CN105536872B - The preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite - Google Patents
The preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite Download PDFInfo
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- CN105536872B CN105536872B CN201610027863.7A CN201610027863A CN105536872B CN 105536872 B CN105536872 B CN 105536872B CN 201610027863 A CN201610027863 A CN 201610027863A CN 105536872 B CN105536872 B CN 105536872B
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 98
- 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
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- 239000002070 nanowire Substances 0.000 title claims abstract description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 113
- 229910052742 iron Inorganic materials 0.000 claims abstract description 56
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 25
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 20
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 19
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 19
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 150000002825 nitriles Chemical class 0.000 claims abstract description 18
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims abstract description 4
- 238000001291 vacuum drying Methods 0.000 claims abstract description 3
- 239000002184 metal Substances 0.000 claims description 52
- 229910052751 metal Inorganic materials 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 33
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 29
- 239000002121 nanofiber Substances 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 12
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000009987 spinning Methods 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000010041 electrostatic spinning Methods 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 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 18
- 239000000835 fiber Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- 229920000049 Carbon (fiber) Polymers 0.000 description 12
- 239000004917 carbon fiber Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 10
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 10
- 206010013786 Dry skin Diseases 0.000 description 6
- 238000001523 electrospinning Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 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
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical group N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000010865 sewage Substances 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
- 239000002023 wood Substances 0.000 description 2
- IYZPEGVSBUNMBE-UHFFFAOYSA-N 2-[[5-[1-[3-[[carboxylatomethyl(carboxymethyl)azaniumyl]methyl]-4-hydroxy-5-methylphenyl]-3-oxo-2-benzofuran-1-yl]-2-hydroxy-3-methylphenyl]methyl-(carboxymethyl)azaniumyl]acetate Chemical compound OC(=O)CN(CC(O)=O)CC1=C(O)C(C)=CC(C2(C3=CC=CC=C3C(=O)O2)C=2C=C(CN(CC(O)=O)CC(O)=O)C(O)=C(C)C=2)=C1 IYZPEGVSBUNMBE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process 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
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 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
- 238000012805 post-processing Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 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
- B01J31/16—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
-
- B01J35/39—
-
- B01J35/58—
Abstract
The preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, belong to the technical field of composite, including the preparation of iron content carbon nano-fiber and the preparation of composite, the preparation of the composite comprise the following steps：Iron content carbon nano-fiber, 4 nitro phthalic nitriles and ammonium molybdate are together poured into reactor, then ethylene glycol is added thereto, reactor is sealed, it is placed in baking oven and heats 7 9h, reactor is taken out, is naturally cooling to room temperature, takes out bottom reaction product, it is placed in after washing in vacuum drying box and dries 4 6h, obtains product.Method preparation technology provided by the present invention is succinct, be a kind of efficient operation it is easy, it is cheap, environment-friendly, be easy to large-scale production.
Description
Technical field
The invention belongs to the technical field of composite, is related to nano wire iron-phthalocyanine/carbon nano-fiber hetero-junctions composite wood
Material, and in particular to the preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite.
Background technology
Metal phthalocyanine is many transition gold of such as iron, cobalt, nickel that hole can accommodate that diameter therewith matches in a kind of ring
The macrocyclic complex of category, phthalocyanine ring are the big two-dimentional conjugated system with 18 pi-electrons in itself, as a kind of macrocyclic complex,
Because it in the visible region of the length more than 400nm has stronger absworption peak by the extensive concern of researchers, it is considered as
It is one of visible light catalyst for most having exploitation potential quality, can thus utilizes solar energy processing effluent problem.Photocatalysis
Light induced electron and the separating effect in hole are depended primarily on, it is more using structure to improve the visible light catalytic efficiency of metal phthalocyanine
Heterojunction material, generally the material with metal phthalocyanine structure hetero-junctions is metal oxide semiconductor, however, its capture and transmission
Light induced electron it is limited in one's ability.Therefore, it is compound with the electrospinning carbon nano-fiber of superpower electron transport ability, can be to a certain extent
Strengthen the transmission campaign of electronics, reduce light induced electron and the recombination probability in hole.
However, organic crystal is typically difficult to grow up, the method that metal phthalocyanine and carbon fibre composite use generally is prepared
It is to disperse metal phthalocyanine and the carbon fiber after thionyl chloride is handled in organic solvent, drying is transferred to metal phthalocyanine
On carbon fiber.This preparation method is usually relatively complex, product yield is relatively low, is mainly manifested in connecing for metal phthalocyanine and carbon fiber
Loose in the degree of touching, even physical attachment is on carbon fiber, it is difficult to forms good hetero-junctions, is unfavorable for catching for light induced electron
Obtain and transmit.
The content of the invention
A kind of the defects of present invention is solves in the prior art, there is provided nano wire iron-phthalocyanine/carbon nano-fiber hetero-junctions
The preparation method of composite, method preparation technology provided by the present invention is succinct, is that a kind of efficient operation is easy, price is low
It is honest and clean, environment-friendly, be easy to large-scale production.
The present invention is to realize that the technical scheme that its purpose uses is：
The preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, including iron content carbon nano-fiber
Prepare and the preparation of composite, the preparation of the composite comprise the following steps：Iron content carbon nano-fiber, 4- nitros is adjacent
Benzene dinitrile and ammonium molybdate are together poured into reactor, then add ethylene glycol thereto, and reactor is sealed, and are placed in 150-160
Heat 7-9h in DEG C baking oven, take out reactor, be naturally cooling to room temperature, take out bottom reaction product, wash, drying, obtain
To product.
4- nitro phthalic nitriles：Ammonium molybdate：The weight ratio of iron content carbon nano-fiber is (1.6-1.8):1:(4-6).
Iron content carbon nano-fiber, 4- nitros phthalic nitrile, the 78%- that the total amount of ammonium molybdate and ethylene glycol is reactor volume
80%.The dosage of further ethylene glycol is 75% ＜ V of reactor volumeEthylene glycol＜ 78%.
During drying, the reaction product after washing is placed in vacuum drying box and dries 4-6h, drying temperature is 40-60 DEG C.
With ethanol and distilled water, respectively cleaning three times, first wash three times with ethanol respectively during washing, then with distilling water washing three
It is secondary.
The preparation of the iron content carbon nano-fiber comprises the following steps：Polyacrylonitrile and molysite are dissolved in N, N- dimethyl methyls
In acid amides, the organic nanofibers containing molysite are then obtained by the method for electrostatic spinning, then again through peroxidating, carbonization at
Reason, obtains iron content carbon nano-fiber.
The preparation of the iron content carbon nano-fiber comprises the following steps that：
(1) it is, 1 by mass ratio：The polyacrylonitrile and FeCl of (0.01-0.03)2·4H2O is dissolved in DMF
In, magnetic agitation 20-24h, obtain mixed solution；
(2), mixed solution is transferred in syringe, and is connected to by a conduit on a metal joint, uses flow
Controller control mixed solution keeps flow velocity in 0.1-10sccm；
(3) plate electrode, parallel metal plate electrode or rotatable drum electrode are used as receiving electrode, by high pressure
The two poles of the earth of electrostatic device are connected on metal joint and receiving electrode, and 10kV high pressure is provided by high voltage electrostatic device, are started
Spinning, obtain the organic nanofibers containing molysite；
(4) organic nanofibers containing molysite are placed in pipe reaction stove and are aoxidized, be carbonized：Regulate and control tubular type reacting furnace
Temperature, the temperature of pipe reaction stove is risen to 270 DEG C from room temperature with 1 DEG C/min programming rate, and 2h are kept in 270 DEG C；
Heat up again, the temperature of pipe reaction stove is risen to 1000 DEG C from 270 DEG C with 5 DEG C/min programming rate, then Temperature fall
To room temperature, iron content carbon nano-fiber is obtained；Fiber can pass through pre-oxidation fully as obtained by the heating mode of the present invention, be easy to
The trapezoidal macromolecular formed crosslinks and is changed into thick cyclic structure.The carbon nano-fiber formed after carbonization not be broken and
Crosslinking phenomena, distribution of fiber diameters is narrower, concentrates in the range of 200-250nm.
Mass percent of the polyacrylonitrile in mixed solution is 11%-12%, preferably 11.7%.
The beneficial effects of the invention are as follows：
The source of iron predecessor prepared needed for iron-phthalocyanine is directly directly spun into by the inventive method by electrostatic spinning technique
In carbon fiber, then by solvent thermal process, make 4- nitros phthalic nitrile and ammonium molybdate, using the source of iron in carbon fiber as core,
Realize growth in situ；And it is 4- nitros phthalic nitrile and ammonium molybdate and iron that tradition, which prepares metal phthalocyanine fiber heterojunction material method,
Salt adheres to or grown iron-phthalocyanine by solvent thermal process in fiber surface.The present invention solves existing compared to existing technique
Preparation technology is cumbersome in technology, and metal phthalocyanine and fiber combine insecure, and surface coverage is difficult to control, and the reaction time is oversize,
Gained catalyst is not easily recycled recycling or even causes secondary pollution problems.Method advantage after improvement：1. realize metal
The strong bonded of phthalocyanine and carbon fiber, the possibility that part iron-phthalocyanine adheres in fiber surface is avoided, fundamentally solves metal
Phthalocyanine and the caducous problem of carbon fiber interfacial instability；2. this method can avoid the waste of raw material, molysite is effectively reduced
Waste；3. shortening the reaction time, 7-9 hours are foreshortened to from traditional 12-32 hours.
Nano wire iron-phthalocyanine/carbon nano-fiber the heterojunction composite prepared using the inventive method has following excellent
Gesture：1. metal phthalocyanine and carbon fiber are firmly combined with；2 metal phthalocyanines are unique in the pattern of fiber surface；3 iron dust phthalocyanines and carbon fiber
Between form extremely stable heterojunction boundary.And nano wire iron-phthalocyanine/carbon nano-fiber hetero-junctions composite wood prepared by the present invention
Material can be used for light catalytic purifying processing sewage, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite formed between the two compared with
Stable interface, see that interface cooperative effect can reduce light induced electron and the recombination probability in hole using hetero-junctions, improve light quantum
Yield, so as to improve photocatalysis efficiency, meanwhile, by the unique one-dimensional nano structure of material so that photochemical catalyst is easy to reclaim
Recycle, improve the practical of catalysis material.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite of the present invention.
Fig. 2 is the ESEM enlarged drawing of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite of the present invention.
Fig. 3 is the XRD of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite of the present invention.
Embodiment
With reference to specific embodiment, the present invention is further illustrated.
Embodiment 1
(1) preparation of iron content carbon nano-fiber
1.5g polyacrylonitrile (PAN) and 0.032g FeCl2·4H2O is dissolved in 12mL DMFs (DMF), magnetic
Power stir 24 hours, stir to transparent and homogeneous it is thick after be transferred in 10ml syringes, will simultaneously be connected to one by a conduit
On metal joint, flow velocity is kept in 0.1-10sccm using flow controller control mixed solution；Use plate electrode, parallel gold
Belong to plate electrode or rotatable drum electrode as receiving electrode, the two poles of the earth of high voltage electrostatic device are connected to metal joint
On receiving electrode, 10kV high pressure is provided by high voltage electrostatic device, starts spinning, obtains the organic nanofibers containing molysite；
Organic nanofibers containing molysite are placed in pipe reaction stove and is aoxidized, is carbonized：Regulate and control tubular type reacting furnace
Temperature, the temperature of pipe reaction stove is risen to 270 DEG C from room temperature with 1 DEG C/min programming rate, and 2h is kept in 270 DEG C；Again
Secondary heating, the temperature of pipe reaction stove is risen to 1000 DEG C from 270 DEG C with 5 DEG C/min programming rate, is then naturally cooling to
Room temperature, obtain iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
By 0.100mmol4- nitro phthalic nitriles, 1mg ammonium molybdates and 5mg iron content carbon nano-fiber together pour into 25ml's
In reactor, rear spent glycol adds to the 80% of reactor volume.Reactor good seal is placed in into the constant temperature that temperature is 160 DEG C to dry
Heated 8 hours in case, take out reactor, be naturally cooling to room temperature.Bottom reaction product is taken out after driving kettle, respectively with ethanol and steaming
Respectively cleaning three times, is subsequently placed in vacuum exsiccator 50 DEG C of dryings 5 hours, nano wire iron-phthalocyanine/carbon nano-fiber is heterogeneous to distilled water
Tie composite, yield 98%.
Embodiment 2
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.015g FeCl2·4H2O is dissolved in DMF (DMF), control
Mass percent of the polyacrylonitrile in DMF be 11.7%, magnetic agitation 21 hours, stir to transparent and homogeneous it is thick after be transferred to
It into 10ml syringes, and will be connected on a metal joint by a conduit, protected using flow controller control mixed solution
Flow velocity is held in 5sccm；, will using plate electrode, parallel metal plate electrode or rotatable drum electrode as receiving electrode
The two poles of the earth of high voltage electrostatic device are connected on metal joint and receiving electrode, and 10kV high pressure is provided by high voltage electrostatic device,
Start spinning, obtain the organic nanofibers containing molysite；
Organic nanofibers containing molysite are placed in pipe reaction stove and is aoxidized, is carbonized：Regulate and control tubular type reacting furnace
Temperature, the temperature of pipe reaction stove is risen to 270 DEG C from room temperature with 1 DEG C/min programming rate, and 2h is kept in 270 DEG C；Again
Secondary heating, the temperature of pipe reaction stove is risen to 1000 DEG C from 270 DEG C with 5 DEG C/min programming rate, is then naturally cooling to
Room temperature, obtain iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
It is 1.6 to take weight ratio:1:5 4- nitros phthalic nitrile, ammonium molybdate, iron content carbon nano-fiber together pour into 25mL's
In reactor, rear spent glycol adds to the 79% of reactor volume, and the addition of ethanol is the 77.8% of reactor volume.Will be anti-
Answer kettle good seal to be placed in the constant temperature oven that temperature is 158 DEG C to heat 7.5 hours, take out reactor, be naturally cooling to room temperature.Open
Bottom reaction product is taken out after kettle, respectively with ethanol and distilled water respectively cleaning three times, be subsequently placed in vacuum exsiccator 45 DEG C it is dry
Dry 6 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, yield 97.2%.
Embodiment 3
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.045g FeCl2·4H2O is dissolved in DMF (DMF), control
Mass percent of the polyacrylonitrile in DMF be 11.5%, magnetic agitation 23 hours, stir to transparent and homogeneous it is thick after be transferred to
It into 10ml syringes, and will be connected on a metal joint by a conduit, protected using flow controller control mixed solution
Flow velocity is held in 6sccm；, will using plate electrode, parallel metal plate electrode or rotatable drum electrode as receiving electrode
The two poles of the earth of high voltage electrostatic device are connected on metal joint and receiving electrode, and 10kV high pressure is provided by high voltage electrostatic device,
Start spinning, obtain the organic nanofibers containing molysite；
Organic nanofibers containing molysite are placed in pipe reaction stove and is aoxidized, is carbonized：Regulate and control tubular type reacting furnace
Temperature, the temperature of pipe reaction stove is risen to 270 DEG C from room temperature with 1 DEG C/min programming rate, and 2h is kept in 270 DEG C；Again
Secondary heating, the temperature of pipe reaction stove is risen to 1000 DEG C from 270 DEG C with 5 DEG C/min programming rate, is then naturally cooling to
Room temperature, obtain iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
It is 1.8 to take weight ratio:1:5.5 4- nitros phthalic nitrile, ammonium molybdate, iron content carbon nano-fiber together pour into 25mL
Reactor in, rear spent glycol adds to the 79% of reactor volume, and the addition of ethanol is the 77.9% of reactor volume.Will
Reactor good seal is placed in the constant temperature oven that temperature is 153 DEG C and heated 8.5 hours, takes out reactor, is naturally cooling to room temperature.
Bottom reaction product is taken out after driving kettle, respectively cleaning three times, is subsequently placed in vacuum exsiccator 55 DEG C with ethanol and distilled water respectively
Dry 5.5 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, yield 98.3%.
Embodiment 4
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.028g FeCl2·4H2O is dissolved in DMF (DMF), control
Mass percent of the polyacrylonitrile in DMF be 11.8%, magnetic agitation 22 hours, stir to transparent and homogeneous it is thick after be transferred to
It into 10ml syringes, and will be connected on a metal joint by a conduit, protected using flow controller control mixed solution
Flow velocity is held in 4sccm；, will using plate electrode, parallel metal plate electrode or rotatable drum electrode as receiving electrode
The two poles of the earth of high voltage electrostatic device are connected on metal joint and receiving electrode, and 10kV high pressure is provided by high voltage electrostatic device,
Start spinning, obtain the organic nanofibers containing molysite；
Organic nanofibers containing molysite are placed in pipe reaction stove and is aoxidized, is carbonized：Regulate and control tubular type reacting furnace
Temperature, the temperature of pipe reaction stove is risen to 270 DEG C from room temperature with 1 DEG C/min programming rate, and 2h is kept in 270 DEG C；Again
Secondary heating, the temperature of pipe reaction stove is risen to 1000 DEG C from 270 DEG C with 5 DEG C/min programming rate, is then naturally cooling to
Room temperature, obtain iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
It is 1.7 to take weight ratio:1:5.1 4- nitros phthalic nitrile, ammonium molybdate, iron content carbon nano-fiber together pour into 25mL
Reactor in, rear spent glycol adds to the 79% of reactor volume, and the addition of ethanol is the 77.8% of reactor volume.Will
Reactor good seal is placed in the constant temperature oven that temperature is 155 DEG C and heated 8.2 hours, takes out reactor, is naturally cooling to room temperature.
Bottom reaction product is taken out after driving kettle, respectively cleaning three times, is subsequently placed in vacuum exsiccator 53 DEG C with ethanol and distilled water respectively
Dry 5.8 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, yield 98.6%.
Embodiment 5
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.03g FeCl2·4H2O is dissolved in DMF (DMF), and control is poly-
Mass percent of the acrylonitrile in DMF be 11.7%, magnetic agitation 24 hours, stir to transparent and homogeneous it is thick after be transferred to
It in 10ml syringes, and will be connected on a metal joint by a conduit, kept using flow controller control mixed solution
Flow velocity is in 7sccm；Using plate electrode, parallel metal plate electrode or rotatable drum electrode as receiving electrode, by height
The two poles of the earth of pressure electrostatic device are connected on metal joint and receiving electrode, and 10kV high pressure is provided by high voltage electrostatic device, is opened
Beginning spinning, obtain the organic nanofibers containing molysite；
Organic nanofibers containing molysite are placed in pipe reaction stove and is aoxidized, is carbonized：Regulate and control tubular type reacting furnace
Temperature, the temperature of pipe reaction stove is risen to 270 DEG C from room temperature with 1 DEG C/min programming rate, and 2h is kept in 270 DEG C；Again
Secondary heating, the temperature of pipe reaction stove is risen to 1000 DEG C from 270 DEG C with 5 DEG C/min programming rate, is then naturally cooling to
Room temperature, obtain iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
It is 1.73 to take weight ratio:1:5.2 4- nitros phthalic nitrile, ammonium molybdate, iron content carbon nano-fiber together pour into
In 25mL reactor, rear spent glycol adds to the 79% of reactor volume, and the addition of ethanol is reactor volume
77.8%.Reactor good seal is placed in the constant temperature oven that temperature is 156 DEG C and heated 8 hours, takes out reactor, Temperature fall
To room temperature.Bottom reaction product is taken out after driving kettle, respectively cleaning three times, is subsequently placed in vacuum exsiccator with ethanol and distilled water respectively
In 50 DEG C of dryings 5 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, yield 98.7%.
Embodiment 6
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.021g FeCl2·4H2O is dissolved in DMF (DMF), control
Mass percent of the polyacrylonitrile in DMF is 11.3%, magnetic agitation 23.5 hours, stirs to transparent and homogeneous thick rear turn
Enter into 10ml syringes, will and be connected to by a conduit on a metal joint, mixed solution is controlled using flow controller
Flow velocity is kept in 8sccm；Using plate electrode, parallel metal plate electrode or rotatable drum electrode as receiving electrode,
The two poles of the earth of high voltage electrostatic device are connected on metal joint and receiving electrode, 10kV height is provided by high voltage electrostatic device
Pressure, start spinning, obtain the organic nanofibers containing molysite；
Organic nanofibers containing molysite are placed in pipe reaction stove and is aoxidized, is carbonized：Regulate and control tubular type reacting furnace
Temperature, the temperature of pipe reaction stove is risen to 270 DEG C from room temperature with 1 DEG C/min programming rate, and 2h is kept in 270 DEG C；Again
Secondary heating, the temperature of pipe reaction stove is risen to 1000 DEG C from 270 DEG C with 5 DEG C/min programming rate, is then naturally cooling to
Room temperature, obtain iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
It is 1.72 to take weight ratio:1:5.3 4- nitros phthalic nitrile, ammonium molybdate, iron content carbon nano-fiber together pour into
In 25mL reactor, rear spent glycol adds to the 80% of reactor volume, and the addition of ethanol is reactor volume
77.8%.Reactor good seal is placed in the constant temperature oven that temperature is 152 DEG C and heated 7.8 hours, takes out reactor, is dropped naturally
Warm to room temperature.Bottom reaction product is taken out after driving kettle, respectively cleaning three times, is subsequently placed in the dry baking of vacuum with ethanol and distilled water respectively
56 DEG C of dryings 5.7 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, yield 97.7% in case.
Embodiment 7
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.04g FeCl2·4H2O is dissolved in DMF (DMF), and control is poly-
Mass percent of the acrylonitrile in DMF be 11.6%, magnetic agitation 22.5 hours, stir to transparent and homogeneous it is thick after be transferred to
It into 10ml syringes, and will be connected on a metal joint by a conduit, protected using flow controller control mixed solution
Flow velocity is held in 6sccm；, will using plate electrode, parallel metal plate electrode or rotatable drum electrode as receiving electrode
The two poles of the earth of high voltage electrostatic device are connected on metal joint and receiving electrode, and 10kV high pressure is provided by high voltage electrostatic device,
Start spinning, obtain the organic nanofibers containing molysite；
Organic nanofibers containing molysite are placed in pipe reaction stove and is aoxidized, is carbonized：Regulate and control tubular type reacting furnace
Temperature, the temperature of pipe reaction stove is risen to 270 DEG C from room temperature with 1 DEG C/min programming rate, and 2h is kept in 270 DEG C；Again
Secondary heating, the temperature of pipe reaction stove is risen to 1000 DEG C from 270 DEG C with 5 DEG C/min programming rate, is then naturally cooling to
Room temperature, obtain iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
It is 1.71 to take weight ratio:1:5.1 4- nitros phthalic nitrile, ammonium molybdate, iron content carbon nano-fiber together pour into
In 25mL reactor, rear spent glycol adds to the 80% of reactor volume, and the addition of ethanol is reactor volume
77.9%.Reactor good seal is placed in the constant temperature oven that temperature is 152 DEG C and heated 8.2 hours, takes out reactor, is dropped naturally
Warm to room temperature.Bottom reaction product is taken out after driving kettle, respectively cleaning three times, is subsequently placed in the dry baking of vacuum with ethanol and distilled water respectively
58 DEG C of dryings 5.8 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, yield 97.3% in case.
Embodiment 8
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.018g FeCl2·4H2O is dissolved in DMF (DMF), control
Mass percent of the polyacrylonitrile in DMF is 11.7%, magnetic agitation 22.5 hours, stirs to transparent and homogeneous thick rear turn
Enter into 10ml syringes, will and be connected to by a conduit on a metal joint, mixed solution is controlled using flow controller
Flow velocity is kept in 8sccm；Using plate electrode, parallel metal plate electrode or rotatable drum electrode as receiving electrode,
The two poles of the earth of high voltage electrostatic device are connected on metal joint and receiving electrode, 10kV height is provided by high voltage electrostatic device
Pressure, start spinning, obtain the organic nanofibers containing molysite；
Organic nanofibers containing molysite are placed in pipe reaction stove and is aoxidized, is carbonized：Regulate and control tubular type reacting furnace
Temperature, the temperature of pipe reaction stove is risen to 270 DEG C from room temperature with 1 DEG C/min programming rate, and 2h is kept in 270 DEG C；Again
Secondary heating, the temperature of pipe reaction stove is risen to 1000 DEG C from 270 DEG C with 5 DEG C/min programming rate, is then naturally cooling to
Room temperature, obtain iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
It is 1.74 to take weight ratio:1:5 4- nitros phthalic nitrile, ammonium molybdate, iron content carbon nano-fiber together pour into 25mL
Reactor in, rear spent glycol adds to the 80% of reactor volume, and the addition of ethanol is the 77.8% of reactor volume.Will
Reactor good seal is placed in the constant temperature oven that temperature is 158 DEG C and heated 7.9 hours, takes out reactor, is naturally cooling to room temperature.
Bottom reaction product is taken out after driving kettle, respectively cleaning three times, is subsequently placed in vacuum exsiccator 54 DEG C with ethanol and distilled water respectively
Dry 5.2 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, yield 97.8%.
Embodiment 9
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.025g FeCl2·4H2O is dissolved in DMF (DMF), control
Mass percent of the polyacrylonitrile in DMF be 11.8%, magnetic agitation 24 hours, stir to transparent and homogeneous it is thick after be transferred to
It into 10ml syringes, and will be connected on a metal joint by a conduit, protected using flow controller control mixed solution
Flow velocity is held in 8sccm；, will using plate electrode, parallel metal plate electrode or rotatable drum electrode as receiving electrode
The two poles of the earth of high voltage electrostatic device are connected on metal joint and receiving electrode, and 10kV high pressure is provided by high voltage electrostatic device,
Start spinning, obtain the organic nanofibers containing molysite；
Organic nanofibers containing molysite are placed in pipe reaction stove and is aoxidized, is carbonized：Regulate and control tubular type reacting furnace
Temperature, the temperature of pipe reaction stove is risen to 270 DEG C from room temperature with 1 DEG C/min programming rate, and 2h is kept in 270 DEG C；Again
Secondary heating, the temperature of pipe reaction stove is risen to 1000 DEG C from 270 DEG C with 5 DEG C/min programming rate, is then naturally cooling to
Room temperature, obtain iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
It is 1.75 to take weight ratio:1:5.1 4- nitros phthalic nitrile, ammonium molybdate, iron content carbon nano-fiber together pour into
In 25mL reactor, rear spent glycol adds to the 80% of reactor volume, and the addition of ethanol is reactor volume
77.8%.Reactor good seal is placed in the constant temperature oven that temperature is 155 DEG C and heated 8 hours, takes out reactor, Temperature fall
To room temperature.Bottom reaction product is taken out after driving kettle, respectively cleaning three times, is subsequently placed in vacuum exsiccator with ethanol and distilled water respectively
In 52 DEG C of dryings 4.7 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, yield 97.1%.
Embodiment 10
(1) preparation of iron content carbon nano-fiber
By 1.5g polyacrylonitrile (PAN) and 0.036g FeCl2·4H2O is dissolved in DMF (DMF), control
Mass percent of the polyacrylonitrile in DMF be 11.6%, magnetic agitation 23 hours, stir to transparent and homogeneous it is thick after be transferred to
It into 10ml syringes, and will be connected on a metal joint by a conduit, protected using flow controller control mixed solution
Flow velocity is held in 8sccm；, will using plate electrode, parallel metal plate electrode or rotatable drum electrode as receiving electrode
The two poles of the earth of high voltage electrostatic device are connected on metal joint and receiving electrode, and 10kV high pressure is provided by high voltage electrostatic device,
Start spinning, obtain the organic nanofibers containing molysite；
Organic nanofibers containing molysite are placed in pipe reaction stove and is aoxidized, is carbonized：Regulate and control tubular type reacting furnace
Temperature, the temperature of pipe reaction stove is risen to 270 DEG C from room temperature with 1 DEG C/min programming rate, and 2h is kept in 270 DEG C；Again
Secondary heating, the temperature of pipe reaction stove is risen to 1000 DEG C from 270 DEG C with 5 DEG C/min programming rate, is then naturally cooling to
Room temperature, obtain iron content carbon nano-fiber.
(2) preparation of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite
It is 1.73 to take weight ratio:1:4.8 4- nitros phthalic nitrile, ammonium molybdate, iron content carbon nano-fiber together pour into
In 25mL reactor, rear spent glycol adds to the 80% of reactor volume, and the addition of ethanol is reactor volume
77.8%.Reactor good seal is placed in the constant temperature oven that temperature is 156 DEG C and heated 8.3 hours, takes out reactor, is dropped naturally
Warm to room temperature.Bottom reaction product is taken out after driving kettle, respectively cleaning three times, is subsequently placed in the dry baking of vacuum with ethanol and distilled water respectively
51 DEG C of dryings 5 hours, nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, yield 97.6% in case.
The above-mentioned nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite prepared by this method is scanned, tied
Fruit as shown in Figure 1-2, from figure 1 it appears that electrospinning carbon nano-fiber is woven into tridimensional network, and surface have it is secondary
Growth-gen, in order to more clearly observe heterojunction material pattern, we are exaggerated to Fig. 1, such as Fig. 2, can be clear from
See that iron-phthalocyanine is immobilized on carbon nano-fiber with nanometer line morphology, and be evenly distributed and do not reunite.We also send out from figure
It is existing, the iron-phthalocyanine nano wire for not having independent nucleation around carbon fiber or coming off, show thoroughly to solve metal phthalocyanine and carbon is fine
Tie up the caducous problem of interfacial instability.
In order to carry out thing mutually certification, the above-mentioned nano wire iron-phthalocyanine/carbon nano-fiber hetero-junctions prepared by this method is answered
Condensation material carries out X-ray diffraction, as shown in figure 3, occurring two kinds of thing phase peaks in figure, in 2 θ=25 ° or so, wide diffraction maximum is
(002) of carbon in carbon nano-fiber, and 2 θ=11.8 °, 17.7 ° and 27.1 ° be iron-phthalocyanine characteristic diffraction peak.Synthesized by explanation
Material be iron-phthalocyanine carbon nano-fiber and carbon nano-fiber composite.
The existing method for preparing metal phthalocyanine/electro spinning nano fiber hetero-junctions, the work mainly hung using fiber surface
Property group is combined with the metal phthalocyanine formed, however, fiber surface activity site and electrospinning parameters, and the later stage
The method close relation of processing is related, therefore the Parameters variation for preparing metal phthalocyanine/nanofiber heterojunction material method is too many,
It is not easy to repeat, the problems such as reaction time is oversize, and operating process is cumbersome, meanwhile, the iron-phthalocyanine formed grows in fiber surface
It is insecure in addition there is attachment phenomenon, should not be with the transmission of light induced electron.And this method is the iron needed for by synthesis iron-phthalocyanine
Source is directly injected into fiber by electrostatic spinning technique, and post-processing need not be carried out to electrospinning fibre, directly allows 4- nitros adjacent
Benzene dinitrile and ammonium molybdate realize the growth in situ of iron-phthalocyanine using the source of iron in fiber as reaction site, in fiber surface, realize
Stable and firm heterojunction boundary, the separative efficiency in light induced electron and hole is improved, so as to improve photocatalysis efficiency.We
Method is simple to operate, is easily manipulated, and the reaction time is 1/3 or so of conventional method, and this method fundamentally solves metal phthalein
Cyanines and the caducous problem of carbon fiber interfacial instability, fiber heterojunction material catalysis material are easily recycled, and are solved
Phthalocyanine comes off the problem of causing secondary pollution in sewage disposal process.
Claims (7)
1. the preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite, include the system of iron content carbon nano-fiber
The standby and preparation of composite, it is characterised in that：The preparation of the composite comprises the following steps：By iron content carbon Nanowire
Dimension, 4- nitros phthalic nitrile and ammonium molybdate are together poured into reactor, then add ethylene glycol thereto, reactor is sealed,
It is placed in 150-160 DEG C of baking oven and heats 7-9h, take out reactor, be naturally cooling to room temperature, takes out bottom reaction product, wash
Wash, dry, obtain product；
The preparation of the iron content carbon nano-fiber comprises the following steps：Polyacrylonitrile and molysite are dissolved in DMF
In, the organic nanofibers containing molysite are then obtained by the method for electrostatic spinning, then obtained again through peroxidating, carbonization treatment
To iron content carbon nano-fiber；Iron is firmly fixed on carbon nano-fiber in the iron content carbon nano-fiber, turns into form iron-phthalocyanine
Anchor point.
2. the preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite according to claim 1, it is special
Sign is, 4- nitro phthalic nitriles：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, it is special
Sign is, iron content carbon nano-fiber, 4- nitros phthalic nitrile, the 78%- that the total amount of ammonium molybdate and ethylene glycol is reactor volume
80%.
4. the preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite according to claim 1, it is special
Sign is, during drying, the reaction product after washing is placed in vacuum drying box and dries 4-6h, drying temperature is 40-60 DEG C.
5. the preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite according to claim 1, it is special
Sign is, with ethanol and distilled water, respectively cleaning three times, first wash three times with ethanol respectively during washing, then with distilling water washing three
It is secondary.
6. the preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite according to claim 1, it is special
Sign is that the preparation of the iron content carbon nano-fiber comprises the following steps that：
(1) it is, 1 by mass ratio：The polyacrylonitrile and FeCl of (0.01-0.03)2·4H2O is dissolved in DMF,
Magnetic agitation 20-24h, obtains mixed solution；
(2), mixed solution is transferred in syringe, and is connected to by a conduit on a metal joint, is controlled using flow
Device control mixed solution keeps flow velocity in 0.1-10sccm；
(3) plate electrode, parallel metal plate electrode or rotatable drum electrode are used as receiving electrode, by high-pressure electrostatic
The two poles of the earth of device are connected on metal joint and receiving electrode, and 10kV high pressure is provided by high voltage electrostatic device, start spinning,
Obtain the organic nanofibers containing molysite；
(4) organic nanofibers containing molysite are placed in pipe reaction stove and are aoxidized, be carbonized：Regulate and control the temperature of tubular type reacting furnace
Degree, the temperature of pipe reaction stove is risen to 270 DEG C from room temperature with 1 DEG C/min programming rate, and 2h is kept in 270 DEG C；Again
Heating, rises to 1000 DEG C from 270 DEG C by the temperature of pipe reaction stove with 5 DEG C/min programming rate, is then naturally cooling to room
Temperature, obtain iron content carbon nano-fiber.
7. the preparation method of nano wire iron-phthalocyanine/carbon nano-fiber heterojunction composite according to claim 6, it is special
Sign is that mass percent of the polyacrylonitrile in mixed solution is 11%-12%.
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