CN106835364A - A kind of preparation method of the carbon nano-fiber composite material of load iron-copper bi-metal in situ - Google Patents
A kind of preparation method of the carbon nano-fiber composite material of load iron-copper bi-metal in situ Download PDFInfo
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- CN106835364A CN106835364A CN201710044098.4A CN201710044098A CN106835364A CN 106835364 A CN106835364 A CN 106835364A CN 201710044098 A CN201710044098 A CN 201710044098A CN 106835364 A CN106835364 A CN 106835364A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Abstract
The invention discloses a kind of preparation method of the carbon nano-fiber composite material of load iron-copper bi-metal in situ.With ferric acetyl acetonade as source of iron, copper acetate be copper source and polyacrylonitrile as carbon source, prepared the polyacrylonitrile fibre containing iron mantoquita using the method for electrostatic spinning.After by the polyacrylonitrile fibre containing iron mantoquita under an inert gas high temperature cabonization, using carbon thermal reduction, the carbon nano-fiber composite material of load iron-copper bi-metal is prepared in original position.The present invention is easy to operate, and low cost, equipment requirement is low, and the control to material structure is strong.The carbon nano-fiber composite material specific surface area of obtained load iron-copper bi-metal in situ of the invention is high, waits orange No. two dyestuff to have excellent catalytic degradation performance.
Description
Technical field
The present invention relates to a kind of preparation method of nano composite material, particularly a kind of carbon of load iron-copper bi-metal in situ
The preparation method of nano-fiber composite material, belongs to field of material preparation.
Background technology
The features such as iron-copper bi-metal nano-particle has that particle diameter is small, specific surface area is big, surface-active is high and is cheap and easy to get,
Had broad application prospects in catalysis, the energy, environment remediation and pollution control.But iron-copper bi-metal nano-particle is present
Easily reunite, it is oxidizable, the problems such as be easy to run off, particle diameter increase after reunion, specific surface area reduction, reactivity reduction is in actual treatment
In exist and apply bottleneck.It is carrier generally using porous material for the shortcoming of iron-copper bi-metal nano-particle, it is double with iron copper
Metal nanoparticle is combined the exsertile composite of the property prepared.The iron-copper bi-metal for being presently used for preparing support type is received
The method of rice corpuscles composite mainly includes nanometer casting method altogether, Liquid infiltration and reduction method and the common construction from part of multicomponent.It is multigroup
Construction from part altogether is divided to have compared with first two method easy to operate, the metal nanoparticle stabilization of load, energy consumption is low, is adapted to industrial
The advantages of metaplasia is produced.
At present, the composite of loading type iron copper bi-metal nano-particle is based primarily upon the carrier of two-dimensional structure.Xia etc.
[M.Xia,et al,W.M.Cai and B.X.Zhou,Appl.Catal.B:Environ.110 (2011) 118-125] pass through
The method of collosol and gel co-precipitation is prepared for loading the Al-MCM-41 composites of iron-copper bi-metal oxide, iron-copper bi-metal
Oxidic particle preferably can be dispersed on the matrix of mesoporous silicon material, and the degraded of Pyrogentisinic Acid shows good catalytic
Energy.[Y.B.Wang, the et al, Appl.Catal.B such as Wang:Environ.164 (2015) 396-406] it is multigroup by one-step method
The method of assembling is prepared for loading the ordered mesoporous carbon composite material of iron-copper bi-metal point altogether, and iron-copper bi-metal nano-particle can be with
The skeleton of preferably embedded mesoporous carbon, and degraded to Some Organic Pollutants shows good catalytic performance.
In recent years, the material of one-dimensional nano structure is due to its unique structural advantage, in light, electricity, sensor and catalysis side
Face is subject to the extensive concern [17715- of A.Yousef, et al, Int.J.Hydrogen Energy 37 (2012) of researcher
17723].It is well known that rate of catalysis reaction is closely bound up with electron transfer rate.Carbon nano-fiber, it is fine as 1-dimention nano
Dimension structure, due to its aspect ratio high, beneficial to characteristics such as electron transmissions, shows great potentiality in catalytic reaction
[X.Q.Zhang,et al.Mater.Chem.A1(2013)9449-9455]。
The content of the invention
It is an object of the invention to provide a kind of preparation side of the carbon nano-fiber composite material of load iron-copper bi-metal in situ
Method, by by ferric acetyl acetonade, electrostatic spinning being carried out after copper acetate and polyacrylonitrile mixing, obtains the polypropylene containing iron mantoquita
Nitrile fiber, then by the polyacrylonitrile fibre carbonization containing iron mantoquita, the carbon nano-fiber for obtaining load iron-copper bi-metal in situ is answered
Condensation material, obtained composite has excellent catalysis activity.
Realize that the technical scheme of the object of the invention is as follows：
A kind of preparation method of the carbon nano-fiber composite material of load iron-copper bi-metal in situ, comprises the following steps that：
Step 1, by ferric acetyl acetonade, copper acetate and polyacrylonitrile (PAN) are added to DMF (DMF)
In, heating stirring obtains electrostatic spinning solution to well mixed；
Step 2, setting spinning voltage is 16-18kV, and it is 14-16cm to receive distance, and the electrostatic spinning that step 1 is obtained is molten
Liquid carries out electrostatic spinning, obtains the polyacrylonitrile fibre containing iron mantoquita；
Step 3, the polyacrylonitrile fibre containing iron mantoquita is placed in Muffle furnace, with the heating rate of 0.5-1 DEG C/min
Rising to 220-240 DEG C carries out activation 2-3h, then in an inert atmosphere, 850-950 DEG C is risen to the heating rate of 3-5 DEG C/min
Lower carbonization 2-3h, obtains the carbon nano-fiber composite material of load iron-copper bi-metal in situ.
In step 1, described ferric acetyl acetonade and the mol ratio of copper acetate is 1-3:3-1；Ferric acetyl acetonade rubs with PAN's
You are than being 1-3:0.0067；Ferric acetyl acetonade is 1-3 with the mol ratio of DMF:260；Mixing time is 2-4h.
In step 2, the driving velocity of electrostatic spinning is 1.4-1.5mL/h.
In step 3, described inert atmosphere is nitrogen or argon gas.
Compared with prior art, its remarkable advantage is the present invention：(1) carbon source and slaine are introduced by one-step method simultaneously,
With simple to operate, low cost, the advantages of equipment requirement is easy；(2) with molysite and mantoquita predecessor as raw material, using being carbonized
Journey reducing metal salt, while the carbonization of material and being formed in situ for nano-particle are realized, it is simple and easy to get, it is pollution-free；(3) in carbon
The nano composite material specific surface area of nanofiber matrix situ load iron-copper bi-metal is big, obtained nano particle diameter compared with
It is small and be uniformly distributed on carrier；(4) carbon nano-fiber matrix situ obtained in the method loads receiving for iron-copper bi-metal
Nano composite material has broad application prospects in the field such as reparation of catalysis, the energy, separation and environmental pollution.
Brief description of the drawings
Fig. 1 is obtained in Fe/CNF (A), FeCu/CNF-1 (B) obtained in embodiment 1 and comparative example 2 obtained in comparative example 1
The scanning electron microscope diagram of Cu/CNF (C) nano composite material.
Fig. 2 is obtained in Fe/CNF (A), FeCu/CNF-1 (B) obtained in embodiment 1 and comparative example 2 obtained in comparative example 1
The transmission electron microscope figure of nano composite material obtained in Cu/CNF (C).
Fig. 3 is Fe/CNF, FeCu/CNF-1 obtained in embodiment 1 and Cu/CNF obtained in comparative example 2 obtained in comparative example 1
The wide-angle X-ray powder diagram of obtained nano composite material.
Fig. 4 is Fe/CNF, FeCu/CNF-1 obtained in embodiment 1 and Cu/CNF obtained in comparative example 2 obtained in comparative example 1
The nitrogen adsorption of obtained nano composite material/desorption isotherm figure.
Fig. 5 is Fe/CNF, FeCu/CNF-1 obtained in embodiment 1 and Cu/CNF obtained in comparative example 2 obtained in comparative example 1
Obtained nano composite material is for the orange No. two catalytic degradation effect figures of dyestuff.
Specific embodiment
With reference to embodiment and accompanying drawing, the invention will be further described.
Embodiment 1
With Fe：Cu：PAN mol ratios are 1:3:As a example by 0.0067, FeCu/CNF-1 is named as.
The first step：The ferric acetyl acetonade of 1mmol, the copper acetate and 1g polyacrylonitrile (PAN) of 3mmol are added in 20mL
In DMF (DMF) solution, heating stirring 2h is forming homogeneous solution at 60 DEG C；
Second step：The solution of above-mentioned preparation is placed in the syringe with metal needle, then this syringe is fixed on quiet
The positive pole of electric spinning device, and the positive pole of high voltage power supply is clipped on metal needle, the speed that pushes away of syringe is 1.47mL/h；
3rd step：Aluminium film is laid on the collecting board of electrostatic spinning apparatus, and adjust collecting board and metal needle away from
From being 15cm, voltage is 18kV, to obtain the polyacrylonitrile fibre containing iron mantoquita of continuous-stable；
4th step：The polyacrylonitrile fibre of the iron content copper obtained by the 3rd step is collected, is placed in Muffle furnace with 1 DEG C/min's
Heating rate rises to 240 DEG C of activation 3h, then the product after activation is placed in tube furnace, in an inert atmosphere with 5 DEG C/min's
Heating rate rises to 900 DEG C of carbonization 2h.
Embodiment 2
With Fe：Cu：PAN mol ratios are 2:2:As a example by 0.0067, FeCu/CNF-2 is named as.
The first step：The ferric acetyl acetonade of 2mmol, the copper acetate and 1g polyacrylonitrile (PAN) of 2mmol are added in 20mL
In DMF (DMF) solution, heating stirring 2h is forming homogeneous solution at 60 DEG C；
Second step：The solution of above-mentioned preparation is placed in the syringe with metal needle, then this syringe is fixed on quiet
The positive pole of electric spinning device, and the positive pole of high voltage power supply is clipped on metal needle, the speed that pushes away of syringe is 1.4mL/h；
3rd step：Aluminium film is laid on the collecting board of electrostatic spinning apparatus, and adjust collecting board and metal needle away from
From being 14cm, voltage is 18kV, to obtain the polyacrylonitrile fibre containing iron mantoquita of continuous-stable；
4th step：The polyacrylonitrile fibre of the iron content copper obtained by the 3rd step is collected, is placed in Muffle furnace with 0.5 DEG C/min
Heating rate rise to 240 DEG C of activation 2h, then the product after activation is placed in tube furnace, in an inert atmosphere with 3 DEG C/min
Heating rate rise to 850 DEG C carbonization 3h.
Embodiment 3
With Fe：Cu：PAN mol ratios are 3:1:As a example by 0.0067, FeCu/CNF-3 is named as.
The first step：The ferric acetyl acetonade of 3mmol, the copper acetate and 1g polyacrylonitrile (PAN) of 1mmol are added in 20mL
In DMF (DMF) solution, heating stirring 4h is forming homogeneous solution at 60 DEG C；
Second step：The solution of above-mentioned preparation is placed in the syringe with metal needle, then this syringe is fixed on quiet
The positive pole of electric spinning device, and the positive pole of high voltage power supply is clipped on metal needle, the speed that pushes away of syringe is 1.5mL/h；
3rd step：Aluminium film is laid on the collecting board of electrostatic spinning apparatus, and adjust collecting board and metal needle away from
From being 16cm, voltage is 16kV, to obtain the polyacrylonitrile fibre containing iron mantoquita of continuous-stable；
4th step：The polyacrylonitrile fibre of the iron content copper obtained by the 3rd step is collected, is placed in Muffle furnace with 1 DEG C/min's
Heating rate rises to 220 DEG C of activation 3h, then the product after activation is placed in tube furnace, in an inert atmosphere with 5 DEG C/min's
Heating rate rises to 950 DEG C of carbonization 2h.
Comparative example 1
With Fe：Cu：PAN mol ratios are 4:0:As a example by 0.0067, Fe/CNF is named as.
The first step：The ferric acetyl acetonade of 4mmol and 1g polyacrylonitrile (PAN) are added in 20mL N, N- dimethyl formyls
In amine (DMF) solution, heating stirring 2h is forming homogeneous solution at 60 DEG C；
Second step：The solution of above-mentioned preparation is placed in the syringe with metal needle, then this syringe is fixed on quiet
The positive pole of electric spinning device, and the positive pole of high voltage power supply is clipped on metal needle, the speed that pushes away of syringe is 1.47mL/h；
3rd step：Aluminium film is laid on the collecting board of electrostatic spinning apparatus, and adjust collecting board and metal needle away from
From being 15cm, voltage is 18kV, to obtain the polyacrylonitrile fibre containing iron mantoquita of continuous-stable；
4th step：The polyacrylonitrile fibre of the iron content obtained by the 3rd step is collected, is placed in Muffle furnace with the liter of 1 DEG C/min
Warm speed rises to 240 DEG C of activation 3h, then the product after activation is placed in tube furnace, in an inert atmosphere with the liter of 5 DEG C/min
Warm speed rises to 900 DEG C of carbonization 2h.
Comparative example 2
With Fe：Cu：PAN mol ratios are 0:4:As a example by 0.0067, Cu/CNF is named as.
The first step：The copper acetate of 4mmol and 1g polyacrylonitrile (PAN) are added in 20mL N,N-dimethylformamides
(DMF) in solution, heating stirring 2h is forming homogeneous solution at 60 DEG C；
Second step：The solution of above-mentioned preparation is placed in the syringe with metal needle, then this syringe is fixed on quiet
The positive pole of electric spinning device, and the positive pole of high voltage power supply is clipped on metal needle, the speed that pushes away of syringe is 1.47mL/h；
3rd step：Aluminium film is laid on the collecting board of electrostatic spinning apparatus, and adjust collecting board and metal needle away from
From being 15cm, voltage is 18kV, to obtain the polyacrylonitrile fibre containing iron mantoquita of continuous-stable；
4th step：The polyacrylonitrile fibre of the cupric obtained by the 3rd step is collected, is placed in Muffle furnace with the liter of 1 DEG C/min
Warm speed rises to 240 DEG C of activation 3h, then the product after activation is placed in tube furnace, in an inert atmosphere with the liter of 5 DEG C/min
Warm speed rises to 900 DEG C of carbonization 2h.
Embodiment 4
The first step：Respectively by catalyst (Fe/CNF, the FeCu/ obtained in embodiment 1 obtained in comparative example 1 of 0.5g/L
CNF-1 and nano composite material obtained in Cu/CNF obtained in comparative example 2) it is added in orange No. two dyestuffs of 10ml.Dyestuff is dense
It is 100mg/L to spend, and pH is 7；
Second step：Add the H of 54.8mM/L2O2Start catalytic reaction, reaction temperature is 30 DEG C.
3rd step：Reaction system is sampled at no time point, determines remaining orange No. two dyes in reaction system
The concentration of material.
Table 1 Fe/CNF, FeCu/CNF-1 and Cu/CNF nano composite material is for orange No. two clearances of dyestuff
By SEM, TEM, XRD and nitrogen adsorption/desorption isotherm (Fig. 1-4) to Fe/CNF, implementation obtained in comparative example 1
FeCu/CNF-1 obtained in example 1 and knowable to Cu/CNF nano composite materials are characterized obtained in comparative example 2：Iron-copper bi-metal is received
Rice corpuscles is supported on the matrix of carbon nano-fiber by the method success original position of carbon thermal reduction；Iron-copper bi-metal carbon nano-fiber
Composite has loose structure, and specific surface area is big；Iron copper is present on carrier in nanocrystalline form respectively, and particle diameter is small,
It is uniformly dispersed.
Fig. 5 is Fe/CNF, FeCu/CNF-1 obtained in embodiment 1 and Cu/CNF obtained in comparative example 2 obtained in comparative example 1
For the orange No. two catalytic degradation effect figures of dyestuff, table 1 is Fe/CNF, reality obtained in comparative example 1 to obtained nano composite material
FeCu/CNF-1 obtained in example 1 and nano composite material obtained in Cu/CNF obtained in comparative example 2 are applied for No. two dyestuffs of orange
Clearance result, knowable to Fig. 5 and Biao 1, the catalytic performance of FeCu/CNF-1 nano composite materials is significantly better than Fe/CNF and Cu/
CNF nano composite materials.
Claims (4)
1. a kind of original position loads the preparation method of the carbon nano-fiber composite material of iron-copper bi-metal, it is characterised in that specific step
It is rapid as follows：
Step 1, by ferric acetyl acetonade, copper acetate and polyacrylonitrile are added in DMF, and heating stirring is to mixed
Close uniform, obtain electrostatic spinning solution；
Step 2, setting spinning voltage is 16-18kV, and it is 14-16cm to receive distance, and the electrostatic spinning solution that step 1 is obtained is entered
Row electrostatic spinning, obtains the polyacrylonitrile fibre containing iron mantoquita；
Step 3, the polyacrylonitrile fibre containing iron mantoquita is placed in Muffle furnace, is risen to the heating rate of 0.5-1 DEG C/min
220-240 DEG C carries out activation 2-3h, then in an inert atmosphere, carbon at rising to 850-950 DEG C with the heating rate of 3-5 DEG C/min
Change 2-3h, obtain the carbon nano-fiber composite material of load iron-copper bi-metal in situ.
2. preparation method according to claim 1, it is characterised in that in step 1, described ferric acetyl acetonade and copper acetate
Mol ratio be 1-3:3-1；Ferric acetyl acetonade is 1-3 with the mol ratio of polyacrylonitrile:0.0067；Ferric acetyl acetonade and N, N- bis-
The mol ratio of NMF is 1-3:260；Mixing time is 2-4h.
3. preparation method according to claim 1, it is characterised in that in step 2, the driving velocity of electrostatic spinning is 1.4-
1.5mL/h。
4. preparation method according to claim 1, it is characterised in that in step 3, described inert atmosphere is nitrogen or argon
Gas.
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Cited By (7)
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| CN108786814A (en) * | 2018-06-06 | 2018-11-13 | 武汉工程大学 | A kind of copper cobalt dual-metal/porous carbon nanofiber composite material and preparation method and application |
| CN108899487A (en) * | 2018-06-15 | 2018-11-27 | 合肥国轩高科动力能源有限公司 | A kind of high conductivity lithium ion battery negative material and preparation method thereof |
| CN108950733A (en) * | 2018-07-11 | 2018-12-07 | 浙江师范大学 | A kind of nucleocapsid heterogeneous structural nano fiber and its preparation and application |
| CN109399691A (en) * | 2018-12-04 | 2019-03-01 | 江苏理工学院 | A kind of Cu-CuO/ carbon nano-fiber composite material and preparation method thereof |
| CN111235695A (en) * | 2020-03-17 | 2020-06-05 | 南京航空航天大学 | Preparation method of porous carbon fiber electromagnetic wave absorbing agent |
| CN112599777A (en) * | 2020-12-14 | 2021-04-02 | 河北工业大学 | Preparation method and application of transition metal sulfide/nitrogen and sulfur co-doped carbon composite fiber electrode material |
| CN115869934A (en) * | 2022-10-31 | 2023-03-31 | 唐山三友集团兴达化纤有限公司 | Metal/carbon nanofiber persulfate catalyst, preparation method and application |
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| CN108786814A (en) * | 2018-06-06 | 2018-11-13 | 武汉工程大学 | A kind of copper cobalt dual-metal/porous carbon nanofiber composite material and preparation method and application |
| CN108899487A (en) * | 2018-06-15 | 2018-11-27 | 合肥国轩高科动力能源有限公司 | A kind of high conductivity lithium ion battery negative material and preparation method thereof |
| CN108950733A (en) * | 2018-07-11 | 2018-12-07 | 浙江师范大学 | A kind of nucleocapsid heterogeneous structural nano fiber and its preparation and application |
| CN108950733B (en) * | 2018-07-11 | 2020-12-29 | 浙江师范大学 | Core-shell heterostructure nanofiber and preparation and application thereof |
| CN109399691A (en) * | 2018-12-04 | 2019-03-01 | 江苏理工学院 | A kind of Cu-CuO/ carbon nano-fiber composite material and preparation method thereof |
| CN111235695A (en) * | 2020-03-17 | 2020-06-05 | 南京航空航天大学 | Preparation method of porous carbon fiber electromagnetic wave absorbing agent |
| CN111235695B (en) * | 2020-03-17 | 2021-09-17 | 南京航空航天大学 | Preparation method of porous carbon fiber electromagnetic wave absorbing agent |
| CN112599777A (en) * | 2020-12-14 | 2021-04-02 | 河北工业大学 | Preparation method and application of transition metal sulfide/nitrogen and sulfur co-doped carbon composite fiber electrode material |
| CN112599777B (en) * | 2020-12-14 | 2022-09-27 | 河北工业大学 | Preparation method and application of transition metal sulfide/nitrogen and sulfur co-doped carbon composite fiber electrode material |
| CN115869934A (en) * | 2022-10-31 | 2023-03-31 | 唐山三友集团兴达化纤有限公司 | Metal/carbon nanofiber persulfate catalyst, preparation method and application |
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Application publication date: 20170613 |