CN101244815A - Method and device for producing carbon nano-tube or nitrogen doping carbon nano-tube with liquid phase forerunner article - Google Patents
Method and device for producing carbon nano-tube or nitrogen doping carbon nano-tube with liquid phase forerunner article Download PDFInfo
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Abstract
The invention provides a chemical vapor deposition method, which takes liquidoid organic precursor as the carbon source and the nitrogen source, adopts an injection pump to inject the precursor into a reaction chamber, regulates the variety and input of the precursor, the variety and load of catalyst, the flow speed of protective atmosphere, and the reaction temperature, so as to produce high-quality carbon nano-tubes of different sizes and appearances, or nitrogen-mixed carbon nano-tubes with different nitrogen contents, classes, sizes and appearances in large quantity. For the chemical vapor phase deposition method of the invention, the carbon atoms in the precursor are transformed into carbon nano-tubes or nitrogen-mixed carbon nano-tubes with the transformation rate up to more than 60%, and the nitrogen content in the obtained nitrogen-mixed carbon nano-tubes is comparatively high; the diameter of the obtained tubes is comparatively uniform and the purity is relatively high; by adopting the CVD method to produce carbon nano-tubes or nitrogen-mixed carbon nano-tubes, the chemical vapor deposition method in the invention has the advantages of easy feasibility, convenient control of the reaction conditions, and no special requirements on the physical properties of the precursor by adopting the injection pump to inject the precursor, and larger selectable range of the precursor.
Description
Technical field
The invention belongs to the carbon nanotube preparation technology field, be specially a kind of method and device for preparing carbon nanotube or nitrogen-doped carbon nanometer pipe with liquid phase forerunner article.
Background technology
Rise the nineties in last century, and carbon nanotube is because its important scientific value and great application prospect have caused the extensive concern and the research of scientific circles and industry member.The carbon nanometer is to obtain [S.Iijima by Ijima by arc discharge method at first, Nature, 1991,354,56.], arc process prepares multi-walled carbon nano-tubes and makes substantial progress subsequently, and P.M.Ajayan etc. have obtained high-purity multi-wall carbon nano-tube [T.W.Ebbesen, the P.M.Ajayan of gram magnitude first by purifying Graphite Electrodes arc-over product, Nature, 1992,358,220.].Nineteen ninety-five, and R.E.Smally etc. [T.Guo,, R.E.Smalley.et.al., J.Phys.Chem., 1995,99,10694] when modifying soccerballene with laser evaporation method research metal, in reference is tested with pure graphite as target, the result has been surprised to find that carbon nanotube in product.The synthetic carbon nanotube degree of graphitization height that obtains of arc-over and laser evaporation high temperature, processing parameter is more easy to control, has become the classical way for preparing carbon nanotube and explore novel nanostructure; but invest bigger; device is complicated, be difficult for scale preparation, and foreign matter content is higher in the product.In recent years, in warm synthesis method mainly be that chemical Vapor deposition process (CVD) is relatively low because of its synthesis temperature, generally at 500 ℃-1200 ℃, cost is low, output is big, the precursor kind abundant, experiment condition is easy to control etc., this class synthetic method is more rising aspect large-scale industrial production, and the carbon nanotube great majority of commercialization supply in the market are synthetic by this method.
With benzene is precursor, can obtain productive rate height, carbon nanotube that purity is good by the CVD growth method, and the existing carbon nanotube six-ring cluster growth mechanism that proposes to do with the benzene six-ring structural unit has obtained the support of original position heat analysis-mass spectrometry experimental result.[(a) Wang, X.Z.et al.Chinese Physics, 2001,10, S76-79 (b) Yang, Y.etal.Nanotechnology 2003,14,733-737. (c) Tian, Y.et al.J.Am.Chem.S ℃ .2004,126,1180-1183.] but entering of benzene precursor is to take saturex out of by carrier gas in the preparation, precursor enters the amount of system and can't measure, and product is subject to the variation of outside air temperature and influences, therefore to the temperature requirements of system than higher.
A lot of physicochemical property height of carbon nanotube rely on the textural defect in its caliber, chirality and the pipe, and these parameters are difficult to control under present experiment condition, have therefore limited the applied research of carbon nanotube to a certain extent.Chemical doping is a very practicable method for the application of expansion carbon nanotube, and chemical doping has been introduced additional electronic state near fermi level, can strengthen the electron emission capability of nanotube, changes its chemical structure and performance.The carbon nanotube of element doping is in electron device [Baughman RH.et.al., Science, 2002,297,787-92], catalyst support material [de Jong KP, Geus JW, Catal.Rev.-Sci.Eng.2000,42 (4), 481-510], and solid base catalyst aspect [van Dommele S, et.al., Chem.Commun.2006,4859-61] applied research to some extent.
From structure and the character of experimentally regulating and control carbon nanotube, doping nitrogen element is a method relatively more commonly used in carbon nanotube.The nitrogen-doped carbon nanometer pipe that obtains behind the doping nitrogen-atoms, owing to introduced the nitrogen element, make the structure and the character of carbon nanotube that variation take place, strengthened the electron emission capability of carbon nanotube, and because the introducing of nitrogen element makes that comparing inert carbon nano tube surface chemically reactive originally comparatively speaking increases, the research of this respect has caused people's extensive interest.[(a) Dos Santos, M.C.; Alvarez, E.Phys.Rev.B 1998,58, and 13918; (b) Terrones, M.et al.Adv.Mater.1999,11,655; (c) Terrones, M.et al.Appl.Phys.A 2002,74,355; (d) Kudashov, A.G.et al.J.Phys.Chem.B 2004,108,9048; (e) Lee, Y.T.et al.J.Phys.Chem.B 2003,107,12958.] correlative study shows that the nitrogen-atoms in the nitrogen-doped carbon nanometer pipe helps at carbon nano tube surface stagnant catalyst particle, and need not carry out functionalization [(a) Zamudio to carbon nanotube in advance, A.et al.Small, 2006,2,346; (b) Jiang, K.et al.Nano Lett.2003,3,275; (c) Bin Yue et al, J.Mater.Chem., 2008, DOI:10.1039/b718283j], and will generally need in advance active higher functional group to be introduced on its surface at carbon nano tube surface stagnant catalyst particle.There are some researches show in the recent period, above the nitrogen-doped carbon nanometer pipe type of N to stagnant catalyst particle decisive role, Biao Mian pyridine nitrogen species especially.[Yang, S.H.et al.Appl.Phys.Lett.2007,90,013103.] synthetic similar with carbon nanotube, nitrogen-doped carbon nanometer pipe synthetic mainly contains following several method: 1) high temperature synthetic method, for example arc-over and laser evaporation [O.St é phan, et.al, Science 266,1683 (1994) .]; 2) the synthetic CVD method [C.P.Ewels, M.Glerup, J.Nanosci.Nanotech., 2005,5 (9) 1345-1363] of low temperature; 3) magnetron sputtering and ion implantation etc. [K.Suenaga, et.al, Chem.Phys.Lett.1999,300,695].But comparatively speaking, the CVD method is thought by everybody and is best suited for scale production, the synthetic method that cost is minimum.
Generally speaking, synthetic for nitrogen-doped carbon nanometer pipe, adopting the nitrogenous organic precursors of liquid phase to do nitrogenous source, to be better than with nitrogenous gas (nitrogen, ammonia) be precursor.Because, comparatively speaking, be that nitrogenous source needs higher synthesis temperature or plasma body to assist with nitrogen, be that nitrogenous source then causes bigger corrosion to system easily with the ammonia, so should select for use itrogenous organic substance to provide carbon source and nitrogenous source simultaneously usually for precursor.
Liquid phase forerunner article sample introduction during the CVD of nitrogen-doped carbon nanometer pipe synthesizes at present mainly contains following several mode: saturex Bubbling method [Chen, H.et al.J.Phys.Chem.B 2006,110,16422-16427.], aerosol is assisted sample introduction equipment [Kamalakaran et al.Appl.Phys.Lett., 2000,77,21, ], CF needle-valve sample introduction [Ayala et al.J.Phys.Chem.C 2007,111 under the condition of high vacuum degree, 2879-2884], the peristaltic pump dead point splashes into [R Che et al, Nanotechnology, 2007,18,355705].
Based on early stage be the research of precursor synthesizing carbon nanotubes with benzene, the employing pyridine is a precursor, bring volatile pyridine into CVD reaction system (Bubbling method) by saturex, nitrogen-doped carbon nanometer pipe [the Chen that under differing temps, has synthesized different nitrogen contents, H.et al.J.Phys.Chem.B 2006,110,16422-16427.].But comparatively speaking, the saturex range of application is little: only be applicable to the precursor that some saturated vapor pressures are higher, for benzylamine (saturation vapour pressure 1600Pa (90 ℃)), organism that this class vapour pressure of aniline (saturation vapour pressure 2000Pa (77 ℃)) is lower and the liquid precursor that some are thick can not reach effective transmission of precursor.And, even adopted high-volatile precursor, when adopting saturex as the liquid precursor sampling device, have only when whole system all to be in the higher temperature that compares, and the temperature head of external environment is very for a short time just can certain meaning be arranged to the preparation rule when being unlikely to influence experimental result.
When can not satisfy this condition, will occur:
(1) carrier gas flux is constant, but the actual amount of substance that enters system is non-constant, causes bigger error;
(2) product that obtains under Various Seasonal and the temperature, output, productive rate and quality product produce than large deviation, can not be used for well probing into the actual response situation, and repeatability is relatively poor;
(3) can not accurately calculate the many a spot of precursors of the system that specifically enters, be unfavorable for amplification test.
Though the aerosol utility appliance can reach the constant continuous sample introduction, but because it is a glasswork, be difficult to processing, frangible, be connected cumbersomely with boiler tube, platform and concrete operations control required very high, and it is not applicable to viscous liquid very much, the historical facts or anecdotes border operates must extreme care, and equipment does not utilize to amplify and produces.Same CF needle-valve requires reaction system to be in higher relatively vacuum condition always, the condition harshness, and cost is too high.Peristaltic pump generally can not reach the flow sample introduction, is similar to human transfusion, belongs to dead point, the excessive and homogeneous not too of sample size.
Along with the continuous increase of industry member and scientific circles to carbon nanotube and nitrogen-doped carbon nanometer pipe demand, and in order better to save cost, develop new technological line high-quality carbon nanotube of a large amount of controlled preparations and nitrogen-doped carbon nanometer pipe, and kind and the content of how regulating nitrogen in the nitrogen-doped carbon nanometer pipe by the change condition, be to be worth the problem explored.
Summary of the invention
The problem to be solved in the present invention is: existing carbon nanotube preparation technology is not suitable for high-quality carbon nanotube of a large amount of controllable preparation and nitrogen-doped carbon nanometer pipe, because the preparation of existing nitrogen-doped carbon nanometer pipe limits to some extent to precursor, the kind of nitrogen and content also are restricted in the nitrogen-doped carbon nanometer pipe.
Technical scheme of the present invention is: a kind of method for preparing carbon nanotube or nitrogen-doped carbon nanometer pipe with liquid phase forerunner article; adopt chemical Vapor deposition process; temperature with reaction chamber under protective atmosphere rises to 550 ℃-850 ℃; with liquid phase organism precursor is carbon source and nitrogenous source; by syringe pump precursor is expelled to reaction chamber; adopt the transition metal loaded catalyst; under protective atmosphere, react; precursor obtains carbon nanotube during for carbon source; precursor obtains nitrogen-doped carbon nanometer pipe when comprising carbon source and nitrogenous source; by regulation and control precursor kind and input; catalyst type and charge capacity thereof, protective atmosphere flow velocity, temperature of reaction; the high-quality carbon nanotube that can prepare the different size pattern in a large number, or different nitrogen content; the nitrogen-doped carbon nanometer pipe of nitrogenous kind and size pattern.
The preferred version of the inventive method is: protective atmosphere adopts nitrogen or argon gas; be to make reaction chamber temperature rise to 550 ℃-850 ℃ under the protective atmosphere of 100sccm at flow; the syringe pump partition ratio is 0.25ml/h; liquid phase forerunner article is injected into reaction chamber, adopts 1.0mmol/g Fe-2.0mmol/g Co/ γ-Al
2O
3Loaded catalyst, reaction times 1-3 hour, reaction was cooled to room temperature after finishing under the protection of protective atmosphere, collect carbon nanotube or nitrogen-doped carbon nanometer pipe.
The device that the inventive method is used comprises tube furnace, liquid phase forerunner article sampling system, gas distributing system and vacuum system, and tube furnace inside adds the thermal center (-tre) reaction chamber is set, the temperature adjustable of reaction chamber; The liquid phase forerunner article sampling system comprises syringe pump and syringe pump control template, and syringe pump output connects the inlet mouth of tube furnace; Gas distributing system comprises source of the gas, gas circuit and mass flow controller, and gas distributing system output connects the inlet mouth of tube furnace; Vacuum tightness that the vacuum system conditioned reaction is indoor and pressure.Wherein, reaction chamber is a crystal reaction tube; Gas distributing system is made up of source of the gas, pressure maintaining valve, flow stabilizing valve, mass flowmeter, and the gas of source of the gas is through pressure maintaining valve, flow stabilizing valve, mass flowmeter output.
The inventive method is by the regulating catalyst kind, temperature of reaction, precursor kind and sample introduction speed, can prepare dissimilar, different mass and nitrogen content, and the carbon nanotube or the nitrogen-doped carbon nanometer pipe of nitrogen distribution, the transformation efficiency that carbon atom is converted into carbon nanotube or nitrogen-doped carbon nanometer pipe in the precursor reaches more than 60%, the output of carbon nanotube or nitrogen-doped carbon nanometer pipe can reach the gram level in common tube furnace, is expected to prepare carbon nanotube or nitrogen-doped carbon nanometer pipe in a large number by amplifying reaction scale; The nitrogen content of the resulting nitrogen-doped carbon nanometer pipe of the inventive method can reach more than 7.5%, the caliber of resultant product is homogeneous relatively, and purity is higher, when temperature of reaction during at 650 ℃, product nanotube diameter is about about 30nm, and length can reach micron dimension; The present invention adopts the CVD method to prepare carbon nanotube or nitrogen-doped carbon nanometer pipe, is easy to realize, reaction conditions is easy to control, adopts syringe pump injection precursor, and the physical properties of precursor is not had particular requirement, has enlarged the selectable scope of precursor.
Description of drawings
Fig. 1: reaction unit synoptic diagram: (1) N2 or Ar gas cylinder and reducing valve, (2) pressure maintaining valve, (3) flow stabilizing valve, (4) mass flowmeter, (5) syringe pump execution module, (6) syringe pump control module, (7) inlet mouth, (8) big silica tube, (9) crystal reaction tube, (10) catalyzer, (11) tube furnace, (12) air outlet
Fig. 2: the present invention is the TEM figure of the carbon nanotube that obtains of precursor with benzene.
Fig. 3: the present invention is that precursor is at the TEM of 650 ℃ of nitrogen-doped carbon nanometer pipes that obtain figure with the pyridine.
Fig. 4 is a): the present invention is that precursor is at the TEM of 650 ℃ of nitrogen-doped carbon nanometer pipes that obtain figure with the benzylamine.
Fig. 4 b): the present invention is the XPS spectrum figure of precursor at 650 ℃ of nitrogen-doped carbon nanometer pipes that obtain with the benzylamine.
Fig. 5 is a): the present invention is that precursor is at the TEM of 650 ℃ of nitrogen-doped carbon nanometer pipes that obtain figure with pyrroles.
Fig. 5 b): the present invention is the XPS spectrum figure of precursor at 650 ℃ of nitrogen-doped carbon nanometer pipes that obtain with pyrroles.
Fig. 6: the present invention is that precursor is at the TEM of 650 ℃ of nitrogen-doped carbon nanometer pipes that obtain figure with the 4-aminomethyl-pyridine.
Fig. 7 is a): the present invention is that precursor is at the TEM of 750 ℃ of nitrogen-doped carbon nanometer pipes that obtain figure with the 3-aminomethyl-pyridine.
Fig. 7 b): the present invention is the XPS spectrum figure of precursor at 750 ℃ of nitrogen-doped carbon nanometer pipes that obtain with the 3-aminomethyl-pyridine.
Fig. 8 is a): the present invention is that precursor is at the TEM of 550 ℃ of nitrogen-doped carbon nanometer pipes that obtain figure with the 3-aminomethyl-pyridine.
Fig. 8 b): the present invention is the XPS spectrum figure of precursor at 550 ℃ of nitrogen-doped carbon nanometer pipes that obtain with the 3-aminomethyl-pyridine.
Fig. 8 c): the present invention is that precursor is at the TEM of 650 ℃ of nitrogen-doped carbon nanometer pipes that obtain figure with the 3-aminomethyl-pyridine.
Fig. 8 d): the present invention is the XPS spectrum figure of precursor at 650 ℃ of nitrogen-doped carbon nanometer pipes that obtain with the 3-aminomethyl-pyridine.
Fig. 8 e): the present invention is that precursor is at the TEM of 850 ℃ of nitrogen-doped carbon nanometer pipes that obtain figure with the 3-aminomethyl-pyridine.
Fig. 8 f): the present invention is the XPS spectrum figure of precursor at 850 ℃ of nitrogen-doped carbon nanometer pipes that obtain with the 3-aminomethyl-pyridine.
Fig. 9: the present invention is precursor with the benzylamine, under the catalyst of 2mmol charge capacity, and the TEM of the nitrogen-doped carbon nanometer pipe that under 650 ℃, obtains figure.
Figure 10: the present invention is precursor with the pyridine, under the 3mmol single component catalyst catalytic growth, and the TEM of the nitrogen-doped carbon nanometer pipe that under 650 ℃, obtains figure.
Figure 11: the present invention is precursor with the pyridine, under the Fe of Prepared by Sol Gel Method, the Mo bimetallic catalyst catalytic growth, and the TEM of the nitrogen-doped carbon nanometer pipe that under 650 ℃, obtains figure.
Embodiment
Below in conjunction with accompanying drawing and embodiment the inventive method is described.
The present invention adopts chemical gaseous phase depositing process (CVD) to prepare carbon nanotube and nitrogen-doped carbon nanometer pipe, and reaction unit comprises tube furnace, liquid phase forerunner article sampling system, gas distributing system and vacuum system.As Fig. 1, tube furnace inside adds the thermal center (-tre) and crystal reaction tube is set as reaction chamber, the temperature adjustable of reaction chamber, the liquid phase forerunner article sampling system comprises syringe pump and syringe pump control template, syringe pump output connects the inlet mouth of tube furnace, gas distributing system is made up of source of the gas, pressure maintaining valve, flow stabilizing valve, mass flowmeter, and the gas of source of the gas is through pressure maintaining valve, flow stabilizing valve, mass flowmeter output, and gas distributing system output connects the inlet mouth of tube furnace.Vacuum system is used for indoor vacuum tightness of conditioned reaction and pressure.When the inventive method realizes; under protective atmosphere; be generally nitrogen or argon gas; the temperature of reaction chamber is risen to 550 ℃-850 ℃; with liquid phase organism precursor is carbon source and nitrogenous source; syringe pump control module control syringe pump with the precursor calibrated shot to reaction chamber; place the transition metal loaded catalyst in the reaction chamber, under protective atmosphere, the CVD reaction takes place in precursor; by regulation and control precursor kind and input; catalyst type and charge capacity thereof, carrier gas air-flow, temperature of reaction; the high-quality carbon nanotube that can prepare the different size pattern in a large number, or different nitrogen content; the nitrogen-doped carbon nanometer pipe of nitrogenous kind and size pattern.
Take by weighing about 0.4g catalyzer; be tiled in the crystal reaction tube; then crystal reaction tube is positioned over tube furnace center warm area; at flow velocity is under the argon gas or nitrogen atmosphere of 100sccm; temperature rise rate with 10 ℃ of per minutes is warmed up to 650 ℃; open syringe pump benzene injection precursor in boiler tube then; syringe pump partition ratio 0.75ml/3hour; reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas or nitrogen (100sccm); collect about carbon nanotube 0.4g, the carbon atom utilization ratio in the benzene precursor is greater than 65%.Transmission electron microscope (TEM) characterizes as shown in Figure 2, and the diameter of nanotube is about 20-30nm, and length can reach micron order.
Embodiment 2 is a precursor with the pyridine, 1.0mmol/g Fe-2.0mmol/g Co/ γ-Al
2O
3Be catalyzer, the preparation nitrogen-doped carbon nanometer pipe.
Take by weighing about 0.4g catalyzer; be tiled in the crystal reaction tube; then crystal reaction tube is positioned over tube furnace center warm area; (100sccm) is warmed up to 650 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon gas or nitrogen atmosphere; open syringe pump (0.75ml/3hour) then and in boiler tube, inject the pyridine precursor; reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas or nitrogen (100sccm), and the carbon atom utilization ratio in the pyridine precursor of the collection carbon nanotube 0.4g left and right sides is greater than 70%.Transmission electron microscope (TEM) characterizes as shown in Figure 3, and the diameter of nanotube is about 20-30nm, and length can reach micron dimension.
Take by weighing about 0.4g catalyzer; be tiled in the crystal reaction tube; then crystal reaction tube is positioned over tube furnace center warm area; (100sccm) is warmed up to 650 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon gas or nitrogen atmosphere; open syringe pump (0.75ml/3hour) then and in boiler tube, inject the benzylamine precursor; reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas or nitrogen (100sccm), and the carbon atom utilization ratio in the benzylamine precursor of the collection carbon nanotube 0.45g left and right sides is greater than 70%.Transmission electron microscope (TEM) and photoelectron spectrum (XPS) characterize as Fig. 4 a) and Fig. 4 b) shown in, TEM figure shows the diameter of nitrogen-doped carbon nanometer pipe of generation about 20-30nm, length can reach micron dimension, XPS test shows nitrogen content is 2.2%.
Take by weighing about 0.4g catalyzer; be tiled in the crystal reaction tube; then crystal reaction tube is positioned over tube furnace center warm area; (100sccm) is warmed up to 650 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon gas or nitrogen atmosphere; open syringe pump (0.75ml/3hour) then and in boiler tube, inject pyrroles's precursor; reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas or nitrogen (100sccm); collect about carbon nanotube 0.40g, the carbon atom utilization ratio in pyrroles's precursor is greater than 80%.Transmission electron microscope (TEM) and photoelectron spectrum (XPS) characterize as Fig. 5 a) with Fig. 5 b) shown in, TEM figure shows that the diameter of the nitrogen-doped carbon nanometer pipe that generates is about 40-50nm, be coaxial ring shape, length reaches micron dimension, and XPS test shows nitrogen content is 7.7%.
Embodiment 5 is a precursor with the 4-aminomethyl-pyridine, 1.0mmol/g Fe-2.0mmol/g Co/ γ-Al
2O
3Be catalyzer, the preparation nitrogen-doped carbon nanometer pipe.
Take by weighing about 0.4g catalyzer; be tiled in the crystal reaction tube; then crystal reaction tube is positioned over tube furnace center warm area; (100sccm) is warmed up to 650 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon gas or nitrogen atmosphere; open syringe pump (0.75ml/3hour) then and in boiler tube, inject 4-aminomethyl-pyridine precursor; reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas or nitrogen (100sccm); collect about carbon nanotube 0.45g, the carbon atom utilization ratio in the 4-aminomethyl-pyridine precursor is greater than 70%.Transmission electron microscope (TEM) characterizes as shown in Figure 6, and the diameter that TEM figure shows the nitrogen-doped carbon nanometer pipe that generates is about 20-30nm, and length can reach micron dimension.
Take by weighing about 0.4g catalyzer; be tiled in the crystal reaction tube; then crystal reaction tube is positioned over tube furnace center warm area; (100sccm) is warmed up to 750 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon gas or nitrogen atmosphere; open syringe pump (0.75ml/3hour) then and in boiler tube, inject 4-aminomethyl-pyridine precursor; reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas or nitrogen (100sccm); collect about carbon nanotube 0.45g, the carbon atom utilization ratio in the 4-aminomethyl-pyridine precursor is greater than 70%.Transmission electron microscope (TEM) and photoelectron spectrum (XPS) characterize as Fig. 7 a) and Fig. 7 b) shown in, TEM figure shows the diameter of nitrogen-doped carbon nanometer pipe of generation about 20-40nm, length can reach micron dimension, XPS test shows nitrogen content is 6.5%.
Embodiment 7 is a precursor with the 3-aminomethyl-pyridine, 1.0mmol/g Fe-2.0mmol/g Co/ γ-Al
2O
3Be catalyzer, the preparation nitrogen-doped carbon nanometer pipe.
Changing temperature of reaction respectively is 550 ℃, and 650 ℃, 850 ℃, other steps are identical with embodiment 6, and to crystal reaction tube injection 3-aminomethyl-pyridine (0.75ml/3hour), the carbon atom transformation efficiency still remains on more than 70%.Dependent transmissive Electronic Speculum (TEM) and photoelectron spectrum (XPS) characterize as Fig. 8 a)-8b) shown in, when temperature of reaction is 550 ℃, the diameter of TEM figure demonstration nitrogen-doped carbon nanometer pipe about 20-30nm, the length distribution broad, XPS test shows nitrogen content is 6.3%; When temperature of reaction was 650 ℃, the diameter of nitrogen-doped carbon nanometer pipe was about 20-30nm, and impurity is more, and length is in micron level, and XPS test shows nitrogen content is 6.6%; In the time of 850 ℃, the diameter of nitrogen-doped carbon nanometer pipe is about 80-100nm, and length is about 200-500nm, and XPS test shows nitrogen content is 5.6%.
Embodiment 8 is a precursor with the benzylamine, 1.0mmol/g Fe-1.0mmol/g Co/ γ-Al
2O
3Be catalyzer, the preparation nitrogen-doped carbon nanometer pipe.
Take by weighing about 0.4g catalyzer; be tiled in the crystal reaction tube; then crystal reaction tube is positioned over tube furnace center warm area; (100sccm) is warmed up to 650 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon gas or nitrogen atmosphere; open syringe pump (0.50ml/2hour) then and in boiler tube, inject the benzylamine precursor; reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas or nitrogen (100sccm); collect about carbon nanotube 0.3g, the carbon atom utilization ratio in the benzylamine precursor is about 60%.Product TEM characterizes as shown in Figure 9, and the diameter that TEM figure shows the nitrogen-doped carbon nanometer pipe that generates is about 20-30nm, and length can reach micron dimension.
Embodiment 9 is a precursor with the pyridine, 3.0mmol/g Fe/ γ-Al
2O
3Be catalyzer, the preparation nitrogen-doped carbon nanometer pipe.
Take by weighing about 0.3g catalyzer; be tiled in the crystal reaction tube; then crystal reaction tube is positioned over tube furnace center warm area; (80sccm) is warmed up to 580 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon gas or nitrogen atmosphere; feed the hydrogen reaction 10 minutes of flow velocity 40sccm then; stop to feed hydrogen subsequently, keep protective atmosphere flow velocity 80sccm constant, continue to be warming up to 650 ℃ with the temperature rise rate of 10 ℃ of per minutes.Open syringe pump (0.50ml/2hour) and inject the pyridine precursor in boiler tube, reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas or nitrogen (80sccm), collects about carbon nanotube 0.1g.Product TEM characterizes as shown in figure 10, and the diameter that TEM figure shows the nitrogen-doped carbon nanometer pipe that generates is about 20-40nm, and length can reach micron dimension.
Embodiment 10 is a precursor with the pyridine, and the Fe of Prepared by Sol Gel Method: Mo/MgO (proportioning 2: 0.1: 13) is a catalyzer, the preparation nitrogen-doped carbon nanometer pipe.
Take by weighing about 0.4g catalyzer; be tiled in the crystal reaction tube; then crystal reaction tube is positioned over tube furnace center warm area; (60sccm) is warmed up to 650 ℃ with the temperature rise rate of 10 ℃ of per minutes under argon gas or nitrogen atmosphere; open syringe pump (0.50ml/2hour) then and in boiler tube, inject the pyridine precursor; reaction finishes the back boiler tube and drops to room temperature in the protection of argon gas or nitrogen (60sccm), collects about carbon nanotube 0.3g, and the carbon atom utilization ratio in the pyridine precursor is about 60%.Product TEM characterizes as shown in figure 11, and the diameter that TEM figure shows the nitrogen-doped carbon nanometer pipe that generates is tangible bamboo-like carbon nano tubes about 30-50nm.
Liquid phase forerunner article in the above-mentioned preparation process can be the liquid organic precursors of various existing carbon containings and nitrogen, a wider range of covering, as 3-aminomethyl-pyridine and 4-aminomethyl-pyridine be in the preparation of original carbon nanotube, do not have used.According to above-mentioned reaction conditions, can regulate and control the content of nitrogen in the relevant nitrogen-doped carbon nanometer pipe by change temperature of reaction and sample introduction speed.
Claims (4)
1; a kind of method for preparing carbon nanotube or nitrogen-doped carbon nanometer pipe with liquid phase forerunner article; it is characterized in that adopting chemical Vapor deposition process; temperature with reaction chamber under protective atmosphere rises to 550 ℃-850 ℃; with liquid phase organism precursor is carbon source and nitrogenous source; by syringe pump precursor is expelled to reaction chamber; adopt the transition metal loaded catalyst; under protective atmosphere, react; precursor obtains carbon nanotube during for carbon source; precursor obtains nitrogen-doped carbon nanometer pipe when comprising carbon source and nitrogenous source; by regulation and control precursor kind and input; catalyst type and charge capacity thereof, protective atmosphere flow velocity, temperature of reaction; the high-quality carbon nanotube that can prepare the different size pattern in a large number, or different nitrogen content; the nitrogen-doped carbon nanometer pipe of nitrogenous kind and size pattern.
2, the method for preparing carbon nanotube or nitrogen-doped carbon nanometer pipe with liquid phase forerunner article according to claim 1; it is characterized in that protective atmosphere adopts nitrogen or argon gas; be to make reaction chamber temperature rise to 550 ℃-850 ℃ under the protective atmosphere of 100sccm at flow; the syringe pump partition ratio is 0.25ml/h; liquid phase forerunner article is injected into reaction chamber, adopts 1.0mmol/g Fe-2.0mmol/g Co/ γ-Al
2O
3Loaded catalyst, reaction times 1-3 hour, reaction was cooled to room temperature after finishing under the protection of protective atmosphere, collect carbon nanotube or nitrogen-doped carbon nanometer pipe.
3, the device for preparing the method for carbon nanotube or nitrogen-doped carbon nanometer pipe with liquid phase forerunner article according to claim 1 and 2, it is characterized in that comprising tube furnace, liquid phase forerunner article sampling system, gas distributing system and vacuum system, tube furnace inside adds the thermal center (-tre) reaction chamber is set, the temperature adjustable of reaction chamber; The liquid phase forerunner article sampling system comprises syringe pump and syringe pump control template, and syringe pump output connects the inlet mouth of tube furnace; Gas distributing system comprises source of the gas, gas circuit and mass flow controller, and gas distributing system output connects the inlet mouth of tube furnace; Vacuum tightness that the vacuum system conditioned reaction is indoor and pressure.
4, according to claim 3ly prepare the device of the method for carbon nanotube or nitrogen-doped carbon nanometer pipe, it is characterized in that reaction chamber is a crystal reaction tube with liquid phase forerunner article; Gas distributing system is made up of source of the gas, pressure maintaining valve, flow stabilizing valve, mass flowmeter, and the gas of source of the gas is through pressure maintaining valve, flow stabilizing valve, mass flowmeter output.
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| CN102698785A (en) * | 2012-06-21 | 2012-10-03 | 中国矿业大学(北京) | Preparation method of diatomite-loaded nitrogen-doped nanometer TiO2 photocatalysis material |
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