CN103706388A - Composite material of nitrogen-doped porous carbon-wrapped carbon nano tube as well as preparation method and application of material - Google Patents
Composite material of nitrogen-doped porous carbon-wrapped carbon nano tube as well as preparation method and application of material Download PDFInfo
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Abstract
The invention relates to a composite material of a nitrogen-doped porous carbon-wrapped carbon nano tube as well as a preparation method and an application of the composite material. The preparation method comprises the following steps: dispersing the carbon nano tube in water, adding a carbon source to obtain a reaction system, subsequently performing hydrothermal reaction, performing thermal treatment on the carbon nano tube wrapped with a carbon layer on the surface, and a nitrogen source at the high temperature so as to obtain the composite material of the nitrogen-doped porous carbon-wrapped carbon nano tube. According to the preparation method, the carbon source is polymerized under a hydrothermal reaction condition so as to obtain the carbon layer, the outer surface of the carbon nano tube is wrapped with the carbon layer, subsequently the carbon layer is carbonized and decomposed to generate a porous structure under high temperature treatment, and at the same time, the gasified nitrogen source is diffused to the carbon layer through ducts to be subjected to in-situ doping. The composite material provided by the invention can be used as a cathode oxidation reduction catalyst of a fuel battery, is excellent in catalysis, and is high in oxidation activity when being compared with other nitrogen-doped materials reported in documents. The preparation method provided by the invention is simple and economic in process, convenient to operate and easy to achieve the large-scale production.
Description
Technical field
The present invention relates to composite of nitrogen doping porous carbon enveloped carbon nanometer tube and preparation method thereof, and this composite is as the application of oxygen reduction catalyst.
Background technology
Fuel cell is a kind of cleanliness without any pollution and the TRT that has very high energies conversion efficiency, in solving great energy problem, is accounting for very important status.Yet its crucial Cathodic oxygen reduction dynamics is slow, need rare noble metal as catalyst, this with regard to serious obstruction the extensive use of fuel cell.Many people start to utilize the special constructions such as noble metal and other transition metal component alloy or nucleocapsid, improve the utilization rate of noble metal and reduce its carrying capacity, but this can not break away from the limitation of noble metal itself all the time.Therefore the non-precious metal catalyst that, exploitation has a hyperoxia reduction catalysts activity more and more receives people's concern.
As far back as the seventies in last century six, the material with carbon element of doping is just considered to good hydrogen reduction non-precious metal catalyst.In recent years, some highly active doping carbon materials were in the news.And due to its cheapness and good anti methanol toxication performance, doping carbon material is considered to one of material likely substituting in future noble metal catalyst.In numerous hetero atoms, the doping of nitrogen-atoms is studied by people the earliest.At present, prepare nitrogen-doped carbon material and mainly contain three kinds of methods: the one, in-situ doped method, in growth carbon skeleton, adulterate, for example chemical vapour deposition (CVD), often can the adulterate hetero atom of high-load of this preparation method, but its expensive equipment and responsive preparation condition are unfavorable for the large-scale production of catalyst.The 2nd, post processing doping method, be generally by the graphitized carbon material of conduction with contain heteroatomic compound and at high temperature process and adulterate, because carbonization structure brings resistance to doping, therefore heteroatomic content is conventionally lower, can not obtain desirable catalytic activity.The problem existing for above-mentioned two kinds of methods, people have proposed the third doping method, be about to low degree of graphitization or do not have the nitrogenous material with carbon element of carbonization structure directly to carry out high-temperature process, solve the problem that content of heteroatoms is lower, and then compound with some conductive carbon skeletons, improve the mobility of electronics in catalytic process.CNT has been widely studied and actual use as the carrier of catalyst, and its specific area and good electric conductivity can effectively improve compound catalyst performance.Yet, how, by CNT and suitable compound of nitrogenous material with carbon element, improve heteroatomic utilization rate and still exist at present very large challenge.
Therefore, develop a kind of simple, economical, green, can make full use of hetero atom, be suitable for large-scale production prepare CNT and the compound technology tool of nitrogenous material with carbon element is of great significance.
Summary of the invention
One of object of the present invention is to provide the composite of nitrogen doping porous carbon enveloped carbon nanometer tube.
Two of object of the present invention is to provide a kind of preparation method of composite of nitrogen doping porous carbon enveloped carbon nanometer tube.
Three of object of the present invention is to provide the composite of nitrogen doping porous carbon enveloped carbon nanometer tube as the application of oxygen reduction catalyst.
The composite of nitrogen of the present invention doping porous carbon enveloped carbon nanometer tube forms by the CNT as internal layer conductive network with at the nitrogen-doped porous carbon material shell of described CNT outer cladding.
The length of described CNT can be 1～30 micron, is preferably 5～15 microns; Diameter can be 10 nanometer～100 nanometers, is preferably 40～60 nanometers.
The thickness of described nitrogen-doped porous carbon material shell can be 10 nanometer～100 nanometers, is preferably 20 nanometer～50 nanometers.
Described nitrogen doping porous carbon, the content of its nitrogen-atoms is 3～15%, is preferably 5～10%.
The pore size in the hole in described porous carbon is 1 nanometer～20 nanometer, is preferably 2 nanometer～5 nanometers.
The specific area of described composite is 100～500m
2/ g, is preferably 200～500m
2/ g.
The preparation method of the composite of nitrogen doping porous carbon enveloped carbon nanometer tube of the present invention is:
In water, add carbon source to obtain reaction system carbon nanotube dispersed, then carry out hydro-thermal reaction, obtain the CNT that surface is coated with carbonaceous layer; The CNT and the nitrogenous source that the surface obtaining are coated with to carbonaceous layer are at high temperature heat-treated, and obtain the composite of nitrogen doping porous carbon enveloped carbon nanometer tube.
The temperature of described hydro-thermal reaction is 120 ℃～190 ℃, is preferably 180 ℃; Reaction time is 6～20 hours, is preferably 10～15 hours.
Described heat treated temperature is 600 ℃～1000 ℃, is preferably 800 ℃～1000 ℃, most preferably is 900 ℃.
In described reaction system, the mass ratio that feeds intake of CNT and carbon source is 1:20～1:60, is preferably 1:40.
Described surface is coated with the CNT of carbonaceous layer and the mass ratio that feeds intake of nitrogenous source is 1:5～1:20, is preferably 1:10.
Described carbon source is selected from one or more in glucose, dopamine, polyaniline, is preferably glucose.
Described nitrogenous source is selected from one or more in melamine, nitrile ammonia, two nitrile ammonia, urea, is preferably melamine.
Preparation method of the present invention is simple, economy, products obtained therefrom nitrogen content are high, the composite of the nitrogen that can be mass-produced doping porous carbon enveloped carbon nanometer tube, and the cathodic oxygen reduction catalyst that this composite can be used as fuel cell is used.
Preparation method of the present invention utilizes carbon source, under hydrothermal reaction condition, polymerization obtains carbonaceous layer, and be coated on the outer surface of CNT, then carbonaceous layer carbonization under high-temperature process decompose to produce loose structure, simultaneously the nitrogenous source of gasification by duct diffuse in carbonaceous layer, carry out in-situ doped.
The present invention compares with other prior art, has following characteristics:
1, in the present invention, adopt hydro-thermal method at the coated carbonaceous layer of outer surface of CNT, compare as concentrated sulfuric acid carbonization sucrose in solution phase with other method, hydro-thermal method is simple, and covered effect is better, and thickness is easy to control, and is suitable for large-scale production.
2, in the present invention, adopt hydro-thermal method to prepare the carbonaceous layer of enveloped carbon nanometer tube, again through high-temperature process doping nitrogen, than other doping of high-temperature process to graphitized carbon material, the nitrogenous source that the loose structure that the carbonization decomposition of carbonaceous layer produces is conducive to gasify carries out original position to carbonaceous layer and efficiently adulterates, and described loose structure can accelerate the mass transport process of electrochemical reaction.
3, in the present invention, adopting cheap melamine, cyanamide etc. is nitrogenous source, compares as ammonia, hydrogen cyanide with other nitrogenous source, and melamine doped process is relatively safe, and inventory is easy to control.
4, the doping method adopting in the present invention is to adulterate when carbon atom trends towards graphitization, the in-situ doped method of this kind and other method are as in-situ doped and post processing doping, can either obtain higher nitrogen atom content, can make again catalyst keep having good electric conductivity.
The catalytic performance of the composite that 5, prepared by the present invention is excellent, compares have higher hydrogen reduction activity with other nitrogen dopant material of bibliographical information.
6, method technique of the present invention is simple, economical, operation is convenient, be easy to large-scale production, at many industrial catalysts or other scientific domain, has huge potential using value.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the composite of embodiment 1 gained nitrogen doping porous carbon enveloped carbon nanometer tube.
Fig. 2 is specific area test curve (a) and the pore-size distribution test curve (b) of the composite of embodiment 1 gained nitrogen doping porous carbon enveloped carbon nanometer tube.
Fig. 3 is that the photoelectron spectroscopy of the composite of embodiment 1 gained nitrogen doping porous carbon enveloped carbon nanometer tube is swept spectrogram (a) and N1s swarming spectrogram (b) entirely.
Fig. 4 is the hydrogen reduction empirical curve of embodiment 1 composite of gained nitrogen doping porous carbon enveloped carbon nanometer tube and the carbon supported platinum catalyst of commercial use.
Fig. 5 is the methanol tolerance test experiments curve (a) of composite of embodiment 1 gained nitrogen doping porous carbon enveloped carbon nanometer tube and the methanol tolerance test experiments curve (b) of the carbon supported platinum catalyst of commercial use.
Fig. 6 is the stability test empirical curve of embodiment 1 composite of gained nitrogen doping porous carbon enveloped carbon nanometer tube and the carbon supported platinum catalyst of commercial use.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described raw material all can obtain from open commercial sources if no special instructions.
By 20mg CNT (diameter 40 nanometer to 60 nanometers, 5 microns to 15 microns of length) ultrasonic dispersion after 1 hour in 10mL water, add 800mg glucose, being transferred to until completely dissolved 25mL and take in the autoclave that polytetrafluoroethylene (PTFE) is liner, is then at 180 ℃, to carry out hydro-thermal reaction 15 hours in temperature, through water, ethanol washing for several times, suction filtration, obtain solid, 60 ℃ of oven dry, spend the night, obtain surface and be coated with the CNT that thickness is about 25～35 nanometer carbonaceous layers; The CNT that the surface obtaining is coated with to carbonaceous layer be take with melamine after ratio that mass ratio is 1:10 mixes; be transferred in porcelain boat; and insert in the quartz ampoule of tube furnace; with argon gas deacration half an hour; be warming up to again 900 ℃; under argon shield, heat-treat after two hours, obtain the composite of nitrogen doping porous carbon enveloped carbon nanometer tube.
The transmission electron microscope photo of the composite of gained nitrogen doping porous carbon enveloped carbon nanometer tube as shown in Figure 1, described composite forms by the CNT as internal layer conductive network with at the nitrogen-doped porous carbon material shell of described CNT outer cladding as seen from the figure, and the thickness of described shell is about 25～35 nanometers.
As shown in Figure 2, adsorption-desorption curve is shown in (a) figure in the specific area test of the composite of gained nitrogen doping porous carbon enveloped carbon nanometer tube, and pore-size distribution test curve is shown in (b) figure.As seen from the figure, described composite has micropore and meso-hole structure, and its specific area is 413m
2/ g.From pore size distribution curve, the aperture major part in the hole in the nitrogen doping porous carbon in described composite is in the scope of 1～4 nanometer.
The photoelectron spectroscopy of the composite of gained nitrogen doping porous carbon enveloped carbon nanometer tube entirely sweeps spectrogram and N1s swarming spectrogram is shown in respectively Fig. 3, and wherein, photoelectron spectroscopy is entirely swept spectrogram and seen (a) figure, and N1s swarming spectrogram is shown in (b) figure.As seen from the figure, nitrogen element is successfully doped in carbonaceous layer, and the content of nitrogen-atoms is 6.93%, and wherein main component is pyridine type nitrogen and the quaternary nitrogen that hydrogen reduction catalytic activity is high.
Therefore from above-mentioned data, described composite forms by the CNT as internal layer conductive network with at the nitrogen-doped porous carbon material shell of described CNT outer cladding, and the cathodic oxygen reduction catalyst that described composite can be used as fuel cell is used; Wherein, heat treatment is after two hours at 900 ℃, and the thickness of the nitrogen-doped porous carbon material shell obtaining is about 25～35 nanometers, and the specific area of described composite is 413m
2/ g, the content of nitrogen-atoms in described composite is 6.93%.
The hydrogen reduction empirical curve of the composite of gained nitrogen doping porous carbon enveloped carbon nanometer tube and the carbon supported platinum catalyst of commercial use as shown in Figure 4.Concrete test method is: hydrogen reduction empirical curve is measured in the potassium hydroxide solution of 0.1 mol/L by rotating disk electrode (r.d.e), and the rotating speed of rotating disk electrode (r.d.e) is 1600 revs/min, and curved scanning speed is 5 millivolts/second.
Contrast is that the business carbon supported platinum catalyst that the platinum weight percentage of ten thousand rich (Johnson-Matthey) (Shanghai) catalyst Co., Ltd is 20% is believed in purchase from the village with the carbon supported platinum catalyst of commercial use.
Compare two curves, can find out, the half wave potential of composite performance in hydrogen reduction experiment of the above-mentioned nitrogen doping porous carbon enveloped carbon nanometer tube preparing with respect to the current potential of silver/silver chlorate reference electrode (electrolyte is the aqueous solution of potassium nitrate mass fraction 10%) is-0.184V, than business, with the half wave potential-0.142V of carbon supported platinum catalyst, only bear 42mV, therefore show good hydrogen reduction electro catalytic activity.
The methanol tolerance test experiments curve of the composite of gained nitrogen doping porous carbon enveloped carbon nanometer tube and the carbon supported platinum catalyst of commercial use is shown in Fig. 5, wherein: the methanol tolerance test experiments curve of described composite is shown in (a) figure, the methanol tolerance test experiments curve of the carbon supported platinum catalyst of commercial use is shown in (b) figure.Concrete test method is: hydrogen reduction empirical curve is measured in the potassium hydroxide solution of 0.1 mol/L that contains 0.5 mol/L methyl alcohol by rotating disk electrode (r.d.e), and the rotating speed of rotating disk electrode (r.d.e) is 1600 revs/min, and curved scanning speed is 5 millivolts/second.
Relatively the curve in two figure, can find out that the relative business of composite of the nitrogen doping porous carbon enveloped carbon nanometer tube that the present embodiment prepares has fabulous anti methanol toxication performance with carbon supported platinum catalyst.
The stability test empirical curve of the composite of gained nitrogen doping porous carbon enveloped carbon nanometer tube and the carbon supported platinum catalyst of commercial use is shown in Fig. 6.Concrete test method is: hydrogen reduction empirical curve is measured in the potassium hydroxide solution of 0.1 saturated mol/L of oxygen by rotating disk electrode (r.d.e), and the rotating speed of rotating disk electrode (r.d.e) is 1600 revs/min, and constant potential is-0.2V that test time is 20000 seconds.
Relatively two curves, can find out that the relative business of composite of the nitrogen doping porous carbon enveloped carbon nanometer tube that the present embodiment prepares has better stability with carbon supported platinum catalyst.
Substantially according to the method identical with embodiment 1, prepare the composite of nitrogen doping porous carbon enveloped carbon nanometer tube, difference is that 900 ℃ of adopting during by heat treatment are changed to 800 ℃, and the specific area of resulting composite is 101m
2/ g, wherein the thickness of the coated shell of nitrogen doping porous carbon is about 30～40 nanometers, and the content of nitrogen-atoms is 15.76%.
Embodiment 3
Substantially according to the method identical with embodiment 1, prepare the composite of nitrogen doping porous carbon enveloped carbon nanometer tube, difference is that 900 ℃ of adopting during by heat treatment are changed to 1000 ℃, and the specific area of resulting composite is 479m
2/ g, wherein the thickness of the coated shell of nitrogen doping porous carbon is about 10～20 nanometers, and the content of nitrogen-atoms is 3.54%.
Embodiment 4
Substantially according to the method identical with embodiment 1, prepare the composite of nitrogen doping porous carbon enveloped carbon nanometer tube, difference is according to mass ratio, to be that 1:60 feeds intake by CNT and glucose, and in resulting composite, the thickness of the coated shell of nitrogen doping porous carbon is about 50～60 nanometers.
Substantially according to the method identical with embodiment 1, prepare the composite of nitrogen doping porous carbon enveloped carbon nanometer tube, difference is that employing length is 1～5 micron, diameter is that the CNT of 10～30 nanometers is raw material, by CNT and glucose, according to mass ratio, be that 1:20 feeds intake, the temperature of hydro-thermal reaction is changed to 120 ℃, the time of hydro-thermal reaction is changed to 6 hours, and in resulting composite, the thickness of the coated shell of nitrogen doping porous carbon is about 10～20 nanometers.
Substantially according to the method identical with embodiment 1, prepare the composite of nitrogen doping porous carbon enveloped carbon nanometer tube, difference is that employing length is 20～30 microns long, diameter is that the CNT of 80～100 nanometers is raw material, by CNT and glucose, according to mass ratio, be that 1:60 feeds intake, the time of hydro-thermal reaction is changed to 20 hours, the temperature of hydro-thermal reaction is changed to 190 ℃, 900 ℃ that during by heat treatment, adopt are changed to 600 ℃, and in resulting composite, the thickness of the coated shell of nitrogen doping porous carbon is about 90～100 nanometers.
Substantially according to the method identical with embodiment 1, prepare the composite of nitrogen doping porous carbon enveloped carbon nanometer tube, difference is to adopt dopamine to replace glucose as carbon source, and according to mass ratio, be that 1:5 feeds intake by CNT and melamine that surface is coated with carbonaceous layer, in resulting composite, the content of nitrogen-atoms is 4.69%.
Substantially according to the method identical with embodiment 1, prepare the composite of nitrogen doping porous carbon enveloped carbon nanometer tube, difference is to adopt nitrile ammonia to replace melamine as nitrogenous source, and according to mass ratio, be that 1:20 feeds intake by CNT and nitrile ammonia that surface is coated with carbonaceous layer, in resulting composite, the content of nitrogen-atoms is 8.37%.
It should be noted that, above-described embodiment is just used for illustrating technical characterictic of the present invention, is not for limiting the claimed scope of the present invention.Such as the carbon source relating in embodiment, nitrogenous source, also can use other reactant, but this type of in-situ doped method still belongs to the claimed category of the present invention.
Claims (10)
1. a composite for nitrogen doping porous carbon enveloped carbon nanometer tube, is characterized in that: described composite forms by the CNT as internal layer conductive network with at the nitrogen-doped porous carbon material shell of described CNT outer cladding.
2. the composite of nitrogen doping porous carbon enveloped carbon nanometer tube according to claim 1, is characterized in that: the length of described CNT is 1～30 micron, and diameter is 10 nanometer～100 nanometers.
3. the composite of nitrogen doping porous carbon enveloped carbon nanometer tube according to claim 1, is characterized in that: the thickness of described nitrogen-doped porous carbon material shell is 10 nanometer～100 nanometers.
4. according to the composite of the nitrogen doping porous carbon enveloped carbon nanometer tube described in claim 1 or 3, it is characterized in that: described nitrogen doping porous carbon, the content of its nitrogen-atoms is 3～15%.
5. the composite of nitrogen doping porous carbon enveloped carbon nanometer tube according to claim 1, is characterized in that: the specific area of described composite is 100～500m
2/ g.
6. the preparation method of the composite of the nitrogen described in claim 1～5 any one doping porous carbon enveloped carbon nanometer tube, it is characterized in that: by carbon nanotube dispersed in water, add carbon source to obtain reaction system, then carry out hydro-thermal reaction, obtain the CNT that surface is coated with carbonaceous layer; The CNT and the nitrogenous source that the surface obtaining are coated with to carbonaceous layer are heat-treated, and obtain the composite of nitrogen doping porous carbon enveloped carbon nanometer tube;
Described carbon source is selected from one or more in glucose, dopamine, polyaniline;
Described nitrogenous source is selected from one or more in melamine, nitrile ammonia, two nitrile ammonia, urea.
7. preparation method according to claim 6, is characterized in that: the temperature of described hydro-thermal reaction is 120 ℃～190 ℃, and the reaction time is 6～20 hours;
Described heat treated temperature is 600 ℃～1000 ℃.
8. preparation method according to claim 6, is characterized in that: in described reaction system, the mass ratio that feeds intake of CNT and carbon source is 1:20～1:60.
9. preparation method according to claim 6, is characterized in that: described surface is coated with the CNT of carbonaceous layer and the mass ratio that feeds intake of nitrogenous source is 1:5～1:20.
10. an application for the composite of the doping of the nitrogen described in claim 1～5 any one porous carbon enveloped carbon nanometer tube, is characterized in that: the composite of described nitrogen doping porous carbon enveloped carbon nanometer tube is used as the cathodic oxygen reduction catalyst of fuel cell.
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