CN104370279A - Carbon nanotube, and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a carbon nanotube, and a preparation method and an application thereof. The carbon nanotube is a heteroatom-doped carbon nanotube, the mass ratio of heteroatoms is 3%-6%, the surface of the carbon nanotube has a mesoporous structure, the mesoporous average pore size is 2 nm-9 nm, and the specific surface area of the carbon nanotube is 150 m<2>/g-1200 m<2>/g. The preparation method comprises the following steps: (1) evenly mixing the carbon nanotube with an etching agent, and making the mass ratio be 1:3 to 1:5; (2) under an oxygen isolated condition, heating up to 500 DEG C-900 DEG C, and calcining for 1 h-3 h; (3) washing and drying; and (4) carrying out heteroatom doping. The specific surface area of the carbon nanotube can be improved, the catalytic activity of the carbon nanotube is increased, and the carbon nanotube has the advantages of simple process and low cost, and is applied to preparation of electrocatalysts having good performance.
Description
Technical field
The invention belongs to field of nanometer material technology, more specifically, relate to a kind of carbon nanotube, Preparation Method And The Use.
Background technology
Carbon nanotube has the electroconductibility of metal or semi-conductor, and the advantages such as wideband electromagnetic ripple absorptivity intensity is high, excellent adsorption, make it have been widely used in physical chemistry field.Particularly have wide application prospects at storage hydrogen, ultracapacitor, molecular filter, sorbent material, fuel-cell catalyst etc.In the application in these fields, except there are certain requirements carbon nanotube crystalline structure, its specific surface area, pore volume are had higher requirements.But what can prepare on a large scale at present is multi-walled carbon nano-tubes, and its specific surface area is lower, generally at 200m
2/ below g, have impact on its effect needing high-specific surface area aspect to apply as hydrogen storage material, ultracapacitor, eelctro-catalyst etc.
Now there are some researches show, adulterate heteroatoms in carbon nanotube, can improve the catalytic performance of carbon nanotube, is applied to prepare fuel battery energy and effectively improve fuel battery performance.Current carbon nano tube-doped technology, mainly by vapour deposition process or acid activation method, adulterate heteroatoms in carbon nanotube.But the productive rate of the doped carbon nanometer pipe prepared of vapour deposition process (CVD) method, Heteroatom doping amount, specific surface area are all lower, and production cost is high, limits its large-scale production.Acid activation method can not improve the specific surface area of carbon nanotube equally very well, and technique comparatively bothers, and is not suitable for large-scale production.
Summary of the invention
For above defect or the Improvement requirement of prior art, the invention provides a kind of carbon nanotube, Preparation Method And The Use, its object is to by adding alkali calcining, etching carbon nanotube is formed mesoporous on its surface, thus raising specific surface area of carbon nanotube, improving Heteroatom doping amount, to solve carbon nanometer pipe catalytic activity thus not high, and the doped carbon nanometer pipe productive rate caused is not high, Heteroatom doping amount and specific surface area is lower, production cost is high and the technical problem of complex process.
For achieving the above object, according to one aspect of the present invention, provide a kind of carbon nanotube, described carbon nanotube is the carbon nanotube of Heteroatom doping, wherein heteroatomic mass ratio is 3% to 6%, described carbon nano tube surface has meso-hole structure, and mesoporous mean pore size is between 2nm to 9nm, and the specific surface area of described carbon nanotube is at 150m
2/ g to 1200m
2between/g.Preferably, described carbon nanotube, heteroatoms described in it is one or both in nitrogen-atoms, boron atom, phosphorus atom and sulphur atom, wherein according to mass percentage, nitrogen element is between 1% to 10%, boron is between 0.3% to 6%, and element sulphur is between 0.5% to 5%, and phosphoric is between 0.2% to 4%.
Preferably, described carbon nanotube, its nitrogen-atoms adulterates with the form of pyridine nitrogen, pyrroles's nitrogen and/or greying nitrogen; Boron atom adulterates with the form of carbon boron singly-bound, oxygen boron singly-bound and/or nitrogen boron singly-bound; Sulphur atom adulterates with the form of carbon sulphur singly-bound and/or carbon sulphur double bond; Phosphorus atom adulterates with the form of carbon phosphorus singly-bound and/or oxygen phosphorus singly-bound.
According to another aspect of the present invention, provide a kind of preparation method of described carbon nanotube, comprise the following steps:
(1) by carbon nanotube and highly basic or alkali-metal carbonate Homogeneous phase mixing, make the mass ratio of carbon nanotube and highly basic or alkali-metal carbonate between 1:3 to 1:5, obtain the mixture of carbon nanotube and highly basic or alkali-metal carbonate;
(2) mixture will obtained in step (1), is warming up between 500 DEG C to 900 DEG C under the condition of starvation, and calcining 1 is little of 3 hours, obtains calcinate;
(3) calcinate will obtained in step (2), washing is dry removes highly basic or alkali-metal carbonate, obtains the carbon nanotube through etching;
(4) carbon nanotube through etching will obtained in step (3), carries out Heteroatom doping, namely obtains carbon nanotube as described in claims 1 to 3 any one.
Preferably, described preparation method, highly basic described in it is KOH or NaOH.
Preferably, described preparation method, alkali-metal carbonate described in it is Na
2cO
3or K
2cO
3.
Preferably, described preparation method, its step (4) described heteroatoms is one or both in nitrogen-atoms, boron atom, phosphorus atom and sulphur atom.
Preferably, described preparation method, the method for its step (4) described doping is high temperature dopant or hydro-thermal doping.According to another aspect of the present invention, provide a kind of described carbon nanotube and be applied to and prepare eelctro-catalyst.
Preferably, described carbon nanotube is applied to prepares eelctro-catalyst, and eelctro-catalyst described in it is used for catalytic fuel cell or lithium-air battery cathode oxygen reduction reaction.
In general, the above technical scheme conceived by the present invention compared with prior art, can obtain following beneficial effect:
(1) Heteroatom doping provided by the invention carbon nanotube be compared with prior art doping type carbon nanotube, specific surface area improves 1 to 10 times, its doping and oxygen reduction activity site quantity are all significantly increased, react for catalytic oxidation-reduction, catalytic efficiency significantly improves, therefore be applied to fuel cell or lithium-air battery, battery reserve of electricity can be significantly improved;
(2) carbon nanotube of Heteroatom doping provided by the invention, because surface has meso-hole structure, therefore can strengthen fully contacting of electrolytic solution and avtive spot, as eelctro-catalyst, catalytic activity significantly improves;
(3) carbon nanotube of Heteroatom doping provided by the invention, when the heteroatoms adulterated especially nitrogen-atoms, boron atom, phosphorus atom and sulphur atom, the electro catalytic activity of described carbon nanotube significantly strengthens;
(4) preparation method of the nanotube of Heteroatom doping provided by the invention, technique is simple, condition is easily controlled, with low cost, be suitable for serialization large-scale mass production.
Accompanying drawing explanation
Fig. 1 is the XPS collection of illustrative plates of embodiment 1 nitrogen sulfur doping etching carbon nanotube;
Fig. 2 is the adsorption desorption curve that embodiment 1 etches carbon nanotube and carbon nanotube;
Fig. 3 is the cyclic voltammetry curve of embodiment 6 nitrogen sulfur doping etching carbon nanotube and carbon nanotube;
Fig. 4 is the linear polarisation curves of embodiment 6 nitrogen sulfur doping etching carbon nanotube and carbon nanotube.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.In addition, if below in described each embodiment of the present invention involved technical characteristic do not form conflict each other and just can mutually combine.
Carbon nanotube provided by the invention, for the carbon nanotube of Heteroatom doping, wherein heteroatomic mass ratio is 1% to 11%, and described carbon nano tube surface has meso-hole structure, mesoporous mean pore size is between 2nm to 9nm, and the specific surface area of described carbon nanotube is at 150m
2/ g to 1200m
2between/g.Described heteroatoms is one or both in nitrogen-atoms, boron atom, phosphorus atom and sulphur atom, wherein according to mass percentage, nitrogen element is between 1% to 10%, and boron is between 0.3% to 6%, element sulphur is between 0.5% to 5%, and phosphoric is between 0.2% to 4%.
The existing way of described nitrogen-atoms is pyridine nitrogen, pyrroles's nitrogen and/or greying nitrogen.Boron atom adulterates with the form of carbon boron singly-bound (C-B-C), oxygen boron singly-bound (O-B-C) and/or nitrogen boron singly-bound (N-B-C).Sulphur atom adulterates with the form of carbon sulphur singly-bound (C-S-C) and/or carbon sulphur double bond (-C=S-); Phosphorus atom adulterates with the form of carbon phosphorus singly-bound (C-P-C) and/or oxygen phosphorus singly-bound (O-P-C).
Carbon nanotube provided by the invention, its preparation method, comprises the following steps:
(1) by carbon nanotube and highly basic or alkali-metal carbonate Homogeneous phase mixing, make the mass ratio of carbon nanotube and highly basic or alkali-metal carbonate between 1:3 to 1:5, obtain the mixture of carbon nanotube and highly basic or alkali-metal carbonate; Described highly basic is preferably KOH or NaOH, and described alkali-metal carbonate is preferably Na
2cO
3or K
2cO
3.
(2) mixture will obtained in step (1), is warming up between 500 DEG C to 900 DEG C under the condition of starvation, and calcining 1 is little of 3 hours, obtains calcinate;
(3) calcinate will obtained in step (2), washing is dry removes highly basic or alkali-metal carbonate, obtains the carbon nanotube through etching;
(4) carbon nanotube through etching will obtained in step (3), carries out Heteroatom doping, namely obtains carbon nanotube provided by the invention.Described heteroatoms is one or both in nitrogen-atoms, boron atom, phosphorus atom and sulphur atom.The method of described doping is high temperature dopant or hydro-thermal doping.
Carbon nanotube provided by the invention is applied to prepares eelctro-catalyst, for catalytic fuel cell or lithium-air battery cathode oxygen reduction reaction, can significantly improve the performance of fuel cell or lithium-air battery.
Be below embodiment:
Embodiment 1
A kind of carbon nanotube, for the carbon nanotube of Heteroatom doping, x-ray photoelectron spectroscopy as shown in Figure 1, wherein heteroatomic mass ratio is 4%, described carbon nano tube surface has meso-hole structure, mesoporous mean pore size is between 5nm, and as shown in Figure 2, the specific surface area of described carbon nanotube is 369.5m to adsorption desorption curve
2between/g.Described heteroatoms is nitrogen-atoms and sulphur atom, and wherein according to mass percentage, nitrogen element is 3%, and element sulphur is 1%.
Adulterating with the form of pyridine nitrogen, pyrroles's nitrogen and greying nitrogen of described nitrogen-atoms.Sulphur atom adulterates with the form of carbon sulphur singly-bound (C-S-C) and carbon sulphur double bond (-C=S-).
Described carbon nanotube, its preparation method, comprises the following steps:
(1) by carbon nanotube and NaOH Homogeneous phase mixing, the mass ratio making carbon nanotube and NaOH is 1:4, obtains the mixture of carbon nanotube and NaOH.
(2) mixture will obtained in step (1), is warming up between 800 DEG C under the condition of starvation, calcines 2 hours, obtains calcinate;
(3) calcinate will obtained in step (2), washing is dry removes NaOH, obtains the carbon nanotube through etching;
(4) carbon nanotube through etching will obtained in step (3), carries out Heteroatom doping, namely obtains carbon nanotube provided by the invention.Its concrete operation step is:
A, by step (3) gained etching carbon nanotube and thiocarbamide carry out Homogeneous phase mixing with the mass ratio of 1:8.
B, steps A gained mixture is risen to 800 DEG C with the temperature rise rate of 5 DEG C/min in protective atmosphere, calcine 2 hours.Described shielding gas is nitrogen.
Embodiment 2
A kind of carbon nanotube, be the carbon nanotube of Heteroatom doping, wherein heteroatomic mass ratio is 11%, and described carbon nano tube surface has meso-hole structure, and mesoporous mean pore size is 2nm, and the specific surface area of described carbon nanotube is 1200m
2between/g.Described heteroatoms is nitrogen-atoms, boron atom, and wherein according to mass percentage, nitrogen element is 9%, and boron is 2%.
Adulterating with the form of pyridine nitrogen, pyrroles's nitrogen and greying nitrogen of described nitrogen-atoms.Boron atom adulterates with the form of carbon boron singly-bound (C-B-C), oxygen boron singly-bound (O-B-C) and nitrogen boron singly-bound (N-B-C).
Described carbon nanotube, its preparation method, comprises the following steps:
(1) by carbon nanotube and KOH Homogeneous phase mixing, the mass ratio making carbon nanotube and KOH is 1:5, obtains the mixture of carbon nanotube and KOH.
(2) mixture will obtained in step (1), is warming up between 500 DEG C under the condition of starvation, calcines 1 hour, obtains calcinate;
(3) calcinate will obtained in step (2), washing is dry removes KOH, obtains the carbon nanotube through etching;
(4) carbon nanotube through etching will obtained in step (3), carries out Heteroatom doping, namely obtains carbon nanotube provided by the invention.Its concrete operation step is:
A, by step (3) gained etching carbon nanotube carry out Homogeneous phase mixing with urea and boric acid with the mass ratio of 1:8 respectively.
B, steps A gained mixture is risen to 800 DEG C with the temperature rise rate of 5 DEG C/min in protective atmosphere, calcine 2 hours.Described shielding gas is nitrogen.
Embodiment 3
A kind of carbon nanotube, be the carbon nanotube of Heteroatom doping, wherein heteroatomic mass ratio is 1%, and described carbon nano tube surface has meso-hole structure, and mesoporous mean pore size is between 9nm, and the specific surface area of described carbon nanotube is 150m
2between/g.Described heteroatoms is nitrogen-atoms and phosphorus atom, and wherein according to mass percentage, nitrogen element is 1%, and phosphoric is 0.3%.
Adulterating with the form of pyridine nitrogen, pyrroles's nitrogen and greying nitrogen of described nitrogen-atoms.Phosphorus atom adulterates with the form of carbon phosphorus singly-bound (C-P-C) and oxygen phosphorus singly-bound (O-P-C).
Described carbon nanotube, its preparation method, comprises the following steps:
(1) by carbon nanotube and Na
2cO
3homogeneous phase mixing, makes carbon nanotube and Na
2cO
3mass ratio be 1:3, obtain carbon nanotube and Na
2cO
3mixture.
(2) mixture will obtained in step (1), is warming up between 900 DEG C under the condition of starvation, calcines 3 hours, obtains calcinate;
(3) calcinate will obtained in step (2), washing is dry removes Na
2cO
3, obtain the carbon nanotube through etching;
(4) carbon nanotube through etching will obtained in step (3), carries out Heteroatom doping, namely obtains carbon nanotube provided by the invention.Its concrete operation step is:
A, by step (3) gained etching carbon nanotube carry out Homogeneous phase mixing with urea and triphenyl phosphorus with the mass ratio of 1:8 respectively.
B, steps A gained mixture is risen to 800 DEG C with the temperature rise rate of 5 DEG C/min in protective atmosphere, calcine 2 hours.Described shielding gas is nitrogen.
Embodiment 4
A kind of carbon nanotube, be the carbon nanotube of Heteroatom doping, wherein heteroatomic mass ratio is 4%, and described carbon nano tube surface has meso-hole structure, and mesoporous mean pore size is 6nm, and the specific surface area of described carbon nanotube is 400m
2/ g.Described heteroatoms is nitrogen-atoms, and wherein according to mass percentage, nitrogen element is 4%.
Adulterating with the form of pyridine nitrogen, pyrroles's nitrogen and greying nitrogen of described nitrogen-atoms.
Described carbon nanotube, its preparation method, comprises the following steps:
(1) by carbon nanotube and NaOH Homogeneous phase mixing, the mass ratio making carbon nanotube and NaOH is 1:3, obtains the mixture of carbon nanotube and NaOH.
(2) mixture will obtained in step (1), is warming up between 800 DEG C under the condition of starvation, calcines 3 hours, obtains calcinate;
(3) calcinate will obtained in step (2), washing is dry removes NaOH, obtains the carbon nanotube through etching;
(4) carbon nanotube through etching will obtained in step (3), carries out Heteroatom doping, namely obtains carbon nanotube provided by the invention.Its concrete operation step is:
A, by step (3) gained etching carbon nanotube with carry out Homogeneous phase mixing with urea with the mass ratio of 1:8.
B, steps A gained mixture is risen to 800 DEG C with the temperature rise rate of 5 DEG C/min in protective atmosphere, calcine 2 hours.Described shielding gas is nitrogen.
Embodiment 5
A kind of carbon nanotube, be the carbon nanotube of Heteroatom doping, wherein heteroatomic mass ratio is 4%, and described carbon nano tube surface has meso-hole structure, and mesoporous mean pore size is 6nm, and the specific surface area of described carbon nanotube is 400m
2/ g.Described heteroatoms is nitrogen-atoms, and wherein according to mass percentage, nitrogen element is 3%.
Adulterating with the form of pyridine nitrogen, pyrroles's nitrogen and greying nitrogen of described nitrogen-atoms.
Described carbon nanotube, its preparation method, comprises the following steps:
(1) by carbon nanotube and NaOH Homogeneous phase mixing, the mass ratio making carbon nanotube and NaOH is 1:3, obtains the mixture of carbon nanotube and NaOH.
(2) mixture will obtained in step (1), is warming up between 800 DEG C under the condition of starvation, calcines 3 hours, obtains calcinate;
(3) calcinate will obtained in step (2), washing is dry removes NaOH, obtains the carbon nanotube through etching;
(4) carbon nanotube through etching will obtained in step (3), carries out Heteroatom doping, namely obtains carbon nanotube provided by the invention.Its concrete operation step is:
A, by step (3) gained etching carbon nanotube be placed in 50mL small beaker with urea with the mass ratio of 1:8, add 40mL deionized water, ultrasonic disperse is even.
B, steps A gained mixture is placed in 50mL hydrothermal reaction kettle, reacts 5 hours at 200 DEG C.
Embodiment 6
In embodiment 1, gained nitrogen sulfur doping carbon nanotube has carried out fuel battery negative pole electrocatalysis test, and as shown in Figure 3 and Figure 4, its concrete operation step is for cyclic voltammetry curve and linear polarisation curves:
A, by carbon nanotube loaded on glass-carbon electrode for gained nitrogen sulfur doping in embodiment 1, and be placed in 50mL electrolyzer, link electrochemical workstation.Wherein reference electrode is reversible hydrogen electrode (RHE), working electrode is glass-carbon electrode, supporting electrode is platinum electrode, and ionogen is the perchloric acid solution of 0.1mol/L.
B, steps A device carried out respectively in nitrogen and oxygen atmosphere cyclic voltammetric and linear polarization test.
C, result show, the carbon nanotube after Heteroatom doping, is applied to fuel battery cathod catalyst, can significantly improve catalytic activity, improve the serviceability of fuel cell.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a carbon nanotube, is characterized in that, described carbon nanotube is the carbon nanotube of Heteroatom doping, wherein heteroatomic mass ratio is 3% to 6%, described carbon nano tube surface has meso-hole structure, and mesoporous mean pore size is between 2nm to 9nm, and the specific surface area of described carbon nanotube is at 150m
2/ g to 1200m
2between/g.
2. carbon nanotube as claimed in claim 1, it is characterized in that, described heteroatoms is one or both in nitrogen-atoms, boron atom, phosphorus atom and sulphur atom, wherein according to mass percentage, nitrogen element is between 1% to 10%, boron is between 0.3% to 6%, and element sulphur is between 0.5% to 5%, and phosphoric is between 0.2% to 4%.
3. carbon nanotube as claimed in claim 2, it is characterized in that, described nitrogen-atoms adulterates with the form of pyridine nitrogen, pyrroles's nitrogen and/or greying nitrogen; Boron atom adulterates with the form of carbon boron singly-bound, oxygen boron singly-bound and/or nitrogen boron singly-bound; Sulphur atom adulterates with the form of carbon sulphur singly-bound and/or carbon sulphur double bond; Phosphorus atom adulterates with the form of carbon phosphorus singly-bound and/or oxygen phosphorus singly-bound.
4. the preparation method of the carbon nanotube as described in claims 1 to 3 any one, is characterized in that, comprises the following steps:
(1) by carbon nanotube and highly basic or alkali-metal carbonate Homogeneous phase mixing, make the mass ratio of carbon nanotube and highly basic or alkali-metal carbonate between 1:3 to 1:5, obtain the mixture of carbon nanotube and highly basic or alkali-metal carbonate;
(2) mixture will obtained in step (1), is warming up between 500 DEG C to 900 DEG C under the condition of starvation, and calcining 1 is little of 3 hours, obtains calcinate;
(3) calcinate will obtained in step (2), washing is dry removes highly basic or alkali-metal carbonate, obtains the carbon nanotube through etching;
(4) carbon nanotube through etching will obtained in step (3), carries out Heteroatom doping, namely obtains carbon nanotube as described in claims 1 to 3 any one.
5. preparation method as claimed in claim 4, it is characterized in that, described highly basic is KOH or NaOH.
6. preparation method as claimed in claim 5, it is characterized in that, described alkali-metal carbonate is Na
2cO
3or K
2cO
3.
7. preparation method as claimed in claim 4, is characterized in that, step (4) described heteroatoms is one or both in nitrogen-atoms, boron atom, phosphorus atom and sulphur atom.
8. preparation method as claimed in claim 4, is characterized in that, the method for step (4) described doping is high temperature dopant or hydro-thermal doping.
9. the carbon nanotube as described in claims 1 to 3 any one is applied to prepares eelctro-catalyst.
10. carbon nanotube as claimed in claim 9 is applied to and prepares eelctro-catalyst, it is characterized in that, described eelctro-catalyst is used for catalytic fuel cell or lithium-air battery cathode oxygen reduction reaction.
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