CN105355934A - Preparation method of nitrogen-doped carbon nanotubes - Google Patents
Preparation method of nitrogen-doped carbon nanotubes Download PDFInfo
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Abstract
The invention relates to a preparation method of nitrogen-doped carbon nanotubes. The technical problems to be solved in the invention are high cost and complex process of present nitrogen-doped carbon nanotube preparation methods. The method comprises the following steps: 1, dissolving FeCl3 in a methyl orange solution, stirring until uniformity, adding ammonium persulfate, continuously stirring until uniformity, adding aniline, adjusting the pH value to 0.8-1.0, and standing at room temperature to obtain a mixture; 2, centrifuging the mixture, washing the obtained solid phase substance, and drying to obtain polyaniline nanotubes; 3, carrying out vacuum sintering on the polyaniline nanotubes under the protection of nitrogen to obtain primarily-nitrogen-doped carbon nanotubes; and 4, carrying out vacuum sintering to obtain the nitrogen-doped carbon nanotubes with the specific surface area of 764-877m<2>/g, containing a hierarchical porous structure and having uniform distribution. The above prepared material can be used as a fuel battery cathode oxygen reduction electrocatalyst.
Description
Technical field
The present invention relates to the preparation method of nitrogen-doped carbon nanometer pipe.
Background technology
In recent years, along with the fast development of industry, the energy that the people such as coal, oil and natural gas commonly use even is on the verge of exhaustion in continuous minimizing, and therefore the price of energy resource also constantly rises.In order to Optimization of Energy Structure, reduce environmental pollution, development secondary energy sources, as solar energy, wind energy and fuel cell etc. become the research emphasis of scholars gradually.Fuel cell (FuelCell) is a kind of the 4th kind of generation mode after waterpower, firepower and nuclear energy power generation, it is as novel energy conversion device, the chemical energy be stored in fuel and oxidant stable power can be provided incessantly, this is because directly can not be converted to electric energy by burning by fuel cell.But still there is the commercialization that two large problems governs fuel cell at present.One, the eelctro-catalyst in conventional fuel cells is the costliness of such as platinum etc. and the limited precious metal material of reserves.Its two, the efficiency of the redox reactions (OxygenReductionReaction, ORR) that negative electrode carries out is poor.Therefore, improving the performance of fuel cell not only needs to find other non-metallic catalysts to substitute now to use noble metal catalyst, also will prepare with simple effective method the eelctro-catalyst that ORR activity is better than noble metal (as platinum etc.) simultaneously.Nitrogen-doped carbon nanometer pipe due to nitrogen-atoms by carbon atom replace after, substantially increase its catalytic activity, therefore often fuel-cell catalyst is used to, the preparation method of existing nitrogen-doped carbon nanometer pipe, as disclosed a kind of preparation method of nitrogen-doped carbon nanometer pipe in the article " preparation of polyaniline-modified nitrogen-doped carbon mitron and ultracapacitor performance thereof " on the Acta PhySico-Chimica Sinica of the 29th volume the 1st phase in 2013, the method: with the carbon nano-tube of commercialization for carbon source, take polyaniline as nitrogenous source, first utilize aniline to form polyaniline 0 DEG C of condition polymerization and wrap in carbon nano tube surface, nitrogen-doped carbon nanometer pipe is obtained again through Pintsch process.The method need cost higher, have requirement to reaction temperature, must carry out in ice-water bath, process is loaded down with trivial details.
Summary of the invention
The present invention is the technical problem that cost is high, process is complicated of the preparation method that will solve existing nitrogen-doped carbon mitron, and provides a kind of preparation method of nitrogen-doped carbon nanometer pipe.
The preparation method of nitrogen-doped carbon nanometer pipe of the present invention, carries out according to the following steps:
One, by FeCl
3, ammonium persulfate and aniline mol ratio be 1:(0.4 ~ 0.6): (1.4 ~ 1.6) take FeCl
3, ammonium persulfate and aniline, by FeCl
3being dissolved in concentration is in 0.006 ~ 0.008mol/L methyl orange solution, after stirred at ambient temperature 20 ~ 35min, then adds ammonium persulfate, after continuing stirring 10 ~ 20min, then adds aniline, finally uses H
2sO
4aqueous solution adjust ph is 0.8 ~ 1.0, and left at room temperature 24 ~ 30h, obtains mixture;
Two, mixture centrifugation step one obtained, outwells supernatant, takes off a layer sediment, with distilled water and the abundant washing precipitate of ethanol, then puts into the vacuum drying chamber 6 ~ 12h of 40 ~ 80 DEG C, obtains polyaniline nanotube;
Three, the polyaniline nanotube obtained in step 2 is directly put into vacuum tube furnace, under the protection of nitrogen, be warming up to 400 ~ 800 DEG C with 1 ~ 10 DEG C/min heating rate and be incubated 2 ~ 7h, naturally obtain elementary nitrogen doped carbon nanotube after cooling;
Four, after elementary nitrogen doped carbon nanotube step 3 obtained places 5 ~ 7 days in atmosphere; again put into vacuum tube furnace; under the protection of nitrogen, be warming up to 900 ~ 1000 DEG C of insulations for 1 ~ 1.5h with the heating rate of 1 ~ 10 DEG C/min, naturally obtain nitrogen-doped carbon nanometer pipe after cooling.
The present invention take conductive polymer polyanaline as Carbon and nitrogen sources, adopts chemical oxidative polymerization to obtain presoma, then prepares nitrogen-doped carbon nanometer pipe by Pintsch process process.The nitrogen-atoms existed in raw material aniline not only ensure that existence and the content of nitrogen-atoms in final material with carbon element, further simplify preparation process, after Pintsch process, the molecular skeleton of polyaniline becomes carbon skeleton, but the nitrogen element still retained wherein, the specific area of the nitrogen-doped carbon nanometer pipe obtained is high, be evenly distributed containing multi-stage artery structure.
The conductance that the present invention utilizes polyaniline higher and structure diversity, unique doping phenomenon, good thermal stability, chemical stability and reversible electrochemical redox performance and potential solution and melt-processable, control polymerization process, prepare the combination of conducting polymer and material with carbon element, its microscopic appearance has uniform tubular feature, and (Open Circuit Potential of nitrogen-doped carbon nanometer pipe prepared by the present invention is E as the Open Circuit Potential shown during ORR electrode material than commercial Pt/C catalyst corrigendum
onsetthe Open Circuit Potential of 0.032Vvs.SCE, Pt/C is E
onset0.028Vvs.SCE), i.e. more excellent activity; And after continuous circulation 32000s, the current density of nitrogen-doped carbon nanometer pipe still can remain to original 93%, and the current density of commercial Pt/C catalyst has been reduced to original 26%, illustrate nitrogen-doped carbon nanometer pipe prepared by the present invention not only good stability and the life-span longer.
This material can be used as fuel battery negative pole hydrogen reduction (ORR) eelctro-catalyst, be widely used in electrical devices, as the electrode material of fuel battery negative pole ORR eelctro-catalyst or ultracapacitor, there is selectivity high, the advantages such as catalytic efficiency is good, and the life-span is long.Nitrogen doped carbon nanotube in the present invention is to the catalytic efficiency of ORR and selectivity, all based on the chemical property of itself, without the need to adding other reagent and special preparation technique, reducing preparation technology's cost, providing new approaches for preparation is used as the efficient ORR eelctro-catalyst of fuel cell.
Accompanying drawing explanation
Fig. 1 is transmission electron microscope (TEM) figure of polyaniline nanotube prepared by test 1;
Fig. 2 is transmission electron microscope (TEM) figure of nitrogen-doped carbon nanometer pipe prepared by test 1;
Fig. 3 is the Raman analysis of spectra of nitrogen-doped carbon nanometer pipe prepared by test 1;
Fig. 4 is the adsorption-desorption curve of nitrogen-doped carbon nanometer pipe prepared by test 1;
Fig. 5 is the pore size distribution curve of nitrogen-doped carbon nanometer pipe prepared by test 1;
Fig. 6 is X-ray diffraction (XRD) figure of nitrogen-doped carbon nanometer pipe prepared by test 1;
Fig. 7 is the XPS spectrum figure (N1s spectrogram) of the nitrogen-doped carbon nanometer pipe prepared by test 1;
Fig. 8 tests the cyclic voltammetry curve (CV) of the nitrogen-doped carbon nanometer pipe prepared by 1;
Fig. 9 is linear sweep voltammetry (LSV) curve of nitrogen-doped carbon nanometer pipe prepared by test 1;
Figure 10 is the time current curve of nitrogen-doped carbon nanometer pipe prepared by test 1;
Figure 11 is the time current curve (also having 3mol/L methyl alcohol in electrolyte) of the nitrogen-doped carbon nanometer pipe of test 1.
Figure 12 is transmission electron microscope (TEM) figure of nitrogen-doped carbon nanometer pipe prepared by test 2;
Figure 13 is the Raman analysis of spectra of nitrogen-doped carbon nanometer pipe prepared by test 2;
Figure 14 is the adsorption-desorption curve of nitrogen-doped carbon nanometer pipe prepared by test 2;
Figure 15 is the pore size distribution curve of nitrogen-doped carbon nanometer pipe prepared by test 2;
Figure 16 is X-ray diffraction (XRD) figure of nitrogen-doped carbon nanometer pipe prepared by test 2;
Figure 17 is the XPS spectrum figure (N1s spectrogram) of the nitrogen-doped carbon nanometer pipe prepared by test 2;
Figure 18 tests the cyclic voltammetry curve (CV) of the nitrogen-doped carbon nanometer pipe prepared by 2;
Figure 19 is linear sweep voltammetry (LSV) curve of nitrogen-doped carbon nanometer pipe prepared by test 2
Embodiment
Embodiment one: the preparation method of the nitrogen-doped carbon nanometer pipe of present embodiment, carry out according to the following steps:
One, by FeCl
3, ammonium persulfate and aniline mol ratio be 1:(0.4 ~ 0.6): (1.4 ~ 1.6) take FeCl
3, ammonium persulfate and aniline, by FeCl
3being dissolved in concentration is in 0.006 ~ 0.008mol/L methyl orange solution, after stirred at ambient temperature 20 ~ 35min, then adds ammonium persulfate, after continuing stirring 10 ~ 20min, then adds aniline, finally uses H
2sO
4aqueous solution adjust ph is 0.8 ~ 1.0, and left at room temperature 24 ~ 30h, obtains mixture;
Two, mixture centrifugation step one obtained, outwells supernatant, takes off a layer sediment, with distilled water and the abundant washing precipitate of ethanol, then puts into the vacuum drying chamber 6 ~ 12h of 40 ~ 80 DEG C, obtains polyaniline nanotube;
Three, the polyaniline nanotube obtained in step 2 is directly put into vacuum tube furnace, under the protection of nitrogen, be warming up to 400 ~ 800 DEG C with 1 ~ 10 DEG C/min heating rate and be incubated 2 ~ 7h, naturally obtain elementary nitrogen doped carbon nanotube after cooling;
Four, after elementary nitrogen doped carbon nanotube step 3 obtained places 5 ~ 7 days in atmosphere; again put into vacuum tube furnace; under the protection of nitrogen, be warming up to 900 ~ 1000 DEG C of insulations for 1 ~ 1.5h with the heating rate of 1 ~ 10 DEG C/min, naturally obtain nitrogen-doped carbon nanometer pipe after cooling.
Embodiment two: present embodiment and embodiment one unlike in step one by FeCl
3be dissolved in after in methyl orange solution, FeCl
3concentration is 0.06 ~ 0.08mol/L; Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two are unlike H in step one
2sO
4the concentration of the aqueous solution is 0.4 ~ 0.5mol/L; Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three are 60 DEG C unlike the temperature of vacuum drying chamber in step 2, and the vacuumize time is 10h; Other is identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike in step 3 under the protection of nitrogen, be warming up to 500 DEG C with 5 DEG C/min heating rate and be incubated 5h; Other is identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to four unlike in step 3 under the protection of nitrogen, be warming up to 600 DEG C with 6 DEG C/min heating rate and be incubated 4h; Other is identical with one of embodiment one to four.
Embodiment seven: one of present embodiment and embodiment one to four unlike in step 3 under the protection of nitrogen, be warming up to 700 DEG C with 8 DEG C/min heating rate and be incubated 3h; Other is identical with one of embodiment one to four.
Embodiment eight: one of present embodiment and embodiment one to seven unlike in step 4 under the protection of nitrogen, be warming up to 950 DEG C of insulations for 1 ~ 1.2h with the heating rate of 8 DEG C/min; Other is identical with one of embodiment one to seven.
With following verification experimental verification beneficial effect of the present invention:
Test 1: the nitrogen-doped carbon nanometer pipe preparation method of this test carries out according to the following steps:
One, by 2mmol solid FeCl
3being dissolved in 30mL concentration is in 0.007mol/L methyl orange solution, after stirred at ambient temperature 30min, adds 1mmol solid ammonium persulfate, continues to stir after 20min, then adds 3mmol aniline, is finally 0.4 ~ 0.5mol/LH by 30mL concentration
2sO
4aqueous solution adjust ph is 0.8, and left at room temperature 24h, obtains mixture;
Two, mixture centrifugation step one obtained, outwells supernatant, takes off a layer sediment, with distilled water and the abundant washing precipitate of ethanol, then puts into the vacuum drying chamber 10h of 70 DEG C, obtains polyaniline nanotube;
Three, the polyaniline nanotube obtained in step 2 is directly put into vacuum tube furnace, under the protection of nitrogen, be warming up to 400 DEG C with 8 DEG C/min heating rate and be incubated 5h, naturally obtain elementary nitrogen doped carbon nanotube after cooling;
Four, after elementary nitrogen doped carbon nanotube step 3 obtained places 5 days in atmosphere, again put into vacuum tube furnace, under the protection of nitrogen, be warming up to 900 DEG C of insulations for 1.5h with the heating rate of 5 DEG C/min, naturally obtain nitrogen-doped carbon nanometer pipe after cooling.
In this test procedure two, transmission electron microscope (TEM) figure of the polyaniline nanotube of preparation as shown in Figure 1, transmission electron microscope (TEM) figure of the nitrogen-doped carbon nanometer pipe obtained in step 4 as shown in Figure 2, as can be seen from Figure 1, polyaniline nanotube is the tubular structure that internal diameter is about 80nm, and the outer wall of pipe is long irregular flocculent substance.The microscopic appearance of the nitrogen-doped carbon nanometer pipe obtained after carbonization polyaniline nanotube is shown in Figure 2, comparison diagram 1 and Fig. 2 known, even if after high-temperature process, the pattern of product still can keep well, and the internal diameter uniquely unlike pipe has become 60nm.This this one dimension tubular structure illustrating prepared by this test can at high temperature keep its original pattern not to be destroyed.
The Raman spectrogram of the nitrogen-doped carbon nanometer pipe obtained in this test procedure four as shown in Figure 3, as can be seen from Figure 3, at 1360cm
-1and 1580cm
-1two characteristic absorption peaks, be respectively the distinctive D peak of material with carbon element and G peak.Wherein, D peak represents the degree of disorder of material with carbon element, also can be described as structural disorder peak.And G peak is the typical Raman peaks of body phase crystalline graphite.Ratio (the I of D peak and G peak relative intensity
d/ I
g) directly indicate defects count in nitrogen-doped carbon material and carbonizing degree.The I of the nitrogen-doped carbon nanometer pipe of this test preparation
d/ I
g=0.71, there is the defect of a greater number in this illustrative material, and the degree of disorder of material is larger.
The nitrogen adsorption desorption isothermal curve of the nitrogen-doped carbon nanometer pipe obtained in this test procedure four as shown in Figure 4, as can be seen from Figure 4, shows to there is more micropore and boundary's pore structure in nitrogen-doped carbon nanometer pipe, and by can be calculated, its BET specific surface area is 877m
2/ g, this illustrates, the novel nitrogen doped carbon nanometer pipe of this test preparation has higher specific area.Pore size distribution curve as shown in Figure 5 can be found out, the main integrated distribution of surface apertures of sample is at 1.0 ~ 2.5nm, and between 20 ~ 45nm, pore-size distribution is more wide in range, illustrates that its surface has hierarchical porous structure.Also specific area test has been carried out to the elementary nitrogen doped carbon nanotube that step 3 obtains simultaneously, known that its specific area is 366m
2/ g, contrasts known, and the secondary carbonization of step 4, improves the specific area of material.
The XRD figure of the nitrogen-doped carbon nanometer pipe obtained in this test procedure four as shown in Figure 6, as can be drawn from Figure 6, there are two characteristic diffraction peaks, appear at 2 θ=25 ° and 43 ° respectively, these two diffraction maximums are respectively the diffraction maximum of amorphous carbon material distinctive (002) and (100) crystal face, this result shows that novel nitrogen doped carbon nanometer pipe prepared by this test there occurs carbonization to a certain degree, and this and Raman result match.
The N1sXPS spectrogram of the nitrogen-doped carbon nanometer pipe obtained in this test procedure four as shown in Figure 7, as can be seen from Figure 7,399.0,400.3,401.4 and 402.6,403.8 and 405.3eV place can see obvious characteristic peak, these peaks correspond respectively to pyridine N, pyrroles N, graphite-phase N and oxidized form N, their existence illustrates that nitrogen-atoms has successfully entered into the carbon skeleton of material intuitively, illustrates that the material that this test prepares is nitrogen-doped carbon nanometer pipe.By calculated by peak area, know that the graphite-phase N content of the nitrogen-doped carbon nanometer pipe obtained in this test procedure four is 51.3% (atomic percent); Also XPS spectrum figure test analysis has been carried out to the elementary nitrogen doped carbon nanotube that step 3 obtains simultaneously, known that the graphite-phase N content of elementary nitrogen doped carbon nanotube is 26.1% (atomic percent); Contrast known, the secondary carbonization of step 4, nitrogen-atoms is reset, and improves the graphite-phase N content of material.
Test the chemical property of the nitrogen-doped carbon nanometer pipe of this test preparation, concrete operations are as follows: be scattered in by 5mg nitrogen-doped carbon nanometer pipe in the 0.8mL ethanol water (volume ratio of second alcohol and water is 1:1) containing 20 μ L5%Nafion, ultrasonic 1h, obtain the liquid as ink shape, then getting the ultrasonic good liquid applicator of 5 μ L is on the glass-carbon electrode of 5mm at diameter, be linked in electrochemical workstation, with the saturated 0.1mol/LKOH aqueous solution of oxygen for electrolyte, adopt cyclic voltammetry technology and its ORR catalytic performance of linear sweep voltammetry technical testing.As shown in Figure 8, as shown in Figure 9, as shown in Figure 10, as can be seen from Fig. 8 and Fig. 9, nitrogen-doped carbon nanometer pipe is at O for time graph for LSV curve for the CV curve of the nitrogen-doped carbon nanometer pipe obtained
2show excellent catalytic performance to ORR in saturated 0.1mol/LKOH solution, catalysis current potential is-0.154V and 0.032Vvs.SCE respectively.This result has exceeded business-like Pt/C catalyst now.Time graph (Figure 10) in conjunction with nitrogen-doped carbon nanometer pipe material can draw, the nitrogen-doped carbon nanometer pipe of this test preparation is when continuous circulation 32000s, its electric current can also remain original 93%, illustrate that it not only has excellent ORR catalytic performance, also indicate good stability simultaneously.
The time current curve of the nitrogen-doped carbon nanometer pipe of Figure 11 prepared by this test in the KOH aqueous solution containing 3mol/L methyl alcohol, can find out, after adding methyl alcohol, the current density of product almost remains unchanged, and illustrates that it has excellent selective catalysis ORR performance.
Characterization result according to the said goods can draw, adopt the disclosed step of this test, successfully prepared there is high-specific surface area, carbon nano-tube that the polyaniline of hierarchical porous structure derives doping, this product not only regular appearance, size uniform, and at high temperature can stable existence, keep its pattern not to be destroyed.And excellent ORR catalytic activity can be shown in the basic conditions.
Test 2: the nitrogen-doped carbon nanometer pipe preparation method of this test carries out according to the following steps:
One, by 2mmol solid FeCl
3being dissolved in 30mL concentration is in 0.007mol/L methyl orange solution, after stirred at ambient temperature 30min, adds 1mmol solid ammonium persulfate, continues to stir after 20min, then adds 3mmol aniline, is finally 0.4 ~ 0.5mol/LH by 30mL concentration
2sO
4aqueous solution adjust ph is 1.0, and left at room temperature 24h, obtains mixture;
Two, mixture centrifugation step one obtained, outwells supernatant, takes off a layer sediment, with distilled water and the abundant washing precipitate of ethanol, then puts into the vacuum drying chamber 10h of 70 DEG C, obtains polyaniline nanotube;
Three, the polyaniline nanotube obtained in step 2 is directly put into vacuum tube furnace, under the protection of nitrogen, be warming up to 600 DEG C with 8 DEG C/min heating rate and be incubated 5h, naturally obtain elementary nitrogen doped carbon nanotube after cooling;
Four, after elementary nitrogen doped carbon nanotube step 3 obtained places 5 days in atmosphere, again put into vacuum tube furnace, under the protection of nitrogen, be warming up to 950 DEG C of insulations for 1.5h with the heating rate of 5 DEG C/min, naturally obtain nitrogen-doped carbon nanometer pipe after cooling.
In this test procedure four, transmission electron microscope (TEM) figure of the polyaniline nanotube of preparation as shown in figure 12, as can be seen from Figure 12, even if after high-temperature process, the pattern of product still can keep well, the irregular flocculent substance of pipe outer wall tails off, pipe interior through having become 50nm.This this one dimension tubular structure illustrating prepared by this test can at high temperature keep its original pattern not to be destroyed.
The Raman spectrogram of the nitrogen-doped carbon nanometer pipe obtained in this test procedure four as shown in figure 13, as can be seen from Figure 13, at 1360cm
-1and 1580cm
-1two characteristic absorption peaks, be respectively the distinctive D peak of material with carbon element and G peak.Wherein, D peak represents the degree of disorder of material with carbon element, also can be described as structural disorder peak.And G peak is the typical Raman peaks of body phase crystalline graphite.Ratio (the I of D peak and G peak relative intensity
d/ I
g) directly indicate defects count in nitrogen-doped carbon material and carbonizing degree.The I of the nitrogen-doped carbon nanometer pipe of this test preparation
d/ I
g=0.72, there is the defect of a greater number in this illustrative material, and the degree of disorder of material is larger.
The nitrogen adsorption desorption isothermal curve of the nitrogen-doped carbon nanometer pipe obtained in this test procedure four as shown in figure 14, as can be seen from Figure 14, shows to there is more micropore and boundary's pore structure in nitrogen-doped carbon nanometer pipe, and by can be calculated, its BET specific surface area is 764m
2/ g, this illustrates, the novel nitrogen doped carbon nanometer pipe of this test preparation has higher specific area.Pore size distribution curve as shown in Figure 15 can be found out, the main integrated distribution of surface apertures of sample is at 1.0 ~ 2.5nm, and between 20 ~ 45nm, pore-size distribution is more wide in range, illustrates that its surface has hierarchical porous structure.Also tested the specific area of the elementary nitrogen-doped carbon nanometer pipe that step 3 obtains, be 407m simultaneously
2/ g, more known, the carbonization treatment of secondary, improves the specific area of material.
The XRD figure of the nitrogen-doped carbon nanometer pipe obtained in this test procedure four as shown in figure 16, as can be drawn from Figure 16, there are two characteristic diffraction peaks, appear at 2 θ=25 ° and 43 ° respectively, these two diffraction maximums are respectively the diffraction maximum of amorphous carbon material distinctive (002) and (100) crystal face, this result shows that novel nitrogen doped carbon nanometer pipe prepared by this test there occurs carbonization to a certain degree, and this and Raman result match.
The N1sXPS spectrogram of the nitrogen-doped carbon nanometer pipe obtained in this test procedure four as shown in figure 17, as can be seen from Figure 17,399.0,400.3,401.4 and 402.6,403.8 and 405.3eV place can see obvious characteristic peak, these peaks correspond respectively to pyridine N, pyrroles N, graphite-phase N and oxidized form N, their existence illustrates that nitrogen-atoms has successfully entered into the carbon skeleton of material intuitively, illustrates that the material that this test prepares is nitrogen-doped carbon nanometer pipe.By calculated by peak area, know that the graphite-phase N content of the nitrogen-doped carbon nanometer pipe obtained in this test procedure four is 42% (atomic percent); Also XPS spectrum figure test analysis has been carried out to the elementary nitrogen doped carbon nanotube that step 3 obtains simultaneously, known that the graphite-phase N content of elementary nitrogen doped carbon nanotube is 24.6% (atomic percent); Contrast known, the secondary carbonization of step 4, nitrogen-atoms is reset, and improves the graphite-phase N content of material.
Test the chemical property of the nitrogen-doped carbon nanometer pipe of this test preparation, concrete operations are as follows: be scattered in by 5mg nitrogen-doped carbon nanometer pipe in the 0.8mL ethanol water (volume ratio of second alcohol and water is 1:1) containing 20 μ L5%Nafion, ultrasonic 1h, obtain the liquid as ink shape, then getting the ultrasonic good liquid applicator of 5 μ L is on the glass-carbon electrode of 5mm at diameter, be linked in electrochemical workstation, with the saturated 0.1mol/LKOH aqueous solution of oxygen for electrolyte, adopt cyclic voltammetry technology and its ORR catalytic performance of linear sweep voltammetry technical testing.As shown in figure 18, as shown in figure 19, as can be seen from Figure 18 and Figure 19, nitrogen-doped carbon nanometer pipe is at O for LSV curve for the CV curve of the nitrogen-doped carbon nanometer pipe obtained
2show excellent catalytic performance to ORR in saturated 0.1mol/LKOH solution, catalysis current potential is-0.21V and 0.013Vvs.SCE respectively.
Characterization result according to the said goods can draw, adopt the disclosed step of this test, successfully prepared there is high-specific surface area, carbon nano-tube that the polyaniline of hierarchical porous structure derives doping, this product not only regular appearance, size uniform, and at high temperature can stable existence, keep its pattern not to be destroyed.And excellent ORR catalytic activity can be shown in the basic conditions.
Claims (8)
1. a preparation method for nitrogen-doped carbon nanometer pipe, is characterized in that the method is carried out according to the following steps:
One, by FeCl
3, ammonium persulfate and aniline mol ratio be 1:(0.4 ~ 0.6): (1.4 ~ 1.6) take FeCl
3, ammonium persulfate and aniline, by FeCl
3being dissolved in concentration is in 0.006 ~ 0.008mol/L methyl orange solution, after stirred at ambient temperature 20 ~ 35min, then adds ammonium persulfate, after continuing stirring 10 ~ 20min, then adds aniline, finally uses H
2sO
4aqueous solution adjust ph is 0.8 ~ 1.0, and left at room temperature 24 ~ 30h, obtains mixture;
Two, mixture centrifugation step one obtained, outwells supernatant, takes off a layer sediment, with distilled water and the abundant washing precipitate of ethanol, then puts into the vacuum drying chamber 6 ~ 12h of 40 ~ 80 DEG C, obtains polyaniline nanotube;
Three, the polyaniline nanotube obtained in step 2 is directly put into vacuum tube furnace, under the protection of nitrogen, be warming up to 400 ~ 800 DEG C with 1 ~ 10 DEG C/min heating rate and be incubated 2 ~ 7h, naturally obtain elementary nitrogen doped carbon nanotube after cooling;
Four, after elementary nitrogen doped carbon nanotube step 3 obtained places 5 ~ 7 days in atmosphere; again put into vacuum tube furnace; under the protection of nitrogen, be warming up to 900 ~ 1000 DEG C of insulations for 1 ~ 1.5h with the heating rate of 1 ~ 10 DEG C/min, naturally obtain nitrogen-doped carbon nanometer pipe after cooling.
2. the preparation method of a kind of nitrogen-doped carbon nanometer pipe according to claim 1, is characterized in that FeCl in step one
3be dissolved in after in methyl orange solution, FeCl
3concentration is 0.06 ~ 0.08mol/L.
3. the preparation method of a kind of nitrogen-doped carbon nanometer pipe according to claim 1 and 2, is characterized in that H in step one
2sO
4the concentration of the aqueous solution is 0.4 ~ 0.5mol/L.
4. the preparation method of a kind of nitrogen-doped carbon nanometer pipe according to claim 1 and 2, it is characterized in that the temperature of vacuum drying chamber in step 2 is 60 DEG C, the vacuumize time is 10h.
5. the preparation method of a kind of nitrogen-doped carbon nanometer pipe according to claim 1 and 2, is characterized in that in step 3 under the protection of nitrogen, is warming up to 500 DEG C with 5 DEG C/min heating rate and is incubated 5h.
6. the preparation method of a kind of nitrogen-doped carbon nanometer pipe according to claim 1 and 2, is characterized in that in step 3 under the protection of nitrogen, is warming up to 600 DEG C with 6 DEG C/min heating rate and is incubated 4h.
7. the preparation method of a kind of nitrogen-doped carbon nanometer pipe according to claim 1 and 2, is characterized in that in step 3 under the protection of nitrogen, is warming up to 700 DEG C with 8 DEG C/min heating rate and is incubated 3h.
8. the preparation method of a kind of nitrogen-doped carbon nanometer pipe according to claim 1 and 2, is characterized in that in step 4 under the protection of nitrogen, is warming up to 950 DEG C of insulations for 1 ~ 1.2h with the heating rate of 8 DEG C/min.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN112007677A (en) * | 2020-07-24 | 2020-12-01 | 同济大学 | Nitrogen-doped iron nanotube, and preparation method and application thereof |
| CN113186565A (en) * | 2021-04-14 | 2021-07-30 | 天津大学 | Preparation method of novel nitrogen-doped carbon material for electrocatalytic reduction of carbon dioxide |
| CN113214506A (en) * | 2021-04-29 | 2021-08-06 | 武汉工程大学 | Polyvinyl alcohol-nitrogen doped carbon nanotube composite conductive hydrogel and preparation method thereof |
| CN113479863A (en) * | 2021-06-03 | 2021-10-08 | 佛山市格瑞芬新能源有限公司 | Hierarchical porous carbon nanotube and preparation method and application thereof |
| CN115677012A (en) * | 2022-11-10 | 2023-02-03 | 四川大学 | Water treatment method for enhancing Fenton oxidation by nitrogen-doped reduced graphene oxide |
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| CN105826572A (en) * | 2016-05-10 | 2016-08-03 | 大连理工大学 | N and S dual-doped carbon nanotube-coated FexC catalyst and preparation method and application thereof |
| CN105826572B (en) * | 2016-05-10 | 2018-06-08 | 大连理工大学 | A kind of N, S codope carbon nanotube coat FexC catalyst, preparation method and applications |
| CN109136979A (en) * | 2018-08-08 | 2019-01-04 | 东华大学 | The nitrogen-doped carbon composite material of hollow zinc doping cobalt oxide nickel coated and its preparation |
| CN110911650A (en) * | 2018-09-14 | 2020-03-24 | 宝山钢铁股份有限公司 | Preparation method of three-dimensional nitrogen-doped carbon tube-carbon tube lithium ion battery cathode material |
| CN111606405A (en) * | 2020-06-03 | 2020-09-01 | 北京林业大学 | Method for degrading organic pollutants in water by activating peracetic acid through nitrogen-doped carbon material |
| CN112007677A (en) * | 2020-07-24 | 2020-12-01 | 同济大学 | Nitrogen-doped iron nanotube, and preparation method and application thereof |
| CN113186565A (en) * | 2021-04-14 | 2021-07-30 | 天津大学 | Preparation method of novel nitrogen-doped carbon material for electrocatalytic reduction of carbon dioxide |
| CN113214506A (en) * | 2021-04-29 | 2021-08-06 | 武汉工程大学 | Polyvinyl alcohol-nitrogen doped carbon nanotube composite conductive hydrogel and preparation method thereof |
| CN113479863A (en) * | 2021-06-03 | 2021-10-08 | 佛山市格瑞芬新能源有限公司 | Hierarchical porous carbon nanotube and preparation method and application thereof |
| CN115677012A (en) * | 2022-11-10 | 2023-02-03 | 四川大学 | Water treatment method for enhancing Fenton oxidation by nitrogen-doped reduced graphene oxide |
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