CN105536872A - Preparing method for nanowire iron phthalocyanine/carbon nanofiber heterojunction composite material - Google Patents
Preparing method for nanowire iron phthalocyanine/carbon nanofiber heterojunction composite material Download PDFInfo
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- CN105536872A CN105536872A CN201610027863.7A CN201610027863A CN105536872A CN 105536872 A CN105536872 A CN 105536872A CN 201610027863 A CN201610027863 A CN 201610027863A CN 105536872 A CN105536872 A CN 105536872A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 54
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002070 nanowire Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229910052742 iron Inorganic materials 0.000 claims abstract description 52
- 238000002360 preparation method Methods 0.000 claims abstract description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 39
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 20
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 20
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 20
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 20
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 54
- 239000002184 metal Substances 0.000 claims description 54
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 35
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 30
- 239000002121 nanofiber Substances 0.000 claims description 28
- 150000002825 nitriles Chemical class 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000003763 carbonization Methods 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000013019 agitation Methods 0.000 claims description 12
- 238000009987 spinning Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 6
- 238000010041 electrostatic spinning Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- NTZMSBAAHBICLE-UHFFFAOYSA-N 4-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(C#N)=C1 NTZMSBAAHBICLE-UHFFFAOYSA-N 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 abstract 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 19
- 239000000835 fiber Substances 0.000 description 16
- 229920000049 Carbon (fiber) Polymers 0.000 description 13
- 239000004917 carbon fiber Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- 206010013786 Dry skin Diseases 0.000 description 10
- 230000009471 action Effects 0.000 description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 9
- 238000001523 electrospinning Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 carbon nano-fiber compound Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- 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
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Fibers (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a preparing method for a nanowire iron phthalocyanine/carbon nanofiber heterojunction composite material, and belongs to the technical field of composite materials. The preparing method includes iron-carbon nanofiber preparation and composite material preparation, composite material preparation includes the following steps that iron-containing carbon nanofibers, 4-nitrophthalonitrile and ammonium molybdate are poured into a reaction kettle together, ethanediol is added into the reaction kettle, the reaction kettle is sealed, placed in a drying oven and heated to be treated for 7-9 h, the reaction kettle is taken out and naturally cooled to room temperature, and a reaction product at the bottom of the kettle is taken out, washed, placed in a vacuum drying box to be dried for 4-6 h to obtain the composite material. The preparing method is simple in process, efficient, easy to operate, low in price and environmentally friendly and achieves large-scale production easily.
Description
Technical field
The invention belongs to the technical field of composite, relate to nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, be specifically related to the preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite.
Background technology
Metal phthalocyanine is that in a kind of ring, hole can hold the macrocyclic complex as many transition metal such as iron, cobalt, nickel that diameter with it matches, phthalocyanine ring itself is the large two-dimentional conjugated system with 18 pi-electrons, as a kind of macrocyclic complex, the extensive concern of researchers is subject to because it has stronger absworption peak at the visible region of the length being greater than 400nm, be considered to have most one of visible light catalyst of exploitation potential quality, solar energy so just can be utilized to dispose of sewage problem.Photocatalysis depends primarily on the separating effect in light induced electron and hole, for improving the visible light catalytic efficiency of metal phthalocyanine, many employings build heterojunction material, the material that usual and metal phthalocyanine builds hetero-junctions is metal oxide semiconductor, but it is caught and transmits the limited in one's ability of light induced electron.Therefore, with the electrospinning carbon nano-fiber compound of superpower electron transport ability, the transmitting moving of electronics can be strengthened to a certain extent, reduce the recombination probability in light induced electron and hole.
But organic crystal is difficult to grow up usually, the method usually preparing metal phthalocyanine and carbon fibre composite employing is, metal phthalocyanine and the carbon fiber after thionyl chloride process is disperseed in organic solvent, dries and metal phthalocyanine is transferred on carbon fiber.The usual more complicated of this preparation method, product yield are lower, loose on the exposure level being mainly manifested in metal phthalocyanine and carbon fiber, or even physical attachment is on carbon fiber, is difficult to form good hetero-junctions, is unfavorable for catching and transmission of light induced electron.
Summary of the invention
The present invention is for solving defect of the prior art; provide the preparation method of a kind of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite; method preparation technology provided by the present invention is succinct, is that a kind of efficient operation is easy, cheap, environmental friendliness, is easy to large-scale production.
The present invention is the technical scheme realizing the employing of its object:
The preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, comprise the preparation of iron content carbon nano-fiber and the preparation of composite, the preparation of described composite comprises the following steps: iron content carbon nano-fiber, 4-nitro phthalic nitrile and ammonium molybdate are together poured in reactor, then ethylene glycol is added wherein, reactor is sealed, be placed in 150-160 DEG C of baking oven and heat 7-9h, take out reactor, Temperature fall is to room temperature, take out product at the bottom of still, washing, dries, obtains product.
4-nitro phthalic nitrile: ammonium molybdate: the weight ratio of iron content carbon nano-fiber is (1.6-1.8): 1:(4-6).
The total amount of iron content carbon nano-fiber, 4-nitro phthalic nitrile, ammonium molybdate and ethylene glycol is the 78%-80% of reactor volume.The consumption of further ethylene glycol is 75% < V of reactor volume
ethylene glycol< 78%.
During oven dry, the product after washing is placed in the dry 4-6h of vacuum drying box, and bake out temperature is 40-60 DEG C.
Respectively clean three times with ethanol and distilled water respectively during washing, first wash three times with ethanol, then wash three times with distilled water.
The preparation of described iron content carbon nano-fiber comprises the following steps: polyacrylonitrile and molysite are dissolved in N, in dinethylformamide, then obtain the organic nanofibers containing molysite by the method for electrostatic spinning, and then through peroxidating, carbonization treatment, obtain iron content carbon nano-fiber.
The concrete steps of the preparation of described iron content carbon nano-fiber are as follows:
(1) be, 1:(0.01-0.03 by mass ratio) polyacrylonitrile and FeCl
24H
2o is dissolved in DMF, and magnetic agitation 20-24h obtains mixed solution;
(2), by mixed solution be transferred in syringe, and by a tubes connection on a metal joint, use traffic controller controls mixed solution and keeps flow velocity at 0.1-10sccm;
(3) use plate electrode, parallel metal plate electrode or rotating drum electrode as collecting electrode, the two poles of the earth of high voltage electrostatic device are connected on metal joint and collecting electrode, the high pressure of 10kV is provided by high voltage electrostatic device, start spinning, obtain the organic nanofibers containing molysite;
(4) by being placed in containing the organic nanofibers of molysite, tubular react furnace carries out being oxidized, carbonization: the temperature of regulation and control tubular react furnace, rises to 270 DEG C by the temperature of tubular react furnace from room temperature with the programming rate of 1 DEG C/min, and keeps 2h in 270 DEG C; Again heat up, with the programming rate of 5 DEG C/min, the temperature of tubular react furnace is risen to 1000 DEG C from 270 DEG C, then Temperature fall is to room temperature, obtains iron content carbon nano-fiber; Can be abundant through pre-oxidation by heating mode gained fiber of the present invention, the trapezoidal large molecule being convenient to be formed occurs crosslinked. change thick circulus into.The carbon nano-fiber formed after carbonization does not rupture and crosslinking phenomena, and distribution of fiber diameters is narrower, concentrates within the scope of 200-250nm.
The mass percent of polyacrylonitrile in mixed solution is 11%-12%, preferably 11.7%.
The invention has the beneficial effects as follows:
The source of iron predecessor prepared needed for iron-phthalocyanine is directly directly spun in carbon fiber by electrostatic spinning technique by the inventive method, then by solvent thermal process, makes 4-nitro phthalic nitrile and ammonium molybdate, with the source of iron in carbon fiber for core, realizes growth in situ; And tradition prepare metal phthalocyanine fiber heterojunction material method be 4-nitro phthalic nitrile and ammonium molybdate and molysite by solvent thermal process at fiber surface attachment or growth iron-phthalocyanine.The present invention, compared to existing technique, solves preparation technology in prior art loaded down with trivial details, and metal phthalocyanine and fiber are in conjunction with insecure, and surface coverage is wayward, and the reaction time is oversize, and gained catalyst not easily recycling even causes secondary pollution problems.Method advantage after improvement: the 1. strong bonded achieving metal phthalocyanine and carbon fiber, avoids the possibility that part iron-phthalocyanine adheres at fiber surface, fundamentally solves metal phthalocyanine and the caducous problem of carbon fiber interfacial instability; 2. the method can avoid raw-material waste, effectively reduces the waste of molysite; 3. shorten the reaction time, foreshorten to 7-9 hour from traditional 12-32 hour.
Nano wire iron-phthalocyanine/carbon nano-fiber the heterojunction composite utilizing the inventive method to prepare has following advantage: 1. metal phthalocyanine and carbon fiber combine firmly; 2 metal phthalocyanines are unique at the pattern of fiber surface; Very stable heterojunction boundary is formed between 3 iron dust phthalocyanines and carbon fiber.And nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite prepared by the present invention can be used for light catalytic purifying disposes of sewage, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite forms more stable interface between the two, interface cooperative effect can reduce the recombination probability in light induced electron and hole to utilize hetero-junctions to see, improve quantum yield, thus raising photocatalysis efficiency, simultaneously, by the one-dimensional nano structure of material uniqueness, make photochemical catalyst be convenient to recycling, improve the practical of catalysis material.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of nano wire of the present invention iron-phthalocyanine/carbon nano-fiber heterojunction composite.
Fig. 2 is the ESEM enlarged drawing of nano wire of the present invention iron-phthalocyanine/carbon nano-fiber heterojunction composite.
Fig. 3 is the XRD figure of nano wire of the present invention iron-phthalocyanine/carbon nano-fiber heterojunction composite.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
(1) preparation of iron content carbon nano-fiber
1.5g polyacrylonitrile (PAN) and 0.032gFeCl
24H
2o is dissolved in 12mLN, dinethylformamide (DMF), magnetic agitation 24 hours, be stirred to transparent and homogeneous thick after be transferred in 10ml syringe, incite somebody to action and pass through a tubes connection on a metal joint, use traffic controller control mixed solution keep flow velocity at 0.1-10sccm; Use plate electrode, parallel metal plate electrode or rotating drum electrode as collecting electrode, the two poles of the earth of high voltage electrostatic device are connected on metal joint and collecting electrode, the high pressure of 10kV is provided by high voltage electrostatic device, starts spinning, obtain the organic nanofibers containing molysite;
By being placed in containing the organic nanofibers of molysite, tubular react furnace carries out being oxidized, carbonization: the temperature of regulation and control tubular react furnace, rises to 270 DEG C by the temperature of tubular react furnace from room temperature with the programming rate of 1 DEG C/min, and keeps 2h in 270 DEG C; Again heat up, with the programming rate of 5 DEG C/min, the temperature of tubular react furnace is risen to 1000 DEG C from 270 DEG C, then Temperature fall is to room temperature, obtains iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
By 0.100mmol4-nitro phthalic nitrile, 1mg ammonium molybdate and 5mg iron content carbon nano-fiber are together poured in the reactor of 25ml, and rear spent glycol adds to 80% of reactor volume.Reactor good seal is placed in temperature be 160 DEG C constant temperature oven heating 8 hours, take out reactor, Temperature fall is to room temperature.Take out product at the bottom of still after driving still, respectively clean three times respectively with ethanol and distilled water, be then placed in vacuum exsiccator 50 DEG C of dryings 5 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, productive rate is 98%.
Embodiment 2
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.015gFeCl
24H
2o is dissolved in N, dinethylformamide (DMF), controlling the mass percent of polyacrylonitrile in DMF is 11.7%, magnetic agitation 21 hours, be stirred to transparent and homogeneous thick after be transferred in 10ml syringe, incite somebody to action and pass through a tubes connection on a metal joint, use traffic controller control mixed solution keep flow velocity at 5sccm; Use plate electrode, parallel metal plate electrode or rotating drum electrode as collecting electrode, the two poles of the earth of high voltage electrostatic device are connected on metal joint and collecting electrode, the high pressure of 10kV is provided by high voltage electrostatic device, starts spinning, obtain the organic nanofibers containing molysite;
By being placed in containing the organic nanofibers of molysite, tubular react furnace carries out being oxidized, carbonization: the temperature of regulation and control tubular react furnace, rises to 270 DEG C by the temperature of tubular react furnace from room temperature with the programming rate of 1 DEG C/min, and keeps 2h in 270 DEG C; Again heat up, with the programming rate of 5 DEG C/min, the temperature of tubular react furnace is risen to 1000 DEG C from 270 DEG C, then Temperature fall is to room temperature, obtains iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
Get 4-nitro phthalic nitrile that weight ratio is 1.6:1:5, ammonium molybdate, iron content carbon nano-fiber together pour in the reactor of 25mL, rear spent glycol adds to 79% of reactor volume, and the addition of ethanol is 77.8% of reactor volume.Reactor good seal is placed in temperature be 158 DEG C constant temperature oven heating 7.5 hours, take out reactor, Temperature fall is to room temperature.Take out product at the bottom of still after driving still, respectively clean three times respectively with ethanol and distilled water, be then placed in vacuum exsiccator 45 DEG C of dryings 6 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, productive rate is 97.2%.
Embodiment 3
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.045gFeCl
24H
2o is dissolved in N, dinethylformamide (DMF), controlling the mass percent of polyacrylonitrile in DMF is 11.5%, magnetic agitation 23 hours, be stirred to transparent and homogeneous thick after be transferred in 10ml syringe, incite somebody to action and pass through a tubes connection on a metal joint, use traffic controller control mixed solution keep flow velocity at 6sccm; Use plate electrode, parallel metal plate electrode or rotating drum electrode as collecting electrode, the two poles of the earth of high voltage electrostatic device are connected on metal joint and collecting electrode, the high pressure of 10kV is provided by high voltage electrostatic device, starts spinning, obtain the organic nanofibers containing molysite;
By being placed in containing the organic nanofibers of molysite, tubular react furnace carries out being oxidized, carbonization: the temperature of regulation and control tubular react furnace, rises to 270 DEG C by the temperature of tubular react furnace from room temperature with the programming rate of 1 DEG C/min, and keeps 2h in 270 DEG C; Again heat up, with the programming rate of 5 DEG C/min, the temperature of tubular react furnace is risen to 1000 DEG C from 270 DEG C, then Temperature fall is to room temperature, obtains iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
Get 4-nitro phthalic nitrile that weight ratio is 1.8:1:5.5, ammonium molybdate, iron content carbon nano-fiber together pour in the reactor of 25mL, rear spent glycol adds to 79% of reactor volume, and the addition of ethanol is 77.9% of reactor volume.Reactor good seal is placed in temperature be 153 DEG C constant temperature oven heating 8.5 hours, take out reactor, Temperature fall is to room temperature.Take out product at the bottom of still after driving still, respectively clean three times respectively with ethanol and distilled water, be then placed in vacuum exsiccator 55 DEG C of dryings 5.5 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, productive rate is 98.3%.
Embodiment 4
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.028gFeCl
24H
2o is dissolved in N, dinethylformamide (DMF), controlling the mass percent of polyacrylonitrile in DMF is 11.8%, magnetic agitation 22 hours, be stirred to transparent and homogeneous thick after be transferred in 10ml syringe, incite somebody to action and pass through a tubes connection on a metal joint, use traffic controller control mixed solution keep flow velocity at 4sccm; Use plate electrode, parallel metal plate electrode or rotating drum electrode as collecting electrode, the two poles of the earth of high voltage electrostatic device are connected on metal joint and collecting electrode, the high pressure of 10kV is provided by high voltage electrostatic device, starts spinning, obtain the organic nanofibers containing molysite;
By being placed in containing the organic nanofibers of molysite, tubular react furnace carries out being oxidized, carbonization: the temperature of regulation and control tubular react furnace, rises to 270 DEG C by the temperature of tubular react furnace from room temperature with the programming rate of 1 DEG C/min, and keeps 2h in 270 DEG C; Again heat up, with the programming rate of 5 DEG C/min, the temperature of tubular react furnace is risen to 1000 DEG C from 270 DEG C, then Temperature fall is to room temperature, obtains iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
Get 4-nitro phthalic nitrile that weight ratio is 1.7:1:5.1, ammonium molybdate, iron content carbon nano-fiber together pour in the reactor of 25mL, rear spent glycol adds to 79% of reactor volume, and the addition of ethanol is 77.8% of reactor volume.Reactor good seal is placed in temperature be 155 DEG C constant temperature oven heating 8.2 hours, take out reactor, Temperature fall is to room temperature.Take out product at the bottom of still after driving still, respectively clean three times respectively with ethanol and distilled water, be then placed in vacuum exsiccator 53 DEG C of dryings 5.8 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, productive rate is 98.6%.
Embodiment 5
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.03gFeCl
24H
2o is dissolved in N, dinethylformamide (DMF), controlling the mass percent of polyacrylonitrile in DMF is 11.7%, magnetic agitation 24 hours, be stirred to transparent and homogeneous thick after be transferred in 10ml syringe, incite somebody to action and pass through a tubes connection on a metal joint, use traffic controller control mixed solution keep flow velocity at 7sccm; Use plate electrode, parallel metal plate electrode or rotating drum electrode as collecting electrode, the two poles of the earth of high voltage electrostatic device are connected on metal joint and collecting electrode, the high pressure of 10kV is provided by high voltage electrostatic device, starts spinning, obtain the organic nanofibers containing molysite;
By being placed in containing the organic nanofibers of molysite, tubular react furnace carries out being oxidized, carbonization: the temperature of regulation and control tubular react furnace, rises to 270 DEG C by the temperature of tubular react furnace from room temperature with the programming rate of 1 DEG C/min, and keeps 2h in 270 DEG C; Again heat up, with the programming rate of 5 DEG C/min, the temperature of tubular react furnace is risen to 1000 DEG C from 270 DEG C, then Temperature fall is to room temperature, obtains iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
Get 4-nitro phthalic nitrile that weight ratio is 1.73:1:5.2, ammonium molybdate, iron content carbon nano-fiber together pour in the reactor of 25mL, rear spent glycol adds to 79% of reactor volume, and the addition of ethanol is 77.8% of reactor volume.Reactor good seal is placed in temperature be 156 DEG C constant temperature oven heating 8 hours, take out reactor, Temperature fall is to room temperature.Take out product at the bottom of still after driving still, respectively clean three times respectively with ethanol and distilled water, be then placed in vacuum exsiccator 50 DEG C of dryings 5 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, productive rate is 98.7%.
Embodiment 6
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.021gFeCl
24H
2o is dissolved in N, dinethylformamide (DMF), controlling the mass percent of polyacrylonitrile in DMF is 11.3%, magnetic agitation 23.5 hours, be stirred to transparent and homogeneous thick after be transferred in 10ml syringe, incite somebody to action and pass through a tubes connection on a metal joint, use traffic controller control mixed solution keep flow velocity at 8sccm; Use plate electrode, parallel metal plate electrode or rotating drum electrode as collecting electrode, the two poles of the earth of high voltage electrostatic device are connected on metal joint and collecting electrode, the high pressure of 10kV is provided by high voltage electrostatic device, starts spinning, obtain the organic nanofibers containing molysite;
By being placed in containing the organic nanofibers of molysite, tubular react furnace carries out being oxidized, carbonization: the temperature of regulation and control tubular react furnace, rises to 270 DEG C by the temperature of tubular react furnace from room temperature with the programming rate of 1 DEG C/min, and keeps 2h in 270 DEG C; Again heat up, with the programming rate of 5 DEG C/min, the temperature of tubular react furnace is risen to 1000 DEG C from 270 DEG C, then Temperature fall is to room temperature, obtains iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
Get 4-nitro phthalic nitrile that weight ratio is 1.72:1:5.3, ammonium molybdate, iron content carbon nano-fiber together pour in the reactor of 25mL, rear spent glycol adds to 80% of reactor volume, and the addition of ethanol is 77.8% of reactor volume.Reactor good seal is placed in temperature be 152 DEG C constant temperature oven heating 7.8 hours, take out reactor, Temperature fall is to room temperature.Take out product at the bottom of still after driving still, respectively clean three times respectively with ethanol and distilled water, be then placed in vacuum exsiccator 56 DEG C of dryings 5.7 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, productive rate is 97.7%.
Embodiment 7
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.04gFeCl
24H
2o is dissolved in N, dinethylformamide (DMF), controlling the mass percent of polyacrylonitrile in DMF is 11.6%, magnetic agitation 22.5 hours, be stirred to transparent and homogeneous thick after be transferred in 10ml syringe, incite somebody to action and pass through a tubes connection on a metal joint, use traffic controller control mixed solution keep flow velocity at 6sccm; Use plate electrode, parallel metal plate electrode or rotating drum electrode as collecting electrode, the two poles of the earth of high voltage electrostatic device are connected on metal joint and collecting electrode, the high pressure of 10kV is provided by high voltage electrostatic device, starts spinning, obtain the organic nanofibers containing molysite;
By being placed in containing the organic nanofibers of molysite, tubular react furnace carries out being oxidized, carbonization: the temperature of regulation and control tubular react furnace, rises to 270 DEG C by the temperature of tubular react furnace from room temperature with the programming rate of 1 DEG C/min, and keeps 2h in 270 DEG C; Again heat up, with the programming rate of 5 DEG C/min, the temperature of tubular react furnace is risen to 1000 DEG C from 270 DEG C, then Temperature fall is to room temperature, obtains iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
Get 4-nitro phthalic nitrile that weight ratio is 1.71:1:5.1, ammonium molybdate, iron content carbon nano-fiber together pour in the reactor of 25mL, rear spent glycol adds to 80% of reactor volume, and the addition of ethanol is 77.9% of reactor volume.Reactor good seal is placed in temperature be 152 DEG C constant temperature oven heating 8.2 hours, take out reactor, Temperature fall is to room temperature.Take out product at the bottom of still after driving still, respectively clean three times respectively with ethanol and distilled water, be then placed in vacuum exsiccator 58 DEG C of dryings 5.8 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, productive rate is 97.3%.
Embodiment 8
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.018gFeCl
24H
2o is dissolved in N, dinethylformamide (DMF), controlling the mass percent of polyacrylonitrile in DMF is 11.7%, magnetic agitation 22.5 hours, be stirred to transparent and homogeneous thick after be transferred in 10ml syringe, incite somebody to action and pass through a tubes connection on a metal joint, use traffic controller control mixed solution keep flow velocity at 8sccm; Use plate electrode, parallel metal plate electrode or rotating drum electrode as collecting electrode, the two poles of the earth of high voltage electrostatic device are connected on metal joint and collecting electrode, the high pressure of 10kV is provided by high voltage electrostatic device, starts spinning, obtain the organic nanofibers containing molysite;
By being placed in containing the organic nanofibers of molysite, tubular react furnace carries out being oxidized, carbonization: the temperature of regulation and control tubular react furnace, rises to 270 DEG C by the temperature of tubular react furnace from room temperature with the programming rate of 1 DEG C/min, and keeps 2h in 270 DEG C; Again heat up, with the programming rate of 5 DEG C/min, the temperature of tubular react furnace is risen to 1000 DEG C from 270 DEG C, then Temperature fall is to room temperature, obtains iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
Get 4-nitro phthalic nitrile that weight ratio is 1.74:1:5, ammonium molybdate, iron content carbon nano-fiber together pour in the reactor of 25mL, rear spent glycol adds to 80% of reactor volume, and the addition of ethanol is 77.8% of reactor volume.Reactor good seal is placed in temperature be 158 DEG C constant temperature oven heating 7.9 hours, take out reactor, Temperature fall is to room temperature.Take out product at the bottom of still after driving still, respectively clean three times respectively with ethanol and distilled water, be then placed in vacuum exsiccator 54 DEG C of dryings 5.2 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, productive rate is 97.8%.
Embodiment 9
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.025gFeCl
24H
2o is dissolved in N, dinethylformamide (DMF), controlling the mass percent of polyacrylonitrile in DMF is 11.8%, magnetic agitation 24 hours, be stirred to transparent and homogeneous thick after be transferred in 10ml syringe, incite somebody to action and pass through a tubes connection on a metal joint, use traffic controller control mixed solution keep flow velocity at 8sccm; Use plate electrode, parallel metal plate electrode or rotating drum electrode as collecting electrode, the two poles of the earth of high voltage electrostatic device are connected on metal joint and collecting electrode, the high pressure of 10kV is provided by high voltage electrostatic device, starts spinning, obtain the organic nanofibers containing molysite;
By being placed in containing the organic nanofibers of molysite, tubular react furnace carries out being oxidized, carbonization: the temperature of regulation and control tubular react furnace, rises to 270 DEG C by the temperature of tubular react furnace from room temperature with the programming rate of 1 DEG C/min, and keeps 2h in 270 DEG C; Again heat up, with the programming rate of 5 DEG C/min, the temperature of tubular react furnace is risen to 1000 DEG C from 270 DEG C, then Temperature fall is to room temperature, obtains iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
Get 4-nitro phthalic nitrile that weight ratio is 1.75:1:5.1, ammonium molybdate, iron content carbon nano-fiber together pour in the reactor of 25mL, rear spent glycol adds to 80% of reactor volume, and the addition of ethanol is 77.8% of reactor volume.Reactor good seal is placed in temperature be 155 DEG C constant temperature oven heating 8 hours, take out reactor, Temperature fall is to room temperature.Take out product at the bottom of still after driving still, respectively clean three times respectively with ethanol and distilled water, be then placed in vacuum exsiccator 52 DEG C of dryings 4.7 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, productive rate is 97.1%.
Embodiment 10
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.036gFeCl
24H
2o is dissolved in N, dinethylformamide (DMF), controlling the mass percent of polyacrylonitrile in DMF is 11.6%, magnetic agitation 23 hours, be stirred to transparent and homogeneous thick after be transferred in 10ml syringe, incite somebody to action and pass through a tubes connection on a metal joint, use traffic controller control mixed solution keep flow velocity at 8sccm; Use plate electrode, parallel metal plate electrode or rotating drum electrode as collecting electrode, the two poles of the earth of high voltage electrostatic device are connected on metal joint and collecting electrode, the high pressure of 10kV is provided by high voltage electrostatic device, starts spinning, obtain the organic nanofibers containing molysite;
By being placed in containing the organic nanofibers of molysite, tubular react furnace carries out being oxidized, carbonization: the temperature of regulation and control tubular react furnace, rises to 270 DEG C by the temperature of tubular react furnace from room temperature with the programming rate of 1 DEG C/min, and keeps 2h in 270 DEG C; Again heat up, with the programming rate of 5 DEG C/min, the temperature of tubular react furnace is risen to 1000 DEG C from 270 DEG C, then Temperature fall is to room temperature, obtains iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
Get 4-nitro phthalic nitrile that weight ratio is 1.73:1:4.8, ammonium molybdate, iron content carbon nano-fiber together pour in the reactor of 25mL, rear spent glycol adds to 80% of reactor volume, and the addition of ethanol is 77.8% of reactor volume.Reactor good seal is placed in temperature be 156 DEG C constant temperature oven heating 8.3 hours, take out reactor, Temperature fall is to room temperature.Take out product at the bottom of still after driving still, respectively clean three times respectively with ethanol and distilled water, be then placed in vacuum exsiccator 51 DEG C of dryings 5 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, productive rate is 97.6%.
The above-mentioned nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite prepared by this method is scanned, result as shown in Figure 1-2, as can be seen from Figure 1, electrospinning carbon nano-fiber is woven into tridimensional network, and there is diauxic growth thing on surface, in order to more clearly observe heterojunction material pattern, we amplify Fig. 1, as Fig. 2, can be clear that iron-phthalocyanine is immobilized on carbon nano-fiber with nano wire form, and be evenly distributed and reunite.From figure, we also find, do not have independent nucleation or the iron-phthalocyanine nano wire come off around carbon fiber, show thoroughly to solve metal phthalocyanine and the caducous problem of carbon fiber interfacial instability.
In order to carry out thing certification mutually, the above-mentioned nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite prepared by this method is carried out X-ray diffraction, as shown in Figure 3, two kinds of thing phase peaks have been there are in figure, about 2 θ=25 °, wide diffraction maximum is carbon in carbon nano-fiber (002), and 2 θ=11.8 °, 17.7 ° and 27.1 ° is the characteristic diffraction peak of iron-phthalocyanine.Material synthesized by explanation is the composite of iron-phthalocyanine carbon nano-fiber and carbon nano-fiber.
The existing method preparing metal phthalocyanine/electro spinning nano fiber hetero-junctions, the active group mainly utilizing fiber surface to hang and the metal phthalocyanine formed combine, but, fiber surface activity site and electrospinning parameters, and the method close relation of post-processed is correlated with, therefore the Parameters variation preparing metal phthalocyanine/nanofiber heterojunction material method is too many, not easily repeat, reaction time is oversize, the problems such as operating process is more loaded down with trivial details, simultaneously, insecurely even there is attachment phenomenon in what the iron-phthalocyanine formed grew at fiber surface, should not with the transmission of light induced electron.And this method is directly injected in fiber by the source of iron needed for synthesis iron-phthalocyanine by electrostatic spinning technique, to electrospinning fibre without the need to carrying out post-processed, directly allow 4-nitro phthalic nitrile and ammonium molybdate with the source of iron in fiber for reaction site, the growth in situ of iron-phthalocyanine is realized at fiber surface, achieve stable heterojunction boundary firmly, improve the separative efficiency in light induced electron and hole, thus improve photocatalysis efficiency.This method is simple to operate, be easy to manipulation, reaction time is about 1/3 of conventional method, and this method fundamentally solves metal phthalocyanine and the caducous problem of carbon fiber interfacial instability, fiber heterojunction material catalysis material is easy to recycling, solves phthalocyanine in sewage disposal process and comes off and cause the problem of secondary pollution.
Claims (8)
1. the preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, comprise the preparation of iron content carbon nano-fiber and the preparation of composite, it is characterized in that: the preparation of described composite comprises the following steps: iron content carbon nano-fiber, 4-nitro phthalic nitrile and ammonium molybdate are together poured in reactor, then ethylene glycol is added wherein, reactor is sealed, be placed in 150-160 DEG C of baking oven and heat 7-9h, take out reactor, Temperature fall is to room temperature, take out product at the bottom of still, washing, dries, obtains product.
2. the preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite according to claim 1, it is characterized in that, 4-nitro phthalic nitrile: ammonium molybdate: the weight ratio of iron content carbon nano-fiber is (1.6-1.8): 1:(4-6).
3. the preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite according to claim 1, is characterized in that, the total amount of iron content carbon nano-fiber, 4-nitro phthalic nitrile, ammonium molybdate and ethylene glycol is the 78%-80% of reactor volume.
4. the preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite according to claim 1, is characterized in that, during oven dry, the product after washing is placed in the dry 4-6h of vacuum drying box, and bake out temperature is 40-60 DEG C.
5. the preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite according to claim 1, is characterized in that, respectively cleans three times respectively, first wash three times with ethanol, then wash three times with distilled water during washing with ethanol and distilled water.
6. the preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite according to claim 1, it is characterized in that, the preparation of described iron content carbon nano-fiber comprises the following steps: polyacrylonitrile and molysite are dissolved in N, in dinethylformamide, then the organic nanofibers containing molysite is obtained by the method for electrostatic spinning, and then through peroxidating, carbonization treatment, obtain iron content carbon nano-fiber.
7. the preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite according to claim 6, is characterized in that, the concrete steps of the preparation of described iron content carbon nano-fiber are as follows:
(1) be, 1:(0.01-0.03 by mass ratio) polyacrylonitrile and FeCl
24H
2o is dissolved in DMF, and magnetic agitation 20-24h obtains mixed solution;
(2), by mixed solution be transferred in syringe, and by a tubes connection on a metal joint, use traffic controller controls mixed solution and keeps flow velocity at 0.1-10sccm;
(3) use plate electrode, parallel metal plate electrode or rotating drum electrode as collecting electrode, the two poles of the earth of high voltage electrostatic device are connected on metal joint and collecting electrode, the high pressure of 10kV is provided by high voltage electrostatic device, start spinning, obtain the organic nanofibers containing molysite;
(4) by being placed in containing the organic nanofibers of molysite, tubular react furnace carries out being oxidized, carbonization: the temperature of regulation and control tubular react furnace, rises to 270 DEG C by the temperature of tubular react furnace from room temperature with the programming rate of 1 DEG C/min, and keeps 2h in 270 DEG C; Again heat up, with the programming rate of 5 DEG C/min, the temperature of tubular react furnace is risen to 1000 DEG C from 270 DEG C, then Temperature fall is to room temperature, obtains iron content carbon nano-fiber.
8. the preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite according to claim 7, is characterized in that, the mass percent of polyacrylonitrile in mixed solution is 11%-12%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110034232A (en) * | 2019-04-05 | 2019-07-19 | 东北师范大学 | Using FePC as the preparation method and application of the field effect transistor of raw material |
| CN114335885A (en) * | 2021-12-22 | 2022-04-12 | 河北工程大学 | NiPc/PVDF modified PE diaphragm and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1367173A (en) * | 2001-01-21 | 2002-09-04 | 中国科学院感光化学研究所 | Metal phthalocyanine compound, its preparation method and application |
| WO2004018564A1 (en) * | 2002-08-23 | 2004-03-04 | Toppan Printing Co., Ltd. | Resin composition having oxygen-absorbing ability, layered product, and package |
| CN1900411A (en) * | 2006-07-14 | 2007-01-24 | 浙江理工大学 | Metal phthalocyanine loaded fiber with catalytic activity and preparing method |
| CN102569831A (en) * | 2012-03-07 | 2012-07-11 | 东华大学 | Carbon load copper phthalocyanine fuel cell catalyst CuPc/C and preparation method and application thereof |
| CN103721747A (en) * | 2013-12-13 | 2014-04-16 | 浙江理工大学 | Catalytic carbon fibers and preparation method |
-
2016
- 2016-01-15 CN CN201610027863.7A patent/CN105536872B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1367173A (en) * | 2001-01-21 | 2002-09-04 | 中国科学院感光化学研究所 | Metal phthalocyanine compound, its preparation method and application |
| WO2004018564A1 (en) * | 2002-08-23 | 2004-03-04 | Toppan Printing Co., Ltd. | Resin composition having oxygen-absorbing ability, layered product, and package |
| CN1900411A (en) * | 2006-07-14 | 2007-01-24 | 浙江理工大学 | Metal phthalocyanine loaded fiber with catalytic activity and preparing method |
| CN102569831A (en) * | 2012-03-07 | 2012-07-11 | 东华大学 | Carbon load copper phthalocyanine fuel cell catalyst CuPc/C and preparation method and application thereof |
| CN103721747A (en) * | 2013-12-13 | 2014-04-16 | 浙江理工大学 | Catalytic carbon fibers and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 郭增彩: "纳米酞菁及其复合材料的制备与光催化性质研究", 《中国博士学文论文全文数据库 工程科技I辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110034232A (en) * | 2019-04-05 | 2019-07-19 | 东北师范大学 | Using FePC as the preparation method and application of the field effect transistor of raw material |
| CN114335885A (en) * | 2021-12-22 | 2022-04-12 | 河北工程大学 | NiPc/PVDF modified PE diaphragm and preparation method thereof |
| CN114335885B (en) * | 2021-12-22 | 2024-01-26 | 河北工程大学 | NiPc/PVDF modified PE diaphragm and preparation method thereof |
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