CN103288072A - Preparation method of iron filled carbon nano tube and reaction device - Google Patents
Preparation method of iron filled carbon nano tube and reaction device Download PDFInfo
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Abstract
The invention provides a preparation method of an iron filled carbon nano tube and a reaction device. The preparation method of the iron filled carbon nano tube comprises the following steps of: preparing the iron filled carbon nano tube by adopting an inorganic covalent compound of iron namely ferric chloride anhydrous as a catalyst precursor and selecting different carbon sources through floating catalysis chemical vapor deposition method, wherein the iron filled carbon nano tube comprises a non-nitrogen-doped iron filled carbon nano tube or a nitrogen-doped iron filled carbon nano tube. The preparation method of the iron filled carbon nano tube disclosed by the invention is simple and scientific in steps and can prepare a high-iron filled carbon nano tube. The invention further discloses a reaction device of the preparation method of the iron filled carbon nano tube. According to the preparation method of the iron filled carbon nano tube and the reaction device, a plurality of disadvantages in the prior art can be overcome; and the advantages that the preparation method is simple and the obtained iron filled carbon nano tube has high iron filling rate are realized.
Description
Technical field
The present invention relates to the ceramic technology, relate in particular to a kind of preparation method and reaction unit of iron filling carbon nano-pipe.
Background technology
Carbon nanotube (CNTs) is [Iijima S, et al. Nature, 1991,354 (6348): 56] since being found in 1991, owing to its particular structure and excellent electricity and mechanical property have caused investigator's extensive concern.Also become the focus of research in recent years gradually about the modification of carbon nanotube.The modification of carbon nanotube can be divided into two kinds: the filling of the outside modification of carbon nanotube and carbon nanotube internal cavities.The outside modification of carbon nanotube mainly comprises carries out functionalization to it, specific functional group is to improve the problem such as water-soluble of carbon nanotube in the loading, or it is carried out doping treatment, to change crystalline structure and the electronic structure of carbon nanotube, thereby improve its chemical property, as replacing platinum as eelctro-catalyst [Gong KP, the et al. Science of oxygen reduction reaction (ORRs), 2009,323 (5915): 760].Because carbon nanotube has the cavity structure of one dimension, so can fill the carbon nanotube internal cavities, it is important research direction in recent years that foreign matter is filled carbon nanotube that ferromagnetic metal especially fills.Carbon nanotube can prevent ferromagnetic metal oxidized and corrosion of long-time placement in external environment as the protective layer of ferromagnetic metal.And this nano composite material can be with good electrical properties and magnetic property, at data storage [Geng FX, et al. Physica B, 2006,382:300], microwave absorbing [Che RC, et al. Advanced Materials, 2004,16 (5): 401] and magnetic microscope probe [Winkler A, et al. Journal of Applied Physics, 2006,99 (10): 104905] etc. there is potential application the aspect.
The method that present single stage method prepares metal filling carbon nano-pipe mainly is divided into fused salt electrolysis process, arc discharge method, template and pyrolysis method.Fused salt electrolysis process is to be anode with the carbon crucible, in crucible, put into metal-salt, when being heated to the metal-salt thawing, graphite-rod cathode inserted carry out method [the Hsu WK that electrolytic reaction prepares the filled-type carbon nanotube in the metal fused salt (electrolytic solution), et al. Chemical Physics Letters, 1999,301,159], but this method is not suitable for preparing the carbon nanotube that refractory metal is filled.Arc discharge method is after graphite anode rod boring, in the hole, insert the powder of graphite and metal to be filled, carry out arc-over then, on the negative electrode graphite rod, just can collect carbon nanotube [the Bera D that metal or metallic compound are filled, et al. Chemical Physics Letters, 2004,386:364], but the filling ratio of the metal that this method obtains is generally lower.Template need synthesize the template with certain size and structure earlier, grow carbon nanotube [the Che RC of filled-type then at mould material by the method for physics or chemistry, Advanced Materials, 2004,16 (5): 401], but also need after reaction finishes template is removed, technology is comparatively complicated, also has the low shortcoming of filling ratio.
Pyrolysis method is the preparation method of carbon nano-tube of using always the most, this method is to make it decompose the carbon nanotube that preparation iron is filled by heating of metal organism such as ferrocene, ferrocene is simultaneously as source of iron and carbon source [Rao CNR in this process, et al. Chemical Communications, 1998,15:1525], but the rate of volatilization of ferrocene is wayward in this method, there is the investigator that this method is improved: to adopt ferrocene and nickelocene as catalyst precursor, it is dissolved in the trichlorobenzene solution by accurate flow pump carries out the rate of volatilization that sample presentation can more accurate control ferrocene, can prepare thin wall carbon nano-tube [the Lv RT that iron-nickel alloy is filled, et al. Carbon, 2007,45 (7): 1433].Ferrocene is the most frequently used a kind of catalyst precursor in pyrolysis method, and it is cheap and easy to get and be easy to volatilization, and volatilization temperature is more than 100 ℃, but from the molecular formula (C of ferrocene
10H
10Fe) can find out, Fe:C atomic ratio in the ferrocene molecule is 1:10, this means that each iron atom will inevitably be attended by corresponding 10 carbon atoms when participating in reaction and also participate in reaction, therefore also only be 1:10 even do not add extraneous carbon source the Fe:C atomic ratio in the prepared iron filled with nanotubes is the highest when using ferrocene as source of iron and carbon source merely, this has limited the filling ratio of the interior iron of carbon nanotube greatly.
Usually complex catalyst precursor commonly used is organometallics in the pyrolysis method, as ferrocene, and nickelocene, iron carbonyl or nickle carbonoxide etc., these materials are expensive and toxic; In the selection of carbon source, adopt gaseous carbon sources such as methane or acetylene more, and liquid carbon source benzene or trichloro-benzene etc., operating equipment is numerous and diverse relatively, the investment cost height, and also the filling of iron is discontinuous in the products therefrom, and filling ratio is very low.
[Rao C N R, Govindaraj A. Accounts Chem Res. 2002,35 (12) such as Rao for example, 998-1007.] by the heating ferrocene it is decomposed, prepare the carbon nanotube that iron fills (Fe/CNT, as shown in Figure 1), operational condition: 900 ℃, atmosphere 75% Ar/25% H
2, flow 900 sccm.Ferrocene is simultaneously as source of iron, carbon source and catalyst precursor in this process, and the Fe:C atomic ratio that still is subject in the ferrocene molecule only is 1:10, and the yield of product and the filling ratio of iron are extremely low.Observe as can be known from the images of transmissive electron microscope (Fig. 1) of product, the filling of iron mainly occurs in pipe end in the carbon nanotube, and the middle part does not almost have weighting material.
Che etc. [Che R C, et al. Nanotechnology. 2007,18 (35), 355705.] are raw material with ferrocene and acetonitrile solution, at H
2900 ℃ of single step reactions prepare the carbon-nitrogen nano tube (Fe/CNx) that iron is filled in/Ar the mixed gas.Observe as can be known from the images of transmissive electron microscope (Fig. 2) of product, the caliber of nitrogen-doped carbon nanometer pipe changes obviously, be the ring shape, the filling of inner iron is discontinuous, iron-free filling place caliber is 20-30 nm, and the filling of iron makes caliber increase to left side among 40-50 nm(Fig. 2)), and the length of the iron nano-particle of filling is no more than right side among 50 nm(Fig. 2).
To sum up, there is the low and preparation method's complicated problems of iron filling ratio in the iron filling carbon nano-pipe for preparing in the existing method for preparing the iron filling carbon nano-pipe, so it is simple to demand a kind of preparation method urgently, and the higher preparation method of carbon nano-tube of iron filling ratio.
Summary of the invention
The objective of the invention is to, low and the preparation method's challenge of metal filled rate in the iron carbon nanotube for preparing at the above-mentioned existing method for preparing the iron filling carbon nano-pipe, a kind of preparation method of iron filling carbon nano-pipe is proposed, to realize iron filling ratio height, the simple advantage of preparation method.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of iron filling carbon nano-pipe when carbon source is solid-state organic compound, may further comprise the steps:
(1) two containers that take up carbon source and catalyst precursor respectively is positioned over two ends and is respectively arranged with in the quartz tube reactor of gas inlet and pneumatic outlet, and make two containers near the gas inlet; (2) quartz tube reactor is placed the tubular type heating installation; (3) in quartz tube reactor, feed inertia protection gas, open heating installation to temperature of reaction, volatilization for the catalyst precursor of gaseous state and carbon source under the drive of inert protective gas carrier gas, chemical vapour deposition reaction is carried out in the high-temperature zone that enters the quartz tube reactor middle part, treats to stop heating after the material volatilization finishes in the container; (4) quartz tube reactor is cooled to room temperature under inert protective atmosphere, collects the product in the quartz tube reactor, obtain the iron filling carbon nano-pipe;
When described carbon source is gaseous state and/or liquid organic compound, may further comprise the steps:
(1) container that will take up catalyst precursor is positioned over two ends and is respectively arranged with in the quartz tube reactor of gas inlet and pneumatic outlet, and makes container near the gas inlet; (2) quartz tube reactor is placed the tubular type heating installation; (3) in quartz tube reactor, feed inertia protection gas, open heating installation to temperature of reaction, feed carbon source and hydrogen, with volatilization for the catalyst precursor of gaseous state under the drive of inert protective gas carrier gas, chemical vapour deposition reaction is carried out in the high-temperature zone that enters the quartz tube reactor middle part, treats to stop heating after the volatilization of container inner catalyst presoma finishes; (4) quartz tube reactor is cooled to room temperature under inert protective atmosphere, collects the product in the quartz tube reactor, obtain the iron filling carbon nano-pipe.
Wherein, described catalyst precursor is FERRIC CHLORIDE ANHYDROUS.
Further, described solid-state organic compound comprises nitrogenous solid-state organic compound or nonnitrogenous solid-state organic compound; Described gaseous organic compound is gaseous hydrocarbons, and described liquid organic compound is nonnitrogenous liquefied hydrocarbon or nitrogenous liquid organic compound.
Further, the mass ratio of described solid-state organic compound and catalyst precursor is 1:0.5-5, preferred 1:1-3.The mass ratio of described gaseous state and/or liquid organic compound and catalyst precursor is 1:0.1-10.The flow range of used rare gas element is 100-800sccm.The flow range of used gaseous state and/or liquid carbon source is 5-80sccm, and the flow range of used hydrogen is 100-300sccm.
Further, described nitrogenous solid-state organic compound is one or more in trimeric cyanamide, Dyhard RU 100, vulkacit H and the imidazoles.Described unazotized solid-state organic compound is camphor.Described gaseous hydrocarbons is one or more in methane, ethene and the acetylene, and described unazotized liquefied hydrocarbon is hexanaphthene or benzene, and described nitrogenous liquid organic compound is one or more in nitrogenous liquid nitrile, amine and the heterocycle hydro carbons.Particularly, described nitrogenous liquid organic compound is one or more in acetonitrile, pyridine, dimethyl formamide and the pyrimidine.
Further, described inertia protection gas is one or more in argon gas, helium and the nitrogen.
Further, described temperature of reaction is 700～1000 ℃.
Another object of the present invention also provides a kind of reaction unit of realizing the preparation method of iron filling carbon nano-pipe, this iron filling carbon nano-pipe reaction unit comprises: tubular oven, the container, the two ends that are used for taking up solid-state reactants are respectively arranged with the quartz tube reactor of gas inlet and pneumatic outlet, describedly be placed in the quartz tube reactor a end near the gas inlet be used to the container that takes up solid-state reactants, described quartz tube reactor is positioned in the tubular oven.
Further, be porcelain boat for the container that takes up solid-state reactants; Described tubular type heating installation is tube type resistance furnace.Iron filling carbon nano-pipe reaction unit of the present invention also comprises device for recovering tail gas, and the pneumatic outlet on the described quartz tube reactor is communicated with device for recovering tail gas by pipeline.
Further, describedly be positioned over the 1/5-1/3 place of quartz tube reactor length overall, preferably 1/4 place be used to the container that takes up solid-state reactants.
Another object of the present invention also provides a kind of iron filling carbon nano-pipe, and its iron loading level reaches as high as 43.1wt%.
For achieving the above object, the technical solution used in the present invention is: a kind of iron filling carbon nano-pipe, adopt the preparation method of iron filling carbon nano-pipe to be prepared from.
The preparation method of iron filling carbon nano-pipe of the present invention is with carbon source and catalyst precursor at a certain temperature, by the method for the catalytic chemical gaseous phase deposition that swims, one step of original position prepare have in the pipe that iron is filled, tube wall nitrating or the carbon nanotube of nitrating not.The preparation method of iron filling carbon nano-pipe of the present invention has the following advantages compared with prior art: (1) technology of the present invention is simple, and the product structure controllability is good.The fe that catalyst precursor used in the present invention forms after reducing can be filled in the carbon nanotube in the catalyzed carbon nanotube growth in a large number.(2) the loading level height of iron in the carbon nanotube has good economic benefit.The present invention adopts carbon-free catalyst precursor FERRIC CHLORIDE ANHYDROUS (volatilization temperature at 300 ° more than the C), reactant iron carbon atomic ratio can improve the filling ratio of iron in the carbon nanotube only up to the restriction of 1:10 when having broken through ferrocene as catalyst precursor by the consumption that increases iron trichloride.Utilize the iron filling carbon nano-pipe of this method preparation to have a good application prospect at aspects such as magnetic recording, absorption of electromagnetic wave, Field Emission Display, fuel cells.
In addition, when adopting solid-state itrogenous organic substance simultaneously as carbon source, utilize the characteristics of the higher and easy volatilization of its nitrogen content, thereby can not need to add in addition nitrogenous source, realized that the original position single stage method prepares the carbon nanotube of nitrogen doping iron filled-type, be conducive to simplify technology, reduced cost.
Description of drawings
The iron filling carbon nano-pipe 1 that Fig. 1 prepares for existing iron filling carbon nano-pipe preparation method;
The iron filling carbon nano-pipe 2 that Fig. 2 prepares for existing iron filling carbon nano-pipe preparation method;
Fig. 3 is the structural representation of embodiment 1 preparation method's that realizes the iron filling carbon nano-pipe reaction unit;
Fig. 4 is the transmission electron microscope photo of the prepared nitrogen doping iron filling carbon nano-pipe of embodiment 1;
Fig. 5 is the transmission electron microscope photo of the prepared nitrogen doping iron filling carbon nano-pipe of embodiment 2;
Fig. 6 is the structural representation of embodiment 3 preparation method's that realizes the iron filling carbon nano-pipes reaction unit;
Fig. 7 is the prepared unazotized iron filling carbon nano-pipe transmission electron microscope photo of embodiment 3;
Fig. 8 is the thermogravimetric curve of embodiment 1,2 and 3 products therefroms.
Embodiment
The invention discloses a kind of preparation method and reaction unit of iron filling carbon nano-pipe, it is catalyst precursor that the preparation method of this iron filling carbon nano-pipe adopts the inorganic covalent compound FERRIC CHLORIDE ANHYDROUS of iron, select different carbon sources for use, prepare no nitrogen doping iron filling carbon nano-pipe and nitrogen doping iron filling carbon nano-pipe by the method for the catalytic chemical gaseous phase deposition that swims.The fe that catalyst precursor FERRIC CHLORIDE ANHYDROUS used in the present invention forms after reducing can be filled in the carbon nanotube in the catalyzed carbon nanotube growth in a large number, reactant iron carbon atomic ratio can improve the compactedness of iron in the carbon nanotube only up to the restriction of 1:10 when having broken through ferrocene as catalyst precursor by the consumption that increases FERRIC CHLORIDE ANHYDROUS.
Particularly, when carbon source was solid-state organic compound, the preparation method of nitrogen doping iron filling carbon nano-pipe may further comprise the steps:
(1) two containers that take up carbon source and catalyst precursor respectively being positioned over two ends is respectively arranged with in the quartz tube reactor of gas inlet and pneumatic outlet; and make two containers near the gas inlet, so that can carrying the material of volatilization, the inert protective gas that enters from the gas inlet enters the participation reaction of quartz tube reactor middle part.Be appreciated that except quartz tube reactor the present invention can also adopt other forms of high temperature resistant tubular type reactor;
(2) quartz tube reactor is placed the tubular type heating installation, make two containers in the heated perimeter of tubular type heating installation, and for the ease of observing material surplus in the container, two containers should be tried one's best near the end of tubular type heating installation;
(3) feed inertia protection gas in quartz tube reactor, inert protective gas can be used for carrying volatile material to reaction zone on the one hand, can prevent that on the other hand the product that generates is oxidized.Open heating installation to temperature of reaction, volatilization for the catalyst precursor of gaseous state and carbon source under the drive of inert protective gas, enter the high-temperature zone at quartz tube reactor middle part (because the silica tube two ends contact with atmosphere, the temperature at two ends is a little less than the temperature at silica tube middle part) carry out chemical vapour deposition reaction, treat to stop heating after the material volatilization finishes in the container, be appreciated that, place according to reaction ratio as carbon source and catalyzer, two interior materials of reactor should volatilize totally simultaneously, excessive as certain material, then another material volatilization totally can stop heating;
(4) quartz tube reactor is cooled to room temperature under inert protective atmosphere, collects the product in the quartz tube reactor, obtain the iron filling carbon nano-pipe.
The mass ratio of described carbon source and catalyst precursor is 1:0.5-5, preferred 1:1-3.Nitrogenous solid-state organic compound is one or more in trimeric cyanamide, Dyhard RU 100, vulkacit H and the imidazoles.Trimeric cyanamide preferably, trimeric cyanamide nitrogen content height can be simultaneously prepare the carbon nanotube of nitrogen doping iron filled-type as carbon source and nitrogenous source.And the volatilization temperature of trimeric cyanamide and FERRIC CHLORIDE ANHYDROUS approach, and are about 300 ℃, are a kind of industrial raw material of cheapness.Inertia protection gas of the present invention should not react with reactant and product, and inertia protection gas can be selected one or more in argon gas, helium and the nitrogen for use.Described inert protective gas can not enter in the carbon nanotube substantially, i.e. when inertia protection gas was nitrogen, carbon source was non-nitrogenous carbon source, and the carbon nanotube for preparing also is non-nitrogen-doped carbon nanometer pipe.Described temperature of reaction is 700～1000 ° of C.
The present invention can adopt solid-state itrogenous organic substance as carbon source, and utilizes the characteristics of the higher and easy volatilization of its nitrogen content, need not to add in addition nitrogenous source, has realized that the original position single stage method prepares the carbon nanotube of nitrogen doping iron filled-type, is conducive to simplify technology, reduces cost.
When described carbon source is gaseous hydrocarbons and/or liquid organic compound, preparation method and the aforesaid method of iron filling carbon nano-pipe are basic identical, but because carbon source changes gaseous state and/or liquid state into by solid-state, so adaptive change has taken place the feed way of carbon source, particularly, may further comprise the steps:
(1) container that will take up catalyst precursor is positioned over two ends and is respectively arranged with in the quartz tube reactor of gas inlet and pneumatic outlet; and make container near the end of quartz tube reactor near the gas inlet, so that can carrying the material of volatilization, the inert protective gas that enters from the gas inlet enters the participation reaction of quartz tube reactor middle part.Be appreciated that except quartz tube reactor the present invention can also adopt other forms of high temperature resistant tubular type reactor;
(2) quartz tube reactor is placed the tubular type heating installation, make the container should be in the heated perimeter of tubular type heating installation, and for the ease of observing material surplus in the container, container should be tried one's best near the end of tubular type heating installation;
(3) in quartz tube reactor, feed inertia protection gas, open heating installation to temperature of reaction, feed carbon source (when carbon source is fluent meterial, by changing gaseous state rapidly into behind the fresh feed pump input quartz tube reactor) and hydrogen, with volatilization for the catalyst precursor of gaseous state under the drive of inert protective gas carrier gas, chemical vapour deposition reaction is carried out in the high-temperature zone that enters the quartz tube reactor middle part, treats to stop heating after the volatilization of container inner catalyst presoma finishes; Wherein inert protective gas can be used for carrying volatile material to reaction zone on the one hand, can prevent that on the other hand the product that generates is oxidized.
(4) quartz tube reactor is cooled to room temperature under inert protective atmosphere, collects the product in the quartz tube reactor, same tubular type heating installation middle part temperature is the highest, and product focuses mostly at the reactor middle part, obtains the iron filling carbon nano-pipe.
The mass ratio of gaseous state described in the present invention and/or liquid organic compound and catalyst precursor is 1:0.1-10, preferably 1:1-5.Described temperature of reaction is 700～1000 ℃, preferably 800-900 ℃.Among the present invention, described gaseous organic compound is gaseous hydrocarbons, is specially in methane, ethene and the acetylene one or more.Described liquid organic compound is nonnitrogenous liquefied hydrocarbon or nitrogenous liquid organic compound.Described nonnitrogenous liquid hydrocarbon includes but not limited to hexanaphthene or benzene; Described nitrogenous liquid organic compound is one or more in acetonitrile, pyridine, dimethyl formamide and the pyrimidine.
Discharge relation between each fluid satisfies following proportionlity usually: described gaseous hydrocarbons and/or liquid organic compound flow range are 5-80sccm, preferably 20-60 sccm.Inertia protection gas is one or more in argon gas, helium and the nitrogen, and flow range is 100-800sccm, preferably 200-600 sccm.Used hydrogen is 100-300sccm, is preferably 200sccm.
Above-mentioned solid-state organic compound comprises nitrogenous solid-state organic compound or nonnitrogenous solid-state organic compound; Gaseous organic compound is gaseous hydrocarbons, and described liquid organic compound is nonnitrogenous liquefied hydrocarbon or nitrogenous liquid organic compound.Be appreciated that when carbon source and can prepare nitrogen doping iron filling carbon nano-pipe during for nitrogenous substances, can prepare no nitrogen doping iron filling carbon nano-pipe during for non-nitrogenous substances.
The present invention also provides a kind of reaction unit of realizing the preparation method of iron filling carbon nano-pipe, this iron filling carbon nano-pipe reaction unit comprises: tubular oven, the container, the two ends that are used for taking up solid-state reactants are respectively arranged with the quartz tube reactor of gas inlet and pneumatic outlet, describedly be placed in the quartz tube reactor a end near the gas inlet be used to the container that takes up solid-state reactants, described quartz tube reactor is positioned in the tubular oven.
The container that is used for taking up solid-state reactants is porcelain boat, and the quantity that is used for taking up the container of solid-state reactants can arrange according to reactant species and quantity, and the container that is used for taking up solid-state reactants when being solid-state organic compound as carbon source should be two; A container that is used for taking up solid-state reactants when being unazotized gaseous state and/or liquid organic compound, carbon source only need be set; Described tubular type heating installation is tube type resistance furnace.Iron filling carbon nano-pipe reaction unit of the present invention also comprises device for recovering tail gas, and the pneumatic outlet on the described quartz tube reactor is communicated with device for recovering tail gas by pipeline.
Take up the surplus of material in the container of solid-state reactants for the ease of observation, the container that is used for taking up solid-state reactants among the present invention is positioned over the 1/5-1/3 place of quartz tube reactor length overall, preferably 1/4 place.
The present invention also provides a kind of iron filling carbon nano-pipe, and its iron loading level is up to 43.1wt%.This iron filling carbon nano-pipe adopts the preparation method of iron filling carbon nano-pipe to be prepared from.This iron filling carbon nano-pipe has a good application prospect at aspects such as magnetic recording, absorption of electromagnetic wave, Field Emission Display, fuel cells.
Below the present invention will be described by specific embodiment:
Embodiment 1
Fig. 3 is the structural representation of embodiment 1 preparation method's that realizes the iron filling carbon nano-pipe reaction unit; Fig. 4 is the transmission electron microscope photo of the prepared nitrogen doping iron filling carbon nano-pipe of embodiment 1; Fig. 8 is the thermogravimetric curve of embodiment 1,2 and 3 products therefroms.
Present embodiment discloses a kind of preparation method of nitrogen doping iron filling carbon nano-pipe, adopt iron filling carbon nano-pipe reaction unit shown in Figure 3, this reaction unit comprises: the tube type resistance furnace 3 with temperature regulating device, two porcelain boats 2 that are used for taking up solid-state reactants, two ends are respectively arranged with the quartz tube reactor 5 of gas inlet 7 and pneumatic outlet 4, be placed on ends of close gas inletes 7 in the quartz tube reactor 5 for the porcelain boat 2 that takes up solid-state reactants, the porcelain boat 2 that is specifically used for taking up solid-state reactants is positioned over 1/3 place of quartz tube reactor length overall, and this quartz tube reactor 5 is positioned in the tube type resistance furnace 3.Described under meter 1(is used for the flow of metering inert gas Ar) be communicated with gas inlet 7 on the quartz tube reactor 5.This iron filling carbon nano-pipe reaction unit also comprises device for recovering tail gas, and the pneumatic outlet 4 on the quartz tube reactor 5 is communicated with device for recovering tail gas by pipeline.
The preparation method of nitrogen doping iron filling carbon nano-pipe may further comprise the steps:
Take by weighing trimeric cyanamide and FERRIC CHLORIDE ANHYDROUS by the 1:1 mass ratio, in two porcelain boats 2 that are placed in, sprawl evenly.With two porcelain boats 2 and drain in the quartz tube reactor 5, again quartz tube reactor 5 is placed in the tube type resistance furnace 3.In the quartz tube reactor 5 of good seal, feed inert protective gas Ar; simultaneously with tube type resistance furnace 3 temperature programmings to 800 ℃; regulating the Ar gas flow is 200 mL/min; promote silica tube and make porcelain boat enter the fire door of tube type resistance furnace 3, make trimeric cyanamide and iron trichloride keep slow volatileness always.Stop heating after reaction finishes, silica tube is cooled to room temperature under Ar atmosphere, collect the black product at silica tube middle part, be nitrogen doping iron filling carbon nano-pipe product (product is designated as Fe@N-CNTs-800 ℃).
Product characterizes: transmission electron microscope (TEM) is observed (Fig. 4) and is shown, the external diameter of synthetic nitrogen doping iron filling carbon nano-pipe is about 250 nm when temperature of reaction is 800 ℃, the tube wall of nitrogen doping iron filling carbon nano-pipe shows irregular fold-like structures, very unsmooth of tube wall, this may be because the doping of nitrogen causes.The length of filling iron in the nitrogen doping iron filling carbon nano-pipe can reach 1 μ m between the 2 μ m, and namely this nitrogen doping iron filling carbon nano-pipe is the nitrogen doping iron filling carbon nano-pipe that Fe nanowire is filled, and illustrates that the filling effect of iron under 800 ℃ of conditions is better.To its carry out thermogravimetric analysis (condition: air atmosphere, temperature rise rate be 10 ℃/min), as shown in Figure 8, learn that the iron loading level is up to 43.1 wt%.(XPS) detects its nitrogen content with the x-ray photoelectron power spectrum, learns that nitrogen-atoms proportion in carbon nitrogen total atom number is 3.90 atm%.Magnetism testing shows that the specific magnetising moment of product is 15000 Oe(oersteds in magneticstrength) to locate to reach capacity, saturation magnetization is up to 73.2 emu/g.
Embodiment 2
Fig. 5 is the transmission electron microscope photo of the prepared nitrogen doping iron filling carbon nano-pipe of embodiment 2;
Present embodiment discloses a kind of preparation method of nitrogen doping iron filling carbon nano-pipe, adopts the reaction unit identical with embodiment 1, and the preparation method of nitrogen doping iron filling carbon nano-pipe may further comprise the steps:
Take by weighing trimeric cyanamide and FERRIC CHLORIDE ANHYDROUS by the 1:1 mass ratio, in two porcelain boats 2 that are placed in, sprawl evenly.With two porcelain boats 2 and drain in the quartz tube reactor 5, again quartz tube reactor 5 is placed in the tube type resistance furnace 3.In the quartz tube reactor 5 of good seal, feed inert protective gas Ar; simultaneously with tube type resistance furnace 3 temperature programmings to 700 ℃; regulating the Ar gas flow is 200 mL/min; promote silica tube and make porcelain boat enter the fire door of tube type resistance furnace 3, make trimeric cyanamide and iron trichloride keep slow volatileness always.Stop heating after reaction finishes, silica tube is cooled to room temperature under Ar atmosphere, collect the black product at silica tube middle part, be nitrogen doping iron filling carbon nano-pipe product (product is designated as Fe@N-CNTs-700 ℃).
Product characterizes: use transmission electron microscope (TEM) that prepared iron filling nitrogen doped carbon nanometer pipe is characterized (Fig. 5).The compactedness of iron slightly reduces, and what fill in the cavity of most nitrogen doping iron filled with nanotubes is the nanometer rod of iron, and the diameter of these nanometer rod is between 50-125 nm, and length is about 0.2-1 μ m.It is carried out thermogravimetric analysis, and as shown in Figure 8, the iron loading level reaches 31.9 wt%.(XPS) detects nitrogen content with the x-ray photoelectron power spectrum, learns that nitrogen-atoms proportion in carbon nitrogen total atom number is 5.60 atm%.Magnetism testing shows that the specific magnetising moment of product is that 15000 Oe places reach capacity in magneticstrength, and saturation magnetization is 40.7 emu/g.
Embodiment 3
Fig. 6 is the structural representation of embodiment 3 preparation method's that realizes the iron filling carbon nano-pipes reaction unit; Fig. 7 is the prepared unazotized iron filling carbon nano-pipe transmission electron microscope photo of embodiment 3;
Present embodiment discloses a kind of preparation method of iron filling carbon nano-pipe; the reaction unit that adopts as shown in Figure 6; substantially the same manner as Example 1, different is only to be provided with a porcelain boat 2 in this reaction unit, the same with inertia protection gas 7 addings from the gas inlet with hydrogen of carbon source.
The preparation method of iron filling carbon nano-pipe may further comprise the steps: take by weighing 0.5 g FERRIC CHLORIDE ANHYDROUS and place porcelain boat, and sprawl evenly, porcelain boat 2 is put into quartz tube reactor 5, quartz tube reactor is placed in the tube type resistance furnace 3 again.Feed the Ar shielding gas in the quartz tube reactor 5 of good seal, simultaneously with tube type resistance furnace 3 temperature programmings to 800 ℃; After treating that tube furnace rises to design temperature, regulating the Ar gas flow is 600 mL/min, feeds ethene (20 mL/min) and hydrogen (200 mL/min), promotes silica tube and makes porcelain boat enter fire door, makes iron trichloride keep slow volatileness always.30 min afterreactions finish, and stop heating, close ethene and hydrogen.Silica tube is cooled to room temperature under inert protective atmosphere, collects the black product at silica tube middle part, be the iron filling carbon nano-pipe product (product is designated as Fe@CNTs-800 ℃) that no nitrogen mixes.
Product characterizes: with transmission electron microscope (TEM) prepared no nitrogen doping iron filling carbon nano-pipe is characterized, as shown in Figure 7.Compare for e@N-CNTs-800 ℃ with aforementioned nitrogen doped F, its diameter is less, and about 60-70 nm, and tube wall is level and smooth, visible Fe nanowire (length is in micron level) of filling in the carbon nanotube.Magnetism testing shows that its saturation magnetization is 38.4 emu/g.Thermogravimetric analysis as shown in Figure 8, the result shows, the loading level of iron is 23.4 wt%, though be lower than prepare under the aforementioned uniform temp nitrogen doping iron filled with nanotubes arranged, but the no nitrogen doping iron filling carbon nano-pipe that is higher than bibliographical information is far away compared, L. Vovchenko for example, what people such as et al reported recently is catalyzer with the ferrocene, benzene is carbon source, iron filling carbon nano-pipe [the Physica E. 2012 of preparation, 44 (6), 928 – 931.], thermogravimetric analysis is the result show, the iron loading level has only 6.5wt% (using the concentration of ferrocene to be 40wt%) and 4.0wt% (concentration of ferrocene is 25wt%) in the sample.
The present invention is not limited to preparation method and the reaction unit of the iron filling carbon nano-pipe that above-described embodiment puts down in writing, and the change of the change of carbon source, carbon source and catalyst precursor mass ratio, the change of conversion unit are all within protection scope of the present invention.
It should be noted that at last: above each embodiment is not intended to limit only in order to technical scheme of the present invention to be described; Although the present invention has been described in detail with reference to aforementioned each embodiment, those of ordinary skill in the art is to be understood that: it still can be made amendment to the technical scheme that aforementioned each embodiment puts down in writing, and perhaps some or all of technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution break away from the scope of various embodiments of the present invention technical scheme.
Claims (10)
1. the preparation method of an iron filling carbon nano-pipe is characterized in that, when carbon source is solid-state organic compound, may further comprise the steps:
(1) two containers that take up carbon source and catalyst precursor respectively is positioned over two ends and is respectively arranged with in the quartz tube reactor of gas inlet and pneumatic outlet, and make two containers near the gas inlet; (2) quartz tube reactor is placed the tubular type heating installation; (3) in quartz tube reactor, feed inertia protection gas, open heating installation to temperature of reaction, volatilization for the catalyst precursor of gaseous state and carbon source under the drive of inert protective gas carrier gas, chemical vapour deposition reaction is carried out in the high-temperature zone that enters the quartz tube reactor middle part, treats to stop heating after the material volatilization finishes in the container; (4) quartz tube reactor is cooled to room temperature under inert protective atmosphere, collects the product in the quartz tube reactor, obtain the iron filling carbon nano-pipe;
When described carbon source is gaseous state and/or liquid organic compound, may further comprise the steps:
(1) container that will take up catalyst precursor is positioned over two ends and is respectively arranged with in the quartz tube reactor of gas inlet and pneumatic outlet, and makes container near the gas inlet; (2) quartz tube reactor is placed the tubular type heating installation; (3) in quartz tube reactor, feed inertia protection gas, open heating installation to temperature of reaction, feed carbon source and hydrogen, with volatilization for the catalyst precursor of gaseous state under the drive of inert protective gas carrier gas, chemical vapour deposition reaction is carried out in the high-temperature zone that enters the quartz tube reactor middle part, treats to stop heating after the volatilization of container inner catalyst presoma finishes; (4) quartz tube reactor is cooled to room temperature under inert protective atmosphere, collects the product in the quartz tube reactor, obtain the iron filling carbon nano-pipe;
Wherein, described catalyst precursor is FERRIC CHLORIDE ANHYDROUS.
2. according to the preparation method of the described iron filling carbon nano-pipe of claim 1, it is characterized in that described solid-state organic compound comprises nitrogenous solid-state organic compound or nonnitrogenous solid-state organic compound; Described gaseous organic compound is gaseous hydrocarbons, and described liquid organic compound is nonnitrogenous liquefied hydrocarbon or nitrogenous liquid organic compound.
3. according to the preparation method of the described iron filling carbon nano-pipe of claim 1, it is characterized in that the mass ratio of described solid-state organic compound and catalyst precursor is 1:0.5-5; The mass ratio of described gaseous state and/or liquid organic compound and catalyst precursor is 1:0.1-10.
4. according to the preparation method of the described iron filling carbon nano-pipe of claim 2, it is characterized in that, described nitrogenous solid-state organic compound is one or more in trimeric cyanamide, Dyhard RU 100, vulkacit H and the imidazoles, and described unazotized solid-state organic compound is camphor; Described gaseous hydrocarbons is one or more in methane, ethene and the acetylene; Described unazotized liquefied hydrocarbon is hexanaphthene or benzene, and described nitrogenous liquid organic compound is one or more in nitrogenous liquid nitrile, amine and the heterocycle hydro carbons.
5. according to the preparation method of the described iron filling carbon nano-pipe of claim 1, it is characterized in that described inertia protection gas is one or more in argon gas, helium and the nitrogen.
6. according to the preparation method of the described iron filling carbon nano-pipe of claim 1, it is characterized in that described temperature of reaction is 700～1000 ℃.
7. reaction unit of realizing the preparation method of any described iron filling carbon nano-pipe of claim 1-6, it is characterized in that, container, the two ends that comprise tubular oven, are used for taking up solid-state reactants are respectively arranged with the quartz tube reactor of gas inlet and pneumatic outlet, describedly be placed in the quartz tube reactor a end near the gas inlet be used to the container that takes up solid-state reactants, described quartz tube reactor is positioned in the tubular oven.
8. according to the described reaction unit of claim 7, it is characterized in that described is porcelain boat be used to the container that takes up solid-state reactants, described tubular type heating installation is tube type resistance furnace.
9. according to the described reaction unit of claim 7, it is characterized in that the described 1/5-1/3 place that is positioned over the quartz tube reactor length overall be used to the container that takes up solid-state reactants.
10. an iron filling carbon nano-pipe is characterized in that, adopts the preparation method of any described iron filling carbon nano-pipe of claim 1-6 to be prepared from.
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| CN103934042A (en) * | 2014-04-29 | 2014-07-23 | 中国石油大学(华东) | Vapor-phase deposition preparation method of load type iron catalyst |
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