CN104944410B - A kind of method for synthesizing cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite - Google Patents
A kind of method for synthesizing cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite Download PDFInfo
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- CN104944410B CN104944410B CN201510291943.9A CN201510291943A CN104944410B CN 104944410 B CN104944410 B CN 104944410B CN 201510291943 A CN201510291943 A CN 201510291943A CN 104944410 B CN104944410 B CN 104944410B
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Abstract
The invention discloses a kind of method for synthesizing cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite.By soluble cobalt and amine polymer according to mol ratio 1:(2~200) are dissolved in hydrophilic agent, are evaporated under the conditions of 60 degree, 400~1400 degree of calcinings under grinding, nitrogen atmosphere after cooling.Acid treatment sample is used after calcining, cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite are obtained after washing centrifugal drying.Gained Co nano particle diameters are small and equably by CNT are coated on head, are tightly combined with CNT, and the composite has application prospect at aspects such as fuel cell anode material, lithium ion battery negative materials.There is method designed by the present invention raw material to be easy to get, and process is simple is pollution-free, short preparation period, and reaction condition is gentle, low cost, the advantages of can largely synthesizing.
Description
Technical field
The present invention relates to a kind of method for synthesizing cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite, belong to
CNT one-dimensional composite material preparing technical field.
Background technology
The appearance of CNT opens the new important research field of nano material science and technology, and low-dimension nano material science is ground
Band is studied carefully to one-dimensional (1D) epoch, electron microscope expert's Iijima of Japanese NEC Corporation's basic research laboratories in 1991
(Iijima) doctor has had been surprisingly found that CNT (Carbon nanotube).Used as typical 1D nano structural materials, carbon is received
Mitron shows the physicochemical characteristics of novelty, especially heat endurance high and surface carrier mobility, makes carbon nanometer
Pipe in new energy, be also used widely, in short several years just by sensor, ultracapacitor, the field such as field emission tube
Through being successfully applied to conductive structure material, sensing with display device, new energy storage and the field such as reforming unit.CNT table
The huge research and application value revealed also result in researcher and CNT is doped and is combined.At present for carbon
Nanotube has various heteroatomic doping, such as the electron such as boron, nitrogen phosphate and sulfur or electrophilic hetero atom are doped to change
Become the outer-shell electron number of the surface carbon atom of CNT, electronegativity and atomic size, due to special electronegativity and solely
Special structure, these doped carbon nanometer pipe materials show special characteristic electron and surface defect, with excellent mechanics,
Electricity and catalytic performance, can be widely applied to opto-electronic device, biochemical sensor, catalyst, ultracapacitor, lithium ion
The fields such as battery, fuel cell and solar cell, are especially being highly dependent on the electrochemical reaction of material list interface performance
Field, doped carbon nanometer pipe is even more and shows superior performance.However, a series of performance of these innovations of CNT and
Using with dependence in the controllable prepare with scale of material.The special performance of carbon nano-tube material depends on its length and diameter, because
And it is considered as modern chemistry and material science to design synthesizing carbon nanotubes by the regulation and control of nanoscale and appearance structure
One Some Questions To Be Researched.Transition metal causes many scientific workers' with nitrogen doped corrugated carbon nanotube composite
Interest, due to its unique structure and excellent performance, make its composite, electronic equipment, sensor, lithium ion battery,
The aspects such as ultracapacitor, fuel cell have important potential application.But at present for nitrogen doped corrugated carbon nanotube
It is simple for material, not good method in cheap and substantial amounts of synthesis.And current synthetic method synthesis Bamboo-shaped
CNT, caliber is generally extremely uneven, and impurity is more, relatively costly, it is difficult to which continuous batch is produced.And carbon nanometer
Pipe is compound with transition metal to be typically supported on carbon nanotube outer, and transition metal is easily oxidized into oxide, due to
Its bad electric conductivity, so as to influence the performance of the electrochemistry of CNT.
The widely used method of carbon nano tube compound material is prepared at present for graphite arc discharge method, chemical vapor deposition
And hydro-thermal method etc. (CVD).Although graphite arc discharge method can be prepared on a large scale, and yield is larger, and impurity is more, needs more
Cumbersome subsequent treatment.And although chemical vapor deposition can prepare high-quality CNT, its yield is relatively low, and high
Degree depends on growing substrate, relatively costly, is not suitable for industrial applications.Comparatively speaking, thermal decomposition method is fairly simple quick
Synthetic method, building-up process is simply controllable, and raw material is cheap and easy to get, is adapted to industrialized developing application.
The present invention has synthetic method simple, is obtained that carbon nanotube diameter is uniform, and yield is higher, cobalt nanometer particle it is compound compared with
It is tight, suitable extensive preparation.Simultaneously synthesis cobalt nanometer particle and ring were reported as far as the applicant is aware, having no up to now
The method of shape carbon nano tube compound material.
The content of the invention
The invention aims to solve prior art complex steps, and gained carbon nanotube diameter is uneven, is combined
It is not tight, it is impossible to the problem of a large amount of productions, there is provided a kind of cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite side
Method.
The purpose of the present invention is achieved through the following technical solutions.
The present invention proposes a kind of cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite process, and specific steps are such as
Under：
Step one, by cobalt salt and amine polymer according to mol ratio 1:(2~200) are dissolved in methyl alcohol respectively, under 60 degree
Heating evaporation, to naturally cool to be ground after room temperature after being evaporated and obtains sample powder；
Step 2, the sample powder obtained by step one is put into it is passed through nitrogen in tube furnace and is calcined,
Step 3, by the acid treatment sample of the sample products obtained by step 2, then with deionized water and absolute ethyl alcohol
After washing centrifugation, it is put into after vacuum drying chamber is dried and just obtains Bamboo-shaped nitrogen-doped carbon nanometer pipe.
The cobalt salt raw material is：Cobalt nitrate, cobalt acetate, cobalt chloride, one or more the salt-mixture in cobaltous sulfate；
The amine polymer is：Melamine, dicyan diamino, urea, one or more mixed in cyanamide
Compound；
The acid is：Hydrochloric acid, sulfuric acid, nitric acid, one or more mixed solution of acetic acid.
Beneficial effect
1st, a kind of method for synthesizing cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite of the invention, its is micro-
See structure and morphology and be characterized as Bamboo-shaped nanotube, uniform diameter, cobalt nanometer particle is wrapped in CNT head, can be used to make
Standby fuel cell, electrode of super capacitor active material and catalyst etc..
2nd, a kind of method for synthesizing cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite of the invention, operation
Simply, it is with low cost, can prepare on a large scale, whole course of reaction does not need specific apparatus, reaction temperature 400~1400 DEG C it
Between, Product size and pattern are uniform, and cobalt nanometer particle is compound with bamboo-like carbon nano tubes tight.
3rd, a kind of method for synthesizing cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite of the invention, uses
Thermal decomposition method has the advantages that simple and easy to apply, and reaction time is short, and reaction yield is high, and composite effect is good.And cobalt nanometer particle exists
Wherein CNT is catalyzed, therefore resulting product structure is peculiar, degree of graphitization is high, without other impurities.With it is general
Carbon nano tube compound material is prepared all over methods such as the chemical vapor depositions and hydro-thermal for using, the method designed by the present invention has produces
Thing is uniform, compound tight, the advantages of largely synthesis, is adapted to industrialized production and scale application.
Brief description of the drawings
Fig. 1 is the X-ray diffracting spectrum for illustrating the carbon nano tube compound material material prepared by case study on implementation；
Fig. 2 is the scanning electron microscope diagram for illustrating the carbon nano tube compound material material prepared by case study on implementation；
Fig. 3 is the low power transmission electron microscope figure for illustrating the carbon nano tube compound material material prepared by case study on implementation；
Fig. 4 is the high power transmission electron microscope figure for illustrating the carbon nano tube compound material material prepared by case study on implementation；
Fig. 5 is the high-resolution-ration transmission electric-lens figure for illustrating the carbon nano tube compound material material prepared by case study on implementation；
Fig. 6 is the X-ray photoelectron spectroscopic analysis for illustrating the carbon nano tube compound material material prepared by case study on implementation；
Fig. 7 is the Raman energy spectrum figure for illustrating the carbon nano tube compound material material prepared by case study on implementation；
Specific embodiment
Embodiment 1
(1) by cobalt nitrate and melamine according to mol ratio 1:200 are dissolved in methyl alcohol respectively, magnetic agitation 30 minutes,
To fully dissolving, the then heating evaporation under 60 degree, to naturally cool to be ground after room temperature after being evaporated and obtain sample powder.
(2) resulting sample powder is put into and is passed through nitrogen in tube furnace and is calcined, per minute be warming up to 5 degree
400 degree keep 1 hour, then with 10 degree it is per minute rise to 700 degree holding 3 hours, obtain sample products
(3) sample products for the obtaining HCl treatment sample of 0.5M, then with deionized water and absolute ethanol washing from
After the heart, cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite are just obtained after being put into 80 degree of dryings of vacuum drying chamber.
Embodiment 2
(1) by cobalt acetate and dicyanodiamine according to mol ratio 1:2 are dissolved in ethanol respectively, magnetic agitation 30 minutes, to filling
Divide dissolving.Then the heating evaporation under 60 degree, to naturally cool to be ground after room temperature after being evaporated and obtains sample powder.
(2) resulting sample powder is put into and is passed through nitrogen in tube furnace and is calcined, per minute be warming up to 5 degree
400 degree keep 1 hour, then with 10 degree it is per minute rise to 700 degree holding 3 hours, obtain sample products
(3) sample products for the obtaining sulfuric acid treatment sample of 0.5M, then with deionized water and absolute ethanol washing from
After the heart, cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite are just obtained after being put into 80 degree of dryings of vacuum drying chamber.
Embodiment 3
(1) by cobalt chloride and cyanamide according to mol ratio 1:10 are dissolved in deionized water respectively, magnetic agitation 30 minutes,
To fully dissolving.Then the heating evaporation under 60 degree, to naturally cool to be ground after room temperature after being evaporated and obtains sample powder.
(2) resulting sample powder is put into and is passed through nitrogen in tube furnace and is calcined, per minute be warming up to 2 degree
500 degree of holdings obtain sample products in 3 hours
(3) sample products for the obtaining nitric acid treatment sample of 0.5M, then with deionized water and absolute ethanol washing from
After the heart, cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite are just obtained after being put into 80 degree of dryings of vacuum drying chamber.
Embodiment 4
(1) by cobaltous sulfate and melamine according to mol ratio 1:20 are dissolved in ethylene glycol respectively, magnetic agitation 30 minutes,
To fully dissolving.Then the heating evaporation under 60 degree, to naturally cool to be ground after room temperature after being evaporated and obtains sample powder.
(2) resulting sample powder is put into and is passed through nitrogen in tube furnace and is calcined, per minute be warming up to 5 degree
400 degree keep 3 hours, then with 10 degree it is per minute rise to 1400 degree holding 2 hours, obtain sample products
(3) sample products for the obtaining acetic acid treatment sample of 0.5M, then with deionized water and absolute ethanol washing from
After the heart, cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite are just obtained after being put into 80 degree of dryings of vacuum drying chamber.
Embodiment 5
(1) by cobalt acetate and dicyanodiamine according to mol ratio 1:50 are dissolved in the mixed solvent of ethanol and methyl alcohol respectively, magnetic
Power is stirred 30 minutes, to fully dissolving.Then the heating evaporation under 60 degree, is ground after room temperature is naturally cooled to after being evaporated
To sample powder.
(2) resulting sample powder is put into and is passed through nitrogen in tube furnace and is calcined, per minute be warming up to 5 degree
400 degree keep 3 hours, then with 10 degree it is per minute rise to 1400 degree holding 2 hours, obtain sample products
(3) sample products for the obtaining sulfuric acid treatment sample of 0.5M, then with deionized water and absolute ethanol washing from
After the heart, cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite are just obtained after being put into 80 degree of dryings of vacuum drying chamber.
Embodiment 6
(1) by the mixture of cobalt chloride and dicyanodiamine and melamine according to mol ratio 1:50 are dissolved in methyl alcohol respectively
In mixed solvent, magnetic agitation 30 minutes, to fully dissolving.Then the heating evaporation under 60 degree, room is naturally cooled to after being evaporated
It is ground after temperature and obtains sample powder.
(2) resulting sample powder is put into and is passed through nitrogen in tube furnace and is calcined, per minute be warming up to 3 degree
300 degree keep 3 hours, then with 5 degree it is per minute rise to 900 degree holding 2 hours, obtain sample products
(3) sample products for the obtaining HCl treatment sample of 0.5M, then with deionized water and absolute ethanol washing from
After the heart, cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite are just obtained after being put into 80 degree of dryings of vacuum drying chamber.
Embodiment 7
(1) by the mixture and melamine of cobalt chloride and cobalt acetate according to mol ratio 1:100 are dissolved in the mixed of ethanol respectively
In bonding solvent, magnetic agitation 30 minutes, to fully dissolving.Then the heating evaporation under 60 degree, room temperature is naturally cooled to after being evaporated
After be ground and obtain sample powder.
(2) resulting sample powder is put into and is passed through nitrogen in tube furnace and is calcined, per minute be warming up to 5 degree
1000 degree are kept for 3 hours, obtain sample products
(3) sample products for the obtaining acetic acid treatment sample of 0.5M, then with deionized water and absolute ethanol washing from
After the heart, cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite are just obtained after being put into 80 degree of dryings of vacuum drying chamber.
Embodiment 8
(1) by the mixture and dicyanodiamine melamine of cobaltous sulfate and cobalt acetate according to mol ratio 1:20 are dissolved in respectively
In the mixed solvent of ethanol, magnetic agitation 30 minutes, to fully dissolving.Then the heating evaporation under 60 degree, naturally cold after being evaporated
But sample powder is obtained to being ground after room temperature.
(2) resulting sample powder is put into and is passed through nitrogen in tube furnace and is calcined, per minute be warming up to 2 degree
400 degree are kept for 3 hours, then per minute be warming up to 900 degree and obtained sample products with 3 degree
(3) sample products for obtaining process sample with the hydrochloric acid of 0.5M with sulfuric acid mixture, then with deionized water and nothing
After water-ethanol washing centrifugation, cobalt nanometer particle is just obtained with Bamboo-shaped nitrogen-doped carbon nanometer after being put into 80 degree of dryings of vacuum drying chamber
Pipe composite.
Fig. 1 is the X ray diffracting spectrum of carbon nano tube compound material, and obtained material is cobalt nanometer particle and Bamboo-shaped
Carbon nano tube compound material, and material crystalline is good.Fig. 2 is the scanning electron microscope diagram piece of carbon nano tube compound material, institute
Obtained material diameter and pattern are uniform, and cobalt nanometer particle is wrapped in head,.Fig. 3 is the low power of carbon nano tube compound material
Transmission electron micrograph, obtained material is Bamboo-shaped nano tube structure, and its length is about 1~3um, and diameter is about 80
~100nm.Fig. 4 is the high power transmission electron micrograph of carbon nano tube compound material, and obtained material is received for Bamboo-shaped
Nanotube structures, its uniform diameter, obvious Fig. 5 of bamboo joint structure is the high resolution transmission electron microscopy of carbon nano tube compound material
Piece, obtained material is typical Bamboo-shaped multi-wall carbon nano-tube tubular construction, and is combined closely, can be observed by lattice fringe
To (111) face of cobalt nanometer particle, it was demonstrated that cobalt nanometer particle is wrapped in head, and its diameter is about 80nm.Fig. 6 is CNT
The X-ray photoelectron spectroscopic analysis of composite, due to obtained cobalt nanometer particle and nitrogen doped corrugated shape composite, only
C, N, O, and Co element are detected, is occurred without other impurities element, illustrate prepared CNT by N doping, and receive with Co
Rice corpuscles is compound preferable, without other impurities.Fig. 7 is the Raman energy spectrum figure of carbon nano tube compound material, in 1329D bands and 1573G
It is the characteristic peak of carbon nano-tube material with obvious characteristic peak, the degree of graphitization for indicating composite is high, electric conductivity
Well, with good chemical property.
Claims (5)
1. a kind of method of pyrolyzing synthesis cobalt nanometer particle and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite, its feature exists
In：Comprise the following steps that：
Step one, cobalt salt and amine polymer are dissolved in hydrophilic solvent respectively, mixed proportion is cobalt salt and amine polymer
Mol ratio is 1:(2~200), the heating evaporation under 60 degree to be naturally cooled to be ground after room temperature after being evaporated and obtains sample powder
End；
Step 2, the sample powder obtained by step one is put into it is passed through nitrogen in tube furnace and is calcined；
Step 3, by the acid treatment sample of the sample products obtained by step 2, then with deionized water and absolute ethanol washing
After centrifugation, it is put into after vacuum drying chamber is dried and just obtains Bamboo-shaped nitrogen-doped carbon nanometer pipe.
2. a kind of pyrolyzing synthesis cobalt nanometer particle as claimed in claim 1 and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite
Method, it is characterised in that：The hydrophilic solvent is：Methyl alcohol, ethanol, deionized water, one or more in ethylene glycol
Mixed solvent.
3. a kind of pyrolyzing synthesis cobalt nanometer particle as claimed in claim 1 and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite
Method, it is characterised in that：The cobalt salt raw material is：Cobalt nitrate, cobalt acetate, cobalt chloride, in cobaltous sulfate one or two with
On salt-mixture.
4. a kind of pyrolyzing synthesis cobalt nanometer particle as claimed in claim 1 and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite
Method, it is characterised in that：The amine polymer is：Melamine, dicyan diamino, urea, one kind in cyanamide or two
Plant the mixture of the above.
5. a kind of pyrolyzing synthesis cobalt nanometer particle as claimed in claim 1 and Bamboo-shaped nitrogen-doped carbon nanometer pipe composite
Method, it is characterised in that：Institute's calcining heat any number of degrees from 400~1200 degree of intervals in nitrogen.
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