CN109956463A - A kind of carbon nanotube and preparation method thereof - Google Patents
A kind of carbon nanotube and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of controlled diameter carbon nanotubes and preparation method thereof, the method be by metal organic framework, metal salt and amino-compound in the liquid phase, obtained presoma is heat-treated is carbonized under an inert atmosphere, and the partial size by changing metal organic framework in presoma realizes that carbon nanotube is directly controllable.Compared with prior art, the present invention has the advantage that in preparation process by simply changing solvent, the synthesis conditions such as reaction temperature obtain different-grain diameter metal organic framework can and then control the diameter of carbon nanotube;Preparation process is simple, is not necessarily to arc discharge, the equipment of the tradition preparation carbon nanotube such as chemical vapor deposition.The carbon nanotube of preparation is doped with a large amount of N in situ simultaneously, changes carbon nano tube surface electronic structure, further promotes its chemical property, it is made to have biggish potential application foreground in the conversion of energy and field of storage.
Description
Technical field
The present invention relates to carbon material preparation and its application fields, and in particular to a kind of preparation and application of carbon nanotube.
Background technique
A kind of novel carbon nanomaterial that carbon nanotube is made of carbon atom, unique one-dimentional structure, Gao Shimo
Change degree and excellent electricity and mechanical property cause the broad interest of scientific research personnel, especially in electrochemical energy storage and
Conversion art is considered to have wide application prospect.As a kind of one-dimensional material, diameter is an important knot of carbon nanotube
Structure parameter, and some researches show that as the diameter for changing carbon nanotube can significantly affect its chemical property.
Currently used preparation method of carbon nano-tube mainly has: arc discharge method, laser evaporization method, CVD, solid-phase pyrolysis
Deng.Japanese physicist Iijima in 1991 is given birth to by arc discharge method and has found carbon nanotube for the first time, on this method and technology
Carbon nanotube and C fairly simple, but obtain60Equal products mix, and purity is not high.CVD method is simple to equipment requirement, cost compared with
It is low, be current synthesizing carbon nanotubes it is most viable be also most economical practical method.Recently, direct high temperature cabonization solid phase precursor
The method of (such as fullerene carbon black, organo-metallic compound, polymer) is used to prepare carbon nanotube, and this method is in addition to grasping
On work it is more easy except, it can also be made to adulterate in situ during heating by the way that N, S, B compound are added in presoma
Into carbon nanotube, to change carbon nano tube surface electronic structure, its chemical property can be made further to be promoted.However
The behavior of presoma is difficult to control during high temperature pyrolysis, and the finally formed usual pattern of carbon nanotube is inhomogenous, passes through pyrolysis
Preparing the carbon nanotube of controlled diameter, there are still challenges.
Summary of the invention
The present invention prepares the uncontrollable problem of carbon nanotube pattern for pyrolysis precursor, proposes a kind of controlled diameter
Carbon nanotube gas preparation method, the present invention are realized using scheme in detail below:
A kind of carbon nanotube, it is characterised in that: the carbon nanotube is in Bamboo-shaped pattern, i.e., every carbon nanotube is by 2 sections
Above Bamboo-shaped pipeline section is linked in sequence, and N element is contained in the carbon nanotube, and one end is enclosed with metal nanoparticle;
The outer diameter of the carbon nanotube is 50-300nm.Form existing for the N element is pyridine N, pyrroles N, is graphitized N and oxidation N
One or more of, nitrogen mass content is 2%-8%.Carbon nanotube as described in claim 1, feature exist
In: the metal nanoparticle is iron and/or cobalt, and the diameter of metal nanoparticle is 50-300nm.The metal nanoparticle
Account for the 1%-10% of carbon nanotube gross mass.The more excellent outer diameter of the carbon nanotube is 300nm;The metal nanoparticle it is straight
More excellent diameter is 300nm.
The preparation method of the carbon nanotube the following steps are included:
(1) synthesis of metal organic framework: the mixed solution of zinc salt and organic ligand is prepared;It is carried out at 30-120 DEG C anti-
It answers, then isolated metal organic framework;
(2) preparation of presoma: metal salt and amino-compound are dissolved in solvent, the metal prepared in step (1) is added
Organic backbone after being uniformly dispersed, removes solvent and obtains presoma;
(3) preparation of carbon nanotube: presoma obtained by step (2) is heat-treated under an inert atmosphere, obtains end packet
Wrap up in the carbon nanotube of metal nanoparticle.
Zinc salt described in step (1) is one or more of zinc nitrate, zinc chloride, zinc sulfate, and zinc ion is in mixed
Closing the concentration in solution is 0.0125-0.1mol/L.
Machine ligand described in step (1) is 2-methylimidazole, and concentration of the organic ligand in mixed solution is 0.1-
0.8mol/L。
Solvent in mixed solution described in step (1) is one of methanol, ethyl alcohol, water and DMF.
Metal salt described in step (2) is one or more of chloride, nitrate, acetate of cobalt or iron.
Amino-compound described in step (2) is one or more of urea, dicyandiamide, melamine.
Solvent described in step (2) is the mixed solution of one or more of methanol, second alcohol and water.
The mass ratio 1:1-1:5 of metal salt described in step (2) and amino-compound.
The method that solvent is removed described in step (2) is rotary evaporation and/or vacuum drying.
Step (3) heat treatment process is to be warming up to 800-1100 DEG C and keep 0.5-3h, is then cooled to room temperature;Institute
Stating in temperature-rise period from room temperature to the heating rate of heat treatment temperature is 2-5 DEG C/min;Cool down speed in the temperature-fall period
Rate is 1-10 DEG C/min.
Step (3) inert atmosphere is the gaseous mixture of one or both of nitrogen, argon gas.
The catalyst is polymer dielectric film fuel cell and metal air battery cathodes oxygen reduction reaction electro-catalysis
Agent.
Compared with prior art, the present invention has the advantage that passing through the grain of control metal organic framework in preparation process
Diameter can directly control the diameter of carbon nanotube;Carbon nanotube diameter is uniform controllable, and control range is between 50-300nm;Preparation
Simple process is not necessarily to arc discharge, the equipment of the tradition preparation carbon nanotube such as chemical vapor deposition.The carbon nanotube of preparation simultaneously
Original position is doped with a large amount of N, changes carbon nano tube surface electronic structure, further promotes its chemical property, make it in energy
Conversion has biggish potential application foreground with field of storage.
Detailed description of the invention
Fig. 1: metal organic framework low power SEM photograph
Fig. 2: carbon nanotube low power SEM photograph
Fig. 3: carbon nanotube low power SEM photograph
Fig. 4: carbon nanotube XRD diagram.
Specific embodiment
Comparative example 1
2g dicyandiamide and 1g cobalt acetate are dissolved in 60ml ethyl alcohol, are evaporated after heating stirring 5h at 80 DEG C, solid powder is obtained
End.It takes solid powder to be placed in corundum boat, be heated to 800 DEG C under nitrogen protection with 2 DEG C/min heating rate and keep the temperature 1h, then with
5 DEG C/min rate of temperature fall is cooled to room temperature taking-up product.
There is no metal organic framework as template, the carbon nanotube that diameter is evenly distributed can not be formed
Comparative example 2
At 20 DEG C, the 2-methylimidazole of the cabaltous nitrate hexahydrate of 1.436g and 3.244g are dissolved in 100ml methanol respectively, it is preceding
Person is added slowly with stirring in the latter, continues to stir 12min, is then allowed to stand 20h.Centrifuge separation is washed three times, at 150 DEG C
Lower vacuum drying 8h obtains ZIF-67-300.ZIF-67-300 the and 1g cobalt acetate of 0.2g is dissolved in 60ml ethyl alcohol, at 80 DEG C
Heating stirring 5h, then 48h is stirred at room temperature, then it is evaporated acquisition solid powder for 60 DEG C.Solid powder is taken to be placed in corundum boat,
800 DEG C are heated to 2 DEG C/min heating rate under nitrogen protection and keeps the temperature 1h, then are cooled to room temperature with 5 DEG C/min rate of temperature fall
Take out product.
There is no amino-compound (such as dicyandiamide) as carbon nitrogen source, carbon nanotube can not be grown.
Embodiment 1
At 20 DEG C, the 2-methylimidazole of the cabaltous nitrate hexahydrate of 1.436g and 3.244g are dissolved in 100ml methanol respectively, it is preceding
Person is added slowly with stirring in the latter, continues to stir 12min, is then allowed to stand 20h.Centrifuge separation is washed three times, at 150 DEG C
Lower vacuum drying 8h obtains ZIF-67-300.2g dicyandiamide and 1g cobalt acetate are dissolved in 60ml ethyl alcohol, the heating stirring at 80 DEG C
5h adds the ZIF-67-300 of 0.2g, and after stirring 48h at room temperature, 60 DEG C are evaporated acquisition solid powder.Solid powder is taken to be placed in
Corundum boat is heated to 800 DEG C under nitrogen protection with 2 DEG C/min heating rate and keeps the temperature 1h, then cold with 5 DEG C/min rate of temperature fall
But carbon nanotube is taken out to room temperature.
Using the ZIF-67 of 300nm as template, the carbon nanotube of outer diameter about 200nm is prepared.
Embodiment 2
At 20 DEG C, the 2-methylimidazole of the cabaltous nitrate hexahydrate of 1.436g and 3.244g are dissolved in 200ml methanol respectively, it is preceding
Person is added slowly with stirring in the latter, continues to stir 12min, is then allowed to stand 20h.Centrifuge separation is washed three times, at 150 DEG C
Lower vacuum drying 8h obtains ZIF-67-150.2g dicyandiamide and 1g cobalt acetate are dissolved in 60ml ethyl alcohol, the heating stirring at 80 DEG C
5h adds the ZIF-67-150 of 0.2g, and after stirring 48h at room temperature, 60 DEG C are evaporated acquisition solid powder.Solid powder is taken to be placed in
Corundum boat is heated to 800 DEG C under nitrogen protection with 2 DEG C/min heating rate and keeps the temperature 1h, then cold with 5 DEG C/min rate of temperature fall
But carbon nanotube is taken out to room temperature.
Using the ZIF-67 of 150nm as template, the carbon nanotube of outer diameter about 100nm is prepared.
Embodiment 3
At 20 DEG C, the 2-methylimidazole of the zinc nitrate hexahydrate of 1.470g and 3.260 is dissolved in 50ml methanol respectively, the former
It is added slowly with stirring in the latter, continues to stir 12min, be then allowed to stand 20h.Centrifuge separation is washed three times, in 150 DEG C of temperature
Degree is lower to be dried in vacuo 8h, obtains ZIF-8-80.2g dicyandiamide and 1g cobalt acetate are dissolved in 60ml ethyl alcohol, the heating stirring at 80 DEG C
5h adds the ZIF-8-80 of 0.2g, and after stirring 48h at room temperature, 60 DEG C are evaporated acquisition solid powder.Solid powder is taken to be placed in just
Yu Zhou is heated to 800 DEG C under nitrogen protection with 2 DEG C/min heating rate and keeps the temperature 1h, then cooling with 5 DEG C/min rate of temperature fall
Carbon nanotube is taken out to room temperature.
Using the ZIF-8 of 100nm as template, the carbon nanotube of outer diameter about 50nm is prepared.
Embodiment 4
At 20 DEG C, the 2-methylimidazole of the cabaltous nitrate hexahydrate of 1.436g and 3.244g are dissolved in 100ml methanol respectively, it is preceding
Person is added slowly with stirring in the latter, continues to stir 12min, is then allowed to stand 20h.Centrifuge separation is washed three times, at 150 DEG C
Lower vacuum drying 8h obtains ZIF-67-300.2g dicyandiamide and 1g cobalt acetate are dissolved in 60ml ethyl alcohol, the heating stirring at 80 DEG C
5h adds the ZIF-67-300 of 0.2g, and after stirring 48h at room temperature, 60 DEG C are evaporated acquisition solid powder.Solid powder is taken to be placed in
Corundum boat is heated to 1000 DEG C under nitrogen protection with 2 DEG C/min heating rate and keeps the temperature 1h, then with 5 DEG C/min rate of temperature fall
It is cooled to room temperature taking-up carbon nanotube.
Embodiment 5
At 20 DEG C, the 2-methylimidazole of the cabaltous nitrate hexahydrate of 1.436g and 3.244g are dissolved in 100ml methanol respectively, it is preceding
Person is added slowly with stirring in the latter, continues to stir 12min, is then allowed to stand 20h.Centrifuge separation is washed three times, at 150 DEG C
Lower vacuum drying 8h obtains ZIF-67-300.2g dicyandiamide and 1g cobalt acetate are dissolved in 60ml ethyl alcohol, the heating stirring at 80 DEG C
5h adds the ZIF-67-300 of 0.2g, and after stirring 48h at room temperature, 60 DEG C are evaporated acquisition solid powder.Solid powder is taken to be placed in
Corundum boat is heated to 800 DEG C under nitrogen protection with 2 DEG C/min heating rate and keeps the temperature 2h, then cold with 5 DEG C/min rate of temperature fall
But carbon nanotube is taken out to room temperature.
Embodiment 6
At 20 DEG C, the 2-methylimidazole of the cabaltous nitrate hexahydrate of 1.436g and 3.244g are dissolved in 100ml methanol respectively, it is preceding
Person is added slowly with stirring in the latter, continues to stir 12min, is then allowed to stand 20h.Centrifuge separation is washed three times, at 150 DEG C
Lower vacuum drying 8h obtains ZIF-67-300.2g dicyandiamide and 1g cobalt acetate are dissolved in 60ml ethyl alcohol, the heating stirring at 80 DEG C
5h adds the ZIF-67-300 of 0.1g, and after stirring 48h at room temperature, 60 DEG C are evaporated acquisition solid powder.Solid powder is taken to be placed in
Corundum boat is heated to 800 DEG C under protection of argon gas with 2 DEG C/min heating rate and keeps the temperature 1h, then cold with 5 DEG C/min rate of temperature fall
But carbon nanotube is taken out to room temperature.
Claims (17)
1. a kind of carbon nanotube, it is characterised in that: the carbon nanotube be in Bamboo-shaped pattern, i.e. every carbon nanotube by 2 sections with
On Bamboo-shaped pipeline section be linked in sequence, N element is contained in the carbon nanotube, one end is enclosed with metal nanoparticle;Institute
The outer diameter for stating carbon nanotube is 50-300nm.
2. carbon nanotube as described in claim 1, it is characterised in that: form existing for the N element is pyridine N, pyrroles N, stone
One or more of inkization N and oxidation N, nitrogen mass content are 2%-8%.
3. carbon nanotube as described in claim 1, it is characterised in that: the metal nanoparticle is iron and/or cobalt, metal nano
The diameter of particle is 50-300nm.
4. carbon nanotube as described in claim 1, it is characterised in that: the metal nanoparticle accounts for carbon nanotube gross mass
1%-10%.
5. the carbon nanotube as described in claim 1-4 is any, it is characterised in that: the more excellent outer diameter of the carbon nanotube is 300nm;
The more excellent diameter of the metal nanoparticle is 300nm.
6. a kind of preparation method of any carbon nanotube of claim 1-5, it is characterised in that: include the following steps,
(1) synthesis of metal organic framework: the mixed solution of zinc salt and organic ligand is prepared;It is reacted at 30-120 DEG C, so
Isolated metal organic framework afterwards;
(2) preparation of presoma: metal salt and amino-compound are dissolved in solvent, it is organic that the metal prepared in step (1) is added
Skeleton after being uniformly dispersed, removes solvent and obtains presoma;
(3) preparation of carbon nanotube: presoma obtained by step (2) is heat-treated under an inert atmosphere, obtains end package gold
The carbon nanotube of metal nano-particle.
7. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: zinc salt described in step (1) be zinc nitrate,
One or more of zinc chloride, zinc sulfate, concentration of the zinc ion in mixed solution are 0.0125-0.1mol/L.
8. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: machine ligand described in step (1) is 2- first
Base imidazoles, concentration of the organic ligand in mixed solution are 0.1-0.8mol/L.
9. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: in mixed solution described in step (1)
Solvent is one of methanol, ethyl alcohol, water and DMF.
10. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: metal salt described in step (2) be cobalt or
One or more of the chloride of iron, nitrate, acetate.
11. the preparation method of carbon nanotube as claimed in claim 5, it is characterised in that: amino-compound described in step (2) is
One or more of urea, dicyandiamide, melamine.
12. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: solvent described in step (2) be methanol,
The mixed solution of one or more of second alcohol and water.
13. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: metal salt and amino described in step (2)
The mass ratio 1:1-1:5 of compound.
14. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: remove the side of solvent described in step (2)
Method is rotary evaporation and/or vacuum drying.
15. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: step (3) heat treatment process is to rise
Temperature is to 800-1100 DEG C and keeps 0.5-3h, is then cooled to room temperature;From room temperature to heat treatment temperature in the temperature-rise period
The heating rate of degree is 2-5 DEG C/min;Rate of temperature fall is 1-10 DEG C/min in the temperature-fall period.
16. the preparation method of carbon nanotube as claimed in claim 6, it is characterised in that: step (3) inert atmosphere is nitrogen
The gaseous mixture of one or both of gas, argon gas.
17. the application of carbon nanotube as described in claim 1-5 is any, it is characterised in that: the catalyst is polymer electrolytic
Membrane fuel cell and metal air battery cathodes oxygen reduction reaction elctro-catalyst.
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CN110683530A (en) * | 2019-08-26 | 2020-01-14 | 广西大学 | Method for in-situ synthesis of cobalt-nitrogen co-doped carbon nano tube |
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