
By 5.4060g FeCl3·6H2O, 2.7800g FeSO4·7H2O, 4.04g NH4NO3With 1.9000g molecular weight it is
20000 Polyethylene Glycol is dissolved in 100mL deionized water, is heated to 50 DEG C and is passed through argon 30min, is then slowly added dropwise ammonia
PH value to solution is 11, continues logical argon 20min and obtains black suspension, after this suspension Magneto separate, uses dehydrated alcohol
Wash successively three times with deionized water, product is placed in 60 DEG C of vacuum drying oven 12h is dried, obtain a diameter of 8-10nm's
Fe3O4Nanocrystalline；Take the Fe prepared by 2.0000g3O4Nanocrystalline it is dispersed in the 100mL deionized water being passed through 30min argon
And ultrasonic disperse 20min, then solution is heated to 80 DEG C under argon protection, and adds 1mL Oleic acid, then proceed to react
40min, obtained precipitation is carried out Magneto separate, removes water layer and will be deposited in 60 DEG C of vacuum drying ovens 6h is dried, obtains
The Fe of Coated with Oleic Acid3O4Nanocrystalline；
(2) method of electrostatic spinning combines high-temperature roasting preparation Bi2WO6:Yb3+,Er3+Nanofiber
Weigh 0.0194g Yb2O3With 0.0095g Er2O3It is dissolved in appropriate concentrated nitric acid and evaporative crystallization, obtain dilute
Native nitrate mixture, after adding 5mL deionized water dissolving, adds 0.6085g (NH4)10W12O41With 1.0087g citric acid, in
110 DEG C of stirring evaporations form gel, add 2.3285g Bi (NO after being cooled to room temperature3)3·5H2O and 23.4960g N, N- bis-
Methylformamide DMF, adds Polyvinylpyrrolidone PVP that 2.9431g molecular weight is 1300000, stirring 4h static 4h
Afterwards, form the flaxen spinning solution of homogeneous transparent, spinning solution is injected a 5mL injection carrying 1mL plastic spray gun head
In device, the positive pole of high-voltage DC power supply is connected with copper wire electrode in syringe, and negative pole is connected with reception device wire gauze, lance head
It is in 15 ° of angles with horizontal direction, lance head is 15cm with the distance of wire gauze, and spinning voltage is 13kV, and ambient temperature is 20-25
DEG C, relative humidity is 40%-50%, collects PVP/Bi (NO after carrying out electrostatic spinning on wire gauze3)3/(NH4)10W12O41
Nanofiber, by the PVP/Bi obtaining (NO3)3/(NH4)10W12O41Nanofiber is put in crucible, then crucible is put into program liter
In warm stove, it is warming up to 300 DEG C with the heating rate of 1 DEG C/min, be incubated half an hour, then be warming up to the heating rate of 2 DEG C/min
500 DEG C, after insulation 1h, natural cooling obtains Bi after being down to room temperature2WO6:Yb3+,Er3+Nanofiber；
(3) prepare spinning liquid
Weigh the Bi described in 0.36g2WO6:Yb3+,Er3+Nanofiber, adds 6.0g DMF ultrasonic 20min, adds
0.6g molecular weight is 86000 polyacrylonitrile (PAN), stirs 2h, obtain spinning liquid I after cooling at 70 DEG C；By 0.6g Oleic acid bag
The Fe covering3O4Nanocrystalline be added in 4.0g DMF solvent and ultrasonic 20min, add the polypropylene that 0.6g molecular weight is 86000
Nitrile PAN, stirs 2h at 70 DEG C, adds the aniline ANI and 0.5238g camphorsulfonic acid CSA of 0.42g, room temperature after being cooled to room temperature
Lower magnetic agitation 2h, 1.0291g Ammonium persulfate. APS is dissolved in 2.0g DMF, magnetic agitation 2h, by this two parts of solution in frozen water
Place 1h in bath, afterwards this two parts of solution are mixed in ice-water bath, after magnetic agitation 3h, mixed liquor is put into 5 DEG C of refrigerator
Middle cold preservation 24h, obtains spinning liquid II；
(4) prepare [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function
Two-layer nano-fiber composite film
By spinning liquid I inject one carry 1mL plastic spray gun head 10mL syringe in, the positive pole of high-voltage DC power supply with
In syringe, copper wire electrode is connected, and negative pole is connected with reception device wire gauze, using perpendicular spray mode, lance head and wire gauze away from
From for 15cm, spinning voltage is 15kV, and ambient temperature is 20-25 DEG C, and relative humidity is 40%-50%, carries out electrostatic spinning and obtains
To Bi2WO6:Yb3+,Er3+/ PAN up-conversion luminescence photocatalysis dual-functional nanometer fibrous membrane, after spinning liquid I exhausts, by spinning liquid
II is injected in syringe, proceeds electrostatic spinning, in Bi2WO6:Yb3+,Er3+/ PAN up-conversion luminescence photocatalysis are difunctional
[PANI/Fe is obtained on nano fibrous membrane3O4/ PAN] electromagnetism dual-functional nanometer fibrous membrane, with the volatilization of solvent, finally give
[PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two-layer nanofiber is again
Close film.
Prepared [PANI/Fe in above process3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetically conversion
Light photocatalysis four function two-layer nano-fiber composite film, is composited by double-layer filmses, PANI/Fe3O4/ PAN electromagnetism is difunctional to be received
The fibrolaminar average thickness of rice 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 of 980nm excites, [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3 +,Er3+/ PAN] main peak position is launched in luminous side in electromagnetism up-conversion luminescence photocatalysis four function two-layer nano-fiber composite film
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 function two-layer nano-fiber composite film
8.03×10-3S·cm-1；[PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four work(
The saturation magnetization of energy two-layer nano-fiber composite film is 14.48emu/g；In the ultraviolet light for 365nm for the wavelength
After 300min, [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two-layer receives
Rice composite fiber membrane reaches 88.30% to the photocatalytic activity of rhodamine B, and prepared two-layer nano-fiber composite film has
Good electromagnetism up-conversion luminescence photocatalysis four function is it is achieved that goal of the invention.
Brief description
Fig. 1 is [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two
The XRD spectra of layer nano-fiber composite film；
Fig. 2 is [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two
The SEM photograph of layer nano-fiber composite film, this figure also serves as Figure of abstract；
Fig. 3 is [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two
The optical microscope photograph of layer nano-fiber composite film；
Fig. 4 is [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two
The Up-conversion emission spectrogram of layer nano-fiber composite film；
Fig. 5 is [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two
The layer change curve to rhodamine B photocatalytic degradation absorbance for the nano-fiber composite film；
Fig. 6 is [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two
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] electromagnetism up-conversion luminescence photocatalysis four function two
The hysteresis curve figure of layer nano-fiber composite film.
Specific embodiment
Ytterbium oxide Yb selected by the present invention2O3With Erbia Er2O3Purity be 99.99%, ammonium tungstate (NH4)10W12O41, citric acid, Bi (NO3)3·5H2O, DMF DMF, Iron(III) chloride hexahydrate, seven hydrated sulfuric acid are sub-
Ferrum, ammonium nitrate, molecular weight is 20000 Polyethylene Glycol, nitric acid, and molecular weight is 1300000 Polyvinylpyrrolidone PVP, point
Son measures the polyacrylonitrile (PAN) for 86000, dehydrated alcohol, ammonia, aniline, camphorsulfonic acid, Ammonium persulfate., Oleic acid, and argon is city
Sell analysis net product；Deionized water laboratory is made by oneself；Glass apparatus used and equipment are conventional instruments in laboratory and set
Standby.
Embodiment：By 5.4060g FeCl3·6H2O, 2.7800g FeSO4·7H2O, 4.04g NH4NO3And 1.9000g
Molecular weight is that 20000 Polyethylene Glycol is dissolved in 100mL deionized water, is heated to 50 DEG C and is passed through argon 30min, then slowly
Deca ammonia is 11 to the pH value of solution, continues logical argon 20min and obtains black suspension, after this suspension Magneto separate, uses
Dehydrated alcohol and deionized water wash three times successively, product is placed in 60 DEG C of vacuum drying oven 12h is dried, obtain a diameter of
The Fe of 8-10nm3O4Nanocrystalline；Take the Fe prepared by 2.0000g3O4Nanocrystalline being dispersed in is passed through the 100mL of 30min argon
In ionized water and ultrasonic disperse 20min, then solution is heated to 80 DEG C under argon protection, and adds 1mL Oleic acid, Ran Houji
Continuous reaction 40min, obtained precipitation is carried out Magneto separate, removes water layer and will be deposited in 60 DEG C of vacuum drying ovens dry
6h, obtains the Fe of Coated with Oleic Acid3O4Nanocrystalline；Weigh 0.0194g Yb2O3With 0.0095g Er2O3It is dissolved in appropriate concentrated nitric acid
In and evaporative crystallization, obtain rare earth nitrate mixture, after adding 5mL deionized water dissolving, add 0.6085g (NH4)10W12O41With 1.0087g citric acid, form gel in 110 DEG C of stirring evaporations, after being cooled to room temperature, add 2.3285g Bi
(NO3)3·5H2O and 23.4960g DMF DMF, adds the poly- second that 2.9431g molecular weight is 1300000
Alkene pyrrolidone PVP, after stirring 4h static 4h, forms the flaxen spinning solution of homogeneous transparent, spinning solution is injected one
Prop up in the 5mL syringe with 1mL plastic spray gun head, the positive pole of high-voltage DC power supply is connected with copper wire electrode in syringe, bear
Pole is connected with reception device wire gauze, and lance head and horizontal direction are in 15 ° of angles, and lance head is 15cm with the distance of wire gauze, spins
Filament voltage is 13kV, and ambient temperature is 20-25 DEG C, and relative humidity is 40%-50%, receives after carrying out electrostatic spinning on wire gauze
Collect PVP/Bi (NO3)3/(NH4)10W12O41Nanofiber, by the PVP/Bi obtaining (NO3)3/(NH4)10W12O41Nanofiber is put
Enter in crucible, then crucible put in temperature programming stove, be warming up to 300 DEG C with the heating rate of 1 DEG C/min, be incubated half an hour,
It is warming up to 500 DEG C with the heating rate of 2 DEG C/min again, after insulation 1h, natural cooling obtains flaxen after being down to room temperature
Bi2WO6:Yb3+,Er3+Nanofiber；Weigh the Bi described in 0.36g2WO6:Yb3+,Er3+Nanofiber, adds 6.0g DMF and surpasses
Sound 20min, adds the polyacrylonitrile (PAN) that 0.6g molecular weight is 86000, stirs 2h, obtain spinning liquid after cooling at 70 DEG C
I；Fe by 0.6g Coated with Oleic Acid3O4Nanocrystalline be added in 4.0g DMF solvent and ultrasonic 20min, add 0.6g molecular weight
Polyacrylonitrile (PAN) for 86000, stirs 2h at 70 DEG C, adds aniline ANI and the 0.5238g Camphor tree of 0.42g after being cooled to room temperature
Brain sulfonic acid CSA, magnetic agitation 2h under room temperature, 1.0291g Ammonium persulfate. APS is dissolved in 2.0g DMF, magnetic agitation 2h, by this
Two parts of solution place 1h in ice-water bath, mix this two parts of solution afterwards, after magnetic agitation 3h, by mixed liquor in ice-water bath
Put into cold preservation 24h in 5 DEG C of refrigerator, obtain spinning liquid II；Spinning liquid I is injected a 10mL carrying 1mL plastic spray gun head
In syringe, the positive pole of high-voltage DC power supply is connected with copper wire electrode in syringe, and negative pole is connected with reception device wire gauze, adopts
With erecting spray mode, lance head is 15cm with the distance of wire gauze, and spinning voltage is 15kV, and ambient temperature is 20-25 DEG C, relatively wet
Spend for 40%-50%, carry out electrostatic spinning and obtain Bi2WO6:Yb3+,Er3+/ PAN up-conversion luminescence photocatalysis dual-functional nanometer is fine
Dimension film, after spinning liquid I exhausts, spinning liquid II is injected in syringe, proceeds electrostatic spinning, in Bi2WO6:Yb3+,
Er3+[PANI/Fe is obtained on/PAN up-conversion luminescence photocatalysis dual-functional nanometer fibrous membrane3O4/ PAN] electromagnetism dual-functional nanometer fibre
Dimension film, with the volatilization of solvent, finally gives [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetically conversion
Light photocatalysis four function two-layer nano-fiber composite film.Described [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electricity
Emission in Cubic Fe is contained in magnetic up-conversion luminescence photocatalysis four function two-layer nano-fiber composite film3O4Nanocrystalline and rhombic system
Bi2WO6:Yb3+,Er3+, as shown in Figure 1；Described [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetically change
Luminous photocatalysis four function two-layer nano-fiber composite film, is composited by double-layer filmses, PANI/Fe3O4/ PAN electromagnetism is difunctional
The average thickness of nanofiber layer is 112.35 μm, Bi2WO6:Yb3+,Er3+/ PAN up-conversion luminescence photocatalysis dual-functional nanometer is fine
The average thickness of dimension layer is 133.47 μm, as shown in Figure 2；Described [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/PAN]
The side of electromagnetism up-conversion luminescence photocatalysis four function two-layer nano-fiber composite film comprises dark colour polyaniline and Fe3O4Receive
Meter Jing, opposite side light colour comprises Bi2WO6:Yb3+,Er3+, as shown in Figure 3；Under the diode laser of 980nm excites,
[PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two-layer nanofiber is again
Close luminous side in film and launch main peak positioned at the Green band of 531nm and 545nm and the emitting red light band of 658nm, point
Dui Yingyu not Er3+Ion2H11/2→4I15/2With4S3/2→4I15/2And4F9/2→4I15/2Transition is launched, as shown in Figure 4；Described
[PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two-layer nanofiber
Composite membrane has stronger magnetic, and saturation magnetization is 14.48emu/g, as shown in Figure 5；Application Hall effect tester is surveyed
Obtain [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two-layer nanofiber
In composite membrane, the average conductivity of conductive side is 8.03 × 10-3S·cm-1；Rhodamine B solution has characteristic absorption at 553nm
Peak, in wavelength under 365nm ultraviolet light, [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetically conversion
Light photocatalysis four function two-layer nano-fiber composite film has photocatalytic Degradation to rhodamine B, with prolonging of light irradiation time
The characteristic absorption peak intensity of long rhodamine B gradually weakens, as shown in Figure 6；In wavelength under 365nm ultraviolet light, [PANI/
Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two-layer nano-fiber composite film pair
Rhodamine B has good photocatalytic Degradation, when degradation time is for 300min, the degradation rate of rhodamine B is reached
88.30%, as shown in Figure 7.
Certainly, the present invention also can have other various embodiments, in the case of without departing substantially from present invention spirit and its essence, ripe
Know those skilled in the art and work as and various corresponding changes and deformation can be made according to the present invention, but these corresponding changes and change
Shape all should belong to the protection domain of appended claims of the invention.
Claims (2)
1. electromagnetism lights photocatalysis four function two-layer nano-fiber composite film it is characterised in that by PANI/Fe3O4/ PAN electromagnetism is double
Functional nano-fiber layer and Bi2WO6:Yb3+,Er3+/ PAN up-conversion luminescence photocatalysis dual-functional nanometer fibrous layer up and down be combined and
Become, two-layer nano-fiber composite film has four kinds of functions of electromagnetism up-conversion luminescence photocatalysis, PANI/Fe simultaneously3O4/ PAN electromagnetism is double
The average thickness of functional nano-fiber layer is 112.35 μm, Bi2WO6:Yb3+,Er3+/ PAN up-conversion luminescence photocatalysis are difunctional to be received
The fibrolaminar average thickness of rice is 133.47 μm.
2. the preparation method of the luminous photocatalysis four function two-layer nano-fiber composite film of a kind of electromagnetism as claimed in claim 1,
It is characterized in that, using single spinning head electrostatic spinning technique, preparing product is [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3 +/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two-layer nano-fiber composite film, its step is：
(1) sedimentation method prepare the Fe of Coated with Oleic Acid3O4Nanocrystalline
By 5.4060g FeCl3·6H2O, 2.7800g FeSO4·7H2O, 4.04g NH4NO3With 1.9000g molecular weight it is
20000 Polyethylene Glycol is dissolved in 100mL deionized water, is heated to 50 DEG C and is passed through argon 30min, is then slowly added dropwise ammonia
PH value to solution is 11, continues logical argon 20min and obtains black suspension, after this suspension Magneto separate, uses dehydrated alcohol
Wash successively three times with deionized water, product is placed in 60 DEG C of vacuum drying oven 12h is dried, obtain a diameter of 8-10nm's
Fe3O4Nanocrystalline；Take the Fe prepared by 2.0000g3O4Nanocrystalline it is dispersed in the 100mL deionized water being passed through 30min argon
And ultrasonic disperse 20min, then solution is heated to 80 DEG C under argon protection, and adds 1mL Oleic acid, then proceed to react
40min, obtained precipitation is carried out Magneto separate, removes water layer and will be deposited in 60 DEG C of vacuum drying ovens 6h is dried, obtains
The Fe of Coated with Oleic Acid3O4Nanocrystalline；
(2) method of electrostatic spinning combines high-temperature roasting preparation Bi2WO6:Yb3+,Er3+Nanofiber
Weigh 0.0194g Yb2O3With 0.0095g Er2O3It is dissolved in appropriate concentrated nitric acid and evaporative crystallization, obtain rare earth nitric acid
Salt mixture, after adding 5mL deionized water dissolving, adds 0.6085g (NH4)10W12O41With 1.0087g citric acid, in 110 DEG C
Stirring evaporation forms gel, adds 2.3285g Bi (NO after being cooled to room temperature3)3·5H2O and 23.4960g N, N- dimethyl methyl
Amide DMF, adds Polyvinylpyrrolidone PVP that 2.9431g molecular weight is 1300000, after stirring 4h static 4h, is formed
The flaxen spinning solution of homogeneous transparent, spinning solution is injected in a 5mL syringe carrying 1mL plastic spray gun head, high
The positive pole of pressure DC source is connected with copper wire electrode in syringe, and negative pole is connected with reception device wire gauze, lance head and level
Direction is in 15 ° of angles, and lance head is 15cm with the distance of wire gauze, and spinning voltage is 13kV, and ambient temperature is 20-25 DEG C, relatively
Humidity is 40%-50%, collects PVP/Bi (NO after carrying out electrostatic spinning on wire gauze3)3/(NH4)10W12O41Nanowire
Dimension, by the PVP/Bi obtaining (NO3)3/(NH4)10W12O41Nanofiber is put in crucible, then crucible is put into temperature programming stove
Interior, it is warming up to 300 DEG C with the heating rate of 1 DEG C/min, be incubated half an hour, then be warming up to 500 with the heating rate of 2 DEG C/min
DEG C, after insulation 1h, natural cooling obtains Bi after being down to room temperature2WO6:Yb3+,Er3+Nanofiber；
(3) prepare spinning liquid
Weigh the Bi described in 0.36g2WO6:Yb3+,Er3+Nanofiber, adds 6.0g DMF ultrasonic 20min, adds 0.6g
Molecular weight is 86000 polyacrylonitrile (PAN), stirs 2h, obtain spinning liquid I after cooling at 70 DEG C；By 0.6g Coated with Oleic Acid
Fe3O4Nanocrystalline be added in 4.0g DMF solvent and ultrasonic 20min, add the polyacrylonitrile that 0.6g molecular weight is 86000
PAN, stirs 2h at 70 DEG C, adds the aniline ANI and 0.5238g camphorsulfonic acid CSA of 0.42g, under room temperature after being cooled to room temperature
Magnetic agitation 2h, 1.0291g Ammonium persulfate. APS is dissolved in 2.0g DMF, magnetic agitation 2h, by this two parts of solution in ice-water bath
This two parts of solution are mixed in ice-water bath, after magnetic agitation 3h, mixed liquor are put in 5 DEG C of refrigerator by middle placement 1h afterwards
Cold preservation 24h, obtains spinning liquid II；
(4) prepare [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two-layer
Nano-fiber composite film
Spinning liquid I is injected in a 10mL syringe carrying 1mL plastic spray gun head, the positive pole of high-voltage DC power supply and injection
In device, copper wire electrode is connected, and negative pole is connected with reception device wire gauze, and using perpendicular spray mode, lance head with the distance of wire gauze is
15cm, spinning voltage is 15kV, and ambient temperature is 20-25 DEG C, and relative humidity is 40%-50%, carries out electrostatic spinning and obtains
Bi2WO6:Yb3+,Er3+/ PAN up-conversion luminescence photocatalysis dual-functional nanometer fibrous membrane, after spinning liquid I exhausts, by spinning liquid II
It is injected in syringe, proceeds electrostatic spinning, in Bi2WO6:Yb3+,Er3+/ PAN up-conversion luminescence photocatalysis are difunctional to be received
[PANI/Fe is obtained on rice fibrous membrane3O4/ PAN] electromagnetism dual-functional nanometer fibrous membrane, with the volatilization of solvent, finally give
[PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two-layer nanofiber is again
Close film, PANI/Fe3O4The fibrolaminar average thickness of/PAN electromagnetism dual-functional nanometer is 112.35 μm, Bi2WO6:Yb3+,Er3+/PAN
The fibrolaminar average thickness of up-conversion luminescence photocatalysis dual-functional nanometer is 133.47 μm；Swash in the diode laser of 980nm
Give, [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two-layer Nanowire
In dimension composite membrane, main peak is launched positioned at the Green band of 531nm and 545nm and the emitting red light of 658nm in luminous side
Band；[PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two-layer nanofiber
In composite membrane, the average conductivity of conductive side is 8.03 × 10-3S·cm-1；[PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3 +/ PAN] electromagnetism up-conversion luminescence photocatalysis four function two-layer nano-fiber composite film saturation magnetization be 14.48emu/g；
After wavelength is for ultraviolet light 300min of 365nm, [PANI/Fe3O4/PAN]/[Bi2WO6:Yb3+,Er3+/ PAN] electromagnetically
The luminous photocatalysis four function two-layer nano-fiber composite film of conversion reaches 88.30% to the photocatalytic activity of rhodamine B, made
Standby two-layer nano-fiber composite film has good electromagnetism up-conversion luminescence photocatalysis four function.
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| CN106847382A (en) * | 2017-02-20 | 2017-06-13 | 吉林师范大学 | Function coaxial nano cable of photoelectromagnetic photocatalysis four and preparation method thereof |
| CN108295880A (en) * | 2018-01-23 | 2018-07-20 | 莆田学院 | A kind of magnetic, multi-functional photochemical catalyst nanocomposite and preparation method thereof |
| CN113828288A (en) * | 2020-06-23 | 2021-12-24 | 天津工业大学 | Alveolus-imitated double-layer nano-microfiber membrane photocatalyst and preparation method thereof |
| CN115646221A (en) * | 2022-10-31 | 2023-01-31 | 福州大学 | Light-driven single-layer Janus oil-water separation membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103225128A (en) * | 2013-03-05 | 2013-07-31 | 长春理工大学 | Photo-electromagnetic three-functional two-strands-paralleled nanometer fiber bundle and its preparation method |
-
2016
- 2016-08-30 CN CN201610765905.7A patent/CN106391129B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103225128A (en) * | 2013-03-05 | 2013-07-31 | 长春理工大学 | Photo-electromagnetic three-functional two-strands-paralleled nanometer fiber bundle and its preparation method |
Non-Patent Citations (4)
| Title |
|---|
| WENHUI ZHANG等: "Synthesis of Yb3+/Er3+ co-doped Bi2WO6 nanosheets with enhanced photocatalytic activity", 《MATERIALS LETTERS》 * |
| 侯坤: "静电纺丝技术构筑磁性光催化双功能一维纳米材料", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 王淑红等: "《先进聚合物基复合材料及应用》", 30 June 2009 * |
| 王渝生等: "《走进中国科学技术馆》", 31 August 2002 * |
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| CN106847382A (en) * | 2017-02-20 | 2017-06-13 | 吉林师范大学 | Function coaxial nano cable of photoelectromagnetic photocatalysis four and preparation method thereof |
| CN108295880A (en) * | 2018-01-23 | 2018-07-20 | 莆田学院 | A kind of magnetic, multi-functional photochemical catalyst nanocomposite and preparation method thereof |
| CN108295880B (en) * | 2018-01-23 | 2020-07-31 | 莆田学院 | Magnetic multifunctional photocatalyst nano composite material and preparation method thereof |
| CN113828288A (en) * | 2020-06-23 | 2021-12-24 | 天津工业大学 | Alveolus-imitated double-layer nano-microfiber membrane photocatalyst and preparation method thereof |
| CN113828288B (en) * | 2020-06-23 | 2023-07-07 | 天津工业大学 | Alveolus-imitating double-layer nano-micro fiber membrane photocatalyst and preparation method thereof |
| CN115646221A (en) * | 2022-10-31 | 2023-01-31 | 福州大学 | Light-driven single-layer Janus oil-water separation membrane and preparation method thereof |
| CN115646221B (en) * | 2022-10-31 | 2024-07-26 | 福州大学 | Light-driven single-layer Janus oil-water separation film and preparation method thereof |
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