CN100446854C - Catalyst for preparing carbon nanotube and its prepn - Google Patents
Catalyst for preparing carbon nanotube and its prepn Download PDFInfo
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- CN100446854C CN100446854C CNB03117874XA CN03117874A CN100446854C CN 100446854 C CN100446854 C CN 100446854C CN B03117874X A CNB03117874X A CN B03117874XA CN 03117874 A CN03117874 A CN 03117874A CN 100446854 C CN100446854 C CN 100446854C
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Abstract
The present invention relates to a catalyst for preparing carbon nanometer tubes and a preparation method of the catalyst. The catalyst is in a perovskite or perovskite-like structure, and the general formula of the structure is AM<1-x>L<x>O<y> or A<2>M<1-x>L<x>O<y>, wherein A is rare earth elements or alkaline earth elements, M is one of Fe, Co or Ni, L is the other element contained in Fe, Co and Ni, M is not equal to L, x is equal to. 01 to 0.50, and y is equal to 3 or 4. After the catalyst is reduced by the hydrogen gas under the heating condition, a new substance of A hydroxide is prepared. When the catalyst is prepared, salt or oxide of the corresponding elements is used as raw materials, one or a plurality of citric acid, tartaric acid, glycine and ethylenediamine tetraacetic acid are used as complexing agents and combustion agents, and the catalyst is prepared by a gelation combustion synthesis method in water or ethanol solution. Ammonia or ammonium compounds as hole forming agents can be added in the preparation process if necessary, and the catalyst has a large specific surface area. The catalyst causes the prepared carbon nanometer tubes to have uniform tube diameters and high yield.
Description
Technical field
What the present invention relates to is a kind of method for preparing CNT, specifically is to use the catalyst with calcium titanium or class calcium titanium structure to prepare CNT.
Background technology
CNT is a kind of nano-carbon material of excellent performance, at microelectronics, and composite, there is fine application prospect in all fields such as catalysis.Studies show that in a large number: the caliber of CNT and the size of helical angle are two principal elements of decision carbon nanotube properties.Therefore, no matter be that CNT is carried out the property research or the practical application of CNT, all require CNT to have caliber uniformly.Simultaneously, the key factor of decision CNT cost is the productive rate of CNT with respect to catalyst, and can it also be one of the key factor that be used widely of restriction CNT.The preparation method of CNT is very many, as arc discharge method, and laser ablation method, catalystic pyrolysis etc.Compare with laser ablation method with arc discharge method, catalystic pyrolysis is owing to have the productive rate height of CNT, and cost is low, and preparation condition and CNT pattern are easy to advantages such as control, are had an optimistic view of by people at present.And in the catalytic pyrolysis chemical vapour deposition technique, catalyst is again of paramount importance factor.Currently used most of catalyst all is to load on silica (SiO
2), the single-metal reforming catalyst on the carrier such as zeolite, molecular sieve.Adopt the catalyst of this method preparation, the particle diameter wider distribution, and the catalytic activity for practical application is on the low side relatively, and catalyst-supporting support also is difficult to remove.Therefore, when causing CNT caliber wider distribution and productive rate low, the purge process of CNT also bothers.Thereby this catalyst of traditional form still can not satisfy requirement of actual application at present.
Summary of the invention
In view of the foregoing, the present invention at first will provide a kind of catalyst that is used to prepare CNT, making it can improve the productive rate to the preparation CNT, the cost of reduction CNT, can improve the quality of prepared CNT again, mainly is the uniformity that improves the CNT caliber.Now, the present invention also will provide the method for said this catalyst of preparation.
Experimental result shows, in the catalytic pyrolysis chemical vapour deposition technique, the uniform diameter of CNT mainly is by the uniformity decision of catalyst activity species particle diameter.And the productive rate of CNT is by the character of catalyst own and the decision of active specy particle size to a great extent.Therefore, control the particle size and the distribution of catalyst activity species effectively, just become the key of preparation high yield, high-quality CNT.Studies show that in a large number: under identical preparation condition, the particle diameter of alloy is often littler also more even than monometallic particle diameter.Therefore, as catalyst, increasing the specific area of catalyst with alloy particle, and stop the gathering of catalyst activity species particle, is one of approach that improves CNT quality and productive rate.
The said catalyst that is used to prepare CNT of the present invention has perovskite or perovskite-like structure, and its general structure can be expressed as: AM
1-xL
xO
yOr A
2M
1-xL
xO
y, wherein: the A in the formula is rare earth element or alkaline earth element, and M is a kind of among Fe, Co or the Ni, and L is another element that comprises Fe, Co and Ni, and M ≠ L, x=0.01～0.50, y=2～5.This catalyst under heating condition by hydrogen reducing after, can have the novel substance of the hydroxide of A to generate, be a key character of catalyst of the present invention.
In above-mentioned catalyst, what described rare earth element generally can be among La, Sr, the Ce is a kind of.Therefore, this catalyst under～700 ℃ of heating conditions by hydrogen reducing after, can have the novel substance of the hydroxide of corresponding rare earth element to generate.
Further, the rare earth element in the above-mentioned catalyst is La preferably, and this catalyst can have La (OH) after by hydrogen reducing under 700 ℃
3Novel substance generates.
In above-mentioned catalyst, what it is characterized in that L can be among Fe, Co, the Ni is a kind of.
On the basis of foregoing, can be used as a kind of catalyst example of preferred reference, its general formula can be expressed as: LaNi
1-xFe
xO
y, in the formula: X=0.01～0.50, y=2～3.
In above-mentioned catalyst, can be used as the another kind of catalyst example of preferred reference, its general formula can be expressed as: La
2Ni
1-xFe
xO
y, X=0.01 in the formula～0.40, y=3～5.
In addition, in above-mentioned catalyst, the alkaline earth element of described A composition can be selected magnesium for use.
The above-mentioned form of the present invention is used to prepare the Preparation of catalysts of CNT, can form AM by the catalyst chemical formula of required preparation
1-xL
xO
yOr A
2M
1-xL
xO
yThe proportionate relationship of middle A, M, L, be raw material with salt or the oxide that contains A, M, L three dvielements respectively, with a kind of in citric acid, tartaric acid, glycine, the ethylenediamine tetra-acetic acid or several are as complexing agent and incendiary agent, in the aqueous solution of water or ethanol, prepare by the gel combustion synthetic method.Wherein, the implication of A, M, L is identical, that is: A is rare earth element or alkaline earth element, and M is a kind of among Fe, Co or the Ni, and L is another element that comprises Fe, Co and Ni, and M ≠ L.
In above-mentioned preparation method, in preparation process, can also further use the pore creating material of appropriate format, can make resulting catalyst can have bigger specific area.Can be with reference to the pore creating material that uses when implementing, for example can be in ammonium carbonate, carbonic hydroammonium, ammonium nitrate, ammoniacal liquor, the ammonium acetate at least a.
Experimental result shows that the combustion process among the above-mentioned preparation method generally can adopt calcination in oxygen atmosphere, and calcination temperature can be in 500 ℃ of-1000 ℃ of scopes.
As concrete preparation method's route, the mode that can adopt is: according to the chemical formula AM of prepared catalyst
1-xL
xO
yOr A
2M
1-xL
xO
yComposition, take by weighing the salt compounds that contains A, M, L by stoichiometry respectively.Wherein, elements A and molar ratio (M+L) can be 1: 1 and 2: 1.And with its water or ethanol dissolving, add excessive slightly complexing agent again, as citric acid, tartaric acid, EDTA, a kind of in the glycine or several, or add suitable pore creating material again, and as a kind of of ammonium carbonate, carbonic hydroammonium, ammonium nitrate, ammoniacal liquor, ammonium acetate or several, heating evaporation in 50-200 ℃ of temperature range then, spontaneous combustion takes place at last, generates black powder shape material.With the powder of gained under 500-1000 ℃ of temperature, in air or oxygen atmosphere calcination 3-8 hour, grind to form the particle of size about the 20-150 order again, can obtain required corresponding catalyst AM
1-xL
xO
yOr A
2M
1-xL
xO
y
Experimental result shows, in above-mentioned preparation process, if can add a kind of in ammonium carbonate, carbonic hydroammonium, ammonium nitrate, ammoniacal liquor, the ammonium acetate or several are as pore creating material, or the pore creating material of other form, can obviously increase the specific area of catalyst, thereby can make it when being used to prepare CNT, can obtain higher yield.
With the operating process of the Preparation of Catalyst CNT of the above-mentioned form of the present invention can for: will be loaded with AM
1-xL
xO
yForm or A
2M
1-xL
xO
yThe quartz boat of form catalyst is placed in the quartz tube reactor, adopts fixed-bed process to prepare CNT.Heat up while leading to nitrogen.When being raised to predetermined temperature, during as 550 ℃-1000 ℃, feed hydrogen, after a period of time is carried out in reaction, feed carbon source gas (for example: methane, acetylene, acetone, carbon monoxide etc.), N again
2And H
2Mist, the reaction certain hour can obtain the thick product of CNT.The operation of the CNT that uses Preparation of Catalyst of the present invention to obtain being carried out purification process is very simple: soaks CNT with the acid of heat (for example hydrochloric acid, nitric acid or its mixed acid etc.) and filters after 5-24 hour, and clean with distilled water again.Carbon nanometer behind the purifying gets final product 100 ℃-200 ℃ dry a few hours again.
As above-mentioned, catalyst of the present invention prepares CNT as acetylene, methane, ethene, carbon monoxide, ethane etc. as unstripped gas applicable to the several kinds of carbon source material.
The experimental result of contrast shows, uses the catalyst of the above-mentioned form of the present invention, the productive rate height of resulting CNT, and cost is low, and the caliber narrowly distributing, degree of graphitization height, function admirable
According to foregoing, under the prerequisite that does not break away from the above-mentioned basic fundamental thought of the present invention,, modification, replacement or the change of various ways can also be arranged to its content according to the ordinary skill knowledge and the customary means of this area.
Below in conjunction with the specific embodiment, foregoing of the present invention is described in further detail again by the accompanying drawing illustrated embodiment.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.All technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Description of drawings
Fig. 1 is by LaFe
0.2Ni
0.8O
3Make the CNT transmission electron microscope photo that catalyst decomposes acetylene makes.
Fig. 2 is by LaFe
0.2Ni
0.8O
3Make the CNT transmission electron microscope photo that catalyst decomposes methane makes.
Fig. 3 is the LaFe that calcining obtains in oxygen
0.05Ni
0.95O
3Decompose the CNT transmission electron microscope photo that acetylene makes.
Fig. 4 is by the LaFe that has used the pore creating material preparation
0.05Ni
0.95O
3Make the CNT transmission electron microscope photo that catalyst decomposes acetylene makes.
Fig. 5 is by LaFe
0.4Ni
0.6O
3Decompose the CNT transmission electron microscope photo that acetylene makes
Fig. 6 is by LaCo
0.2Ni
0.8O
3Decompose the CNT transmission electron microscope photo that acetylene makes
Fig. 7 is by LaFe
0.2Co
0.8O
3Decompose the CNT transmission electron microscope photo that acetylene makes
Fig. 8 is by CeFe
0.2Co
0.8O
3Decompose the CNT transmission electron microscope photo that acetylene makes
Fig. 9 is by PrFe
0.2Co
0.8O
3Decompose the CNT transmission electron microscope photo that acetylene makes
Figure 10 is the LaNiO by contrast
3Make the transmission electron microscope photo of the CNT that catalyst decomposes acetylene makes
Figure 11 is catalyst LaFe
0.2Ni
0.8O
3IR spectrogram after the reduction
Figure 12 is catalyst LaFe
0.2Ni
0.8O
3IR spectrogram before the reduction
The specific embodiment
Take by weighing 5.00g La (NO respectively
3)
36H
2O, 0.81g Fe (NO
3)
39H
2O, 2.33gNi (NO
3)
26H
2O dissolves it with distilled water, adds the 4.60g citric acid again.At 80 ℃, and constantly under the condition of stirring the above-mentioned solution of heating until evaporate to dryness, yellow jelly, under 400 ℃, jelly is carried out carbonization again, calcination 4 hours under 800 ℃ and air atmosphere in Muffle furnace at last, black powder.With the black powder of gained grind be 60 order sizes after, promptly get catalyst LaFe
0.2Ni
0.8O
3
To be loaded with 20mg LaFe
0.2Ni
0.8O
yQuartz boat in put into quartz ampoule after, the limit leads to N
2Heat up in the limit.When temperature rises to 700 ℃, logical H
2(40ml/min) reduce half an hour, change logical H again
2(50ml/min), N
2(140ml/min), C
2H
2Mist (16ml/min).Stop reaction after reaction is carried out 1 hour, collect product, product is purified, gets the CNT of 200mg after the drying.The productive rate of the CNT that this catalyst makes is 10g/g.catal., and the external diameter of CNT is 10-20nm, and its CNT transmission electron microscope photo as shown in Figure 1.In the catalyst of the gained under this condition after the reduction novel substance La (OH) is arranged
3Generate.LaFe
0.2Ni
0.8O
3IR analysis result before and after the reduction as shown in Figure 5 and Figure 6.
Embodiment 2
Adopt the catalyst identical with embodiment 1.To be loaded with 20mg LaFe
0.2Ni
0.8O
3Quartz boat in put into quartz ampoule after, the limit leads to N
2Heat up in the limit.When temperature rises to 700 ℃, logical H
2(40ml/min) reduce half an hour, change logical H again
2(50ml/min) and CH
4Mist (50ml/min).Stop reaction after reaction is carried out 1 hour, collect product, product is purified, gets the CNT of 160mg after the drying.The productive rate of the CNT that this catalyst makes is 8g/g.catal., and the external diameter of CNT is 5-10nm.The transmission electron microscope photo of gained carbon nanotube product as shown in Figure 2.
Embodiment 3
Take by weighing 5.0g La (NO respectively
3)
36H
2O, 0.2g Fe (NO
3)
39H
2O, 2.76gNi (NO
3)
26H
2O dissolves it with distilled water, adds the 4.6g citric acid again.At 80 ℃, and constantly under the condition of stirring the above-mentioned solution of heating until evaporate to dryness, yellow jelly, under 400 ℃, jelly is carried out carbonized and semi hour again, calcination 4 hours under 800 ℃ and oxygen (40ml/min) atmosphere in Muffle furnace at last must black powder.With the black powder of gained grind be 60 order sizes after, promptly get catalyst LaFe
0.05Ni
0.95O
3
The preparation condition of CNT is identical with embodiment 1.The productive rate of the CNT that this catalyst makes is 10g/g.catal., and the external diameter of CNT is 30-50nm.The transmission electron microscope photo of gained carbon nanotube product as shown in Figure 3.
Embodiment 4
Take by weighing 5.0g La (NO respectively
3)
36H
2O, 0.2g Fe (NO
3)
39H
2O, 2.76gNi (NO
3)
26H
2O dissolves it with distilled water, adds the 4.6g citric acid again, and a spot of concentrated ammonia liquor is as pore creating material.Also constantly heat above-mentioned solution under the condition of stirring at 80 ℃,, get jelly until evaporate to dryness.Under 400 ℃, jelly is carried out carbonized and semi hour again, at last in Muffle furnace under 800 ℃ and air atmosphere calcination 4 hours black powder.With the black powder of gained grind be 60 order sizes after, promptly get catalyst LaFe
0.05Ni
0.95O
3
The preparation condition of CNT is identical with embodiment 1.The CNT productive rate that this catalyst makes is 21g/g.catal., and the external diameter of CNT is 10-20nm.The transmission electron microscope photo of resulting CNT as shown in Figure 4.
Embodiment 5
Take by weighing 5.00g La (NO respectively
3)
36H
2O, 1.62g Fe (NO
3)
39H
2O, 1.75gNi (NO
3)
26H
2O dissolves it with distilled water, adds the 4.60g citric acid again.At 80 ℃, and constantly heat above-mentioned solution until evaporate to dryness under the condition of stirring, get yellow jelly, under 400 ℃ jelly is carried out carbonization again, (800 ℃, under the air atmosphere) calcination got black powder in 4 hours in Muffle furnace at last.With the black powder of gained grind be 60 order sizes after, promptly get catalyst LaFe
0.4Ni
0.6O
3To be loaded with LaFe
0.4Ni
0.6O
3Quartz boat in put into quartz ampoule after, the limit leads to N
2Heat up in the limit.When temperature rises to 700 ℃, logical H
2(40ml/min) reduce half an hour, change logical H again
2(50ml/min), N
2(140ml/min), C
2H
2Mist (16ml/min).Stop reaction after reaction is carried out 1 hour, collect product, product is purified, gets pure nano-carbon tube after the drying.The productive rate of the CNT that this catalyst makes is 11.2g/g.catal., and the external diameter of CNT is 10-20nm, and its transmission electron microscope photo is seen Fig. 5.
Embodiment 6
Take by weighing 5.00g La (NO respectively
3)
36H
2O, 1.17g Co (NO
3)
26H
2O, 2.33gNi (NO
3)
26H
2O dissolves it with distilled water, adds the 4.60g citric acid again.At 80 ℃, and constantly heat above-mentioned solution until evaporate to dryness under the condition of stirring, get yellow jelly, under 400 ℃ jelly is carried out carbonization again, (800 ℃, under the air atmosphere) calcination got black powder in 4 hours in Muffle furnace at last.With the black powder of gained grind be 60 order sizes after, promptly get catalyst LaCo
0.2Ni
0.8O
3To be loaded with LaCo
0.2Ni
0.8O
3Quartz boat in put into quartz ampoule after, the limit leads to N
2Heat up in the limit.When temperature rises to 650 ℃, logical H
2(40ml/min) reduce half an hour, change logical H again
2(50ml/min), N
2(140ml/min), C
2H
2Mist (16ml/min).Stop reaction after reaction is carried out 1 hour, collect product, product is purified, gets pure nano-carbon tube after the drying.The productive rate of the CNT that this catalyst makes is 13.2g/g.catal., and the external diameter of CNT is 7-13nm, and its transmission electron microscope photo is seen Fig. 6.
Embodiment 7
Take by weighing 5.00g La (NO respectively
3)
36H
2O, 0.81g Fe (NO
3)
29H
2O, 2.33gCo (NO
3)
26H
2O dissolves it with distilled water, adds the 4.60g citric acid again.At 80 ℃, and constantly heat above-mentioned solution until evaporate to dryness under the condition of stirring, get yellow jelly, under 400 ℃ jelly is carried out carbonization again, (800 ℃, under the air atmosphere) calcination got black powder in 4 hours in Muffle furnace at last.With the black powder of gained grind be 60 order sizes after, promptly get catalyst LaFe
0.2Co
0.8O
3To be loaded with LaFe
0.2Co
0.8O
3Quartz boat in put into quartz ampoule after, the limit leads to N
2Heat up in the limit.When temperature rises to 650 ℃, logical H
2(40ml/min) reduce half an hour, change logical H again
2(50ml/min), N
2(140ml/min), C
2H
2Mist (16ml/min).Stop reaction after reaction is carried out 1 hour, collect product, product is purified, gets pure nano-carbon tube after the drying.The productive rate of the CNT that this catalyst makes is 9.2g/g.catal., and the external diameter of CNT is 10-20nm, and its transmission electron microscope photo is seen Fig. 7.
Embodiment 8
Take by weighing 4.34g Ce (NO respectively
3)
36H
2O, 0.81g Fe (NO
3)
39H
2O, 2.33gNi (NO
3)
26H
2O dissolves it with distilled water, adds the 4.60g citric acid again.At 80 ℃, and constantly heat above-mentioned solution until evaporate to dryness under the condition of stirring, get yellow jelly, under 400 ℃ jelly is carried out carbonization again, (800 ℃, under the air atmosphere) calcination got black powder in 4 hours in Muffle furnace at last.With the black powder of gained grind be 60 order sizes after, promptly get catalyst CeFe
0.2Ni
0.8O
3To be loaded with 20mg CeFe
0.2Ni
0.8O
3Quartz boat in put into quartz ampoule after, the limit leads to N
2Heat up in the limit.When temperature rises to 700 ℃, logical H
2(40ml/min) reduce half an hour, change logical H again
2(50ml/min), N
2(140ml/min), C
2H
2Mist (16ml/min).Stop reaction after reaction is carried out 1 hour, collect product, product is purified, gets the CNT of 200mg after the drying.The productive rate of the CNT that this catalyst makes is 8.2g/g.catal., and the external diameter of CNT is 10-20nm, and its transmission electron microscope photo is seen Fig. 8.
Embodiment 9
Take by weighing 4.35g Pr (NO respectively
3)
36H
2O, 0.81g Fe (NO
3)
39H
2O, 2.33gNi (NO
3)
26H
2O dissolves it with distilled water, adds the 4.60g citric acid again.At 80 ℃, and constantly heat above-mentioned solution until evaporate to dryness under the condition of stirring, get yellow jelly, under 400 ℃ jelly is carried out carbonization again, (800 ℃, under the air atmosphere) calcination got black powder in 4 hours in Muffle furnace at last.With the black powder of gained grind be 60 order sizes after, promptly get catalyst P rFe
0.2Ni
0.8O
3To be loaded with 20mg PrFe
0.2Ni
0.8O
3Quartz boat in put into quartz ampoule after, the limit leads to N
2Heat up in the limit.When temperature rises to 700 ℃, logical H
2(40ml/min) reduce half an hour, change logical H again
2(50ml/min), N
2(140ml/min), C
2H
2Mist (16ml/min).Stop reaction after reaction is carried out 1 hour, collect product, product is purified, gets the CNT of 200mg after the drying.The productive rate of the CNT that this catalyst makes is 8.6g/g.catal., and the external diameter of CNT is that its transmission electron microscope photo of 7-14nm. is seen Fig. 9.
Embodiment 10
Take by weighing 10.00g La (NO respectively
3)
36H
2O, 0.81g Fe (NO
3)
39H
2O, 2.33gNi (NO
3)
26H
2O dissolves it with distilled water, adds the 7.60g citric acid again.With reference to embodiment 1 preparation catalyst La
2Fe
0.2Ni
0.8O
4And CNT.The CNT productive rate is 9.9g/g.catal., and the external diameter of CNT is 10-20nm.
Embodiment 11
Take by weighing 10.00g La (NO respectively
3)
36H
2O, 0.42g Cu (NO
3)
2, 2.33gNi (NO
3)
26H
2O dissolves it with distilled water, adds the 8.30g citric acid again.With reference to embodiment 1 preparation catalyst La
2Cu
0.15Ni
0.85O
3.7And CNT.The CNT productive rate is 11.2g/g.catal., and the external diameter of CNT is 10-15nm.
Comparative Examples
Take by weighing 5.00g La (NO respectively
3)
36H
2O, 2.91g Ni (NO
3)
26H
2O dissolves it with distilled water, adds the 4.60g citric acid again.At 80 ℃, and constantly under the condition of stirring the above-mentioned solution of heating until evaporate to dryness, yellow jelly, under 400 ℃, jelly is carried out carbonization again, at last in Muffle furnace under 800 ℃ and air atmosphere calcination 4 hours black powder.With the black powder of gained grind be 60 order sizes after, promptly get catalyst LaNiO
3
To be loaded with 20mg LaNiO
3Quartz boat in put into quartz ampoule after, the limit leads to N
2Heat up in the limit.When temperature rises to 700 ℃, logical H
2(40ml/min) reduce half an hour, change logical H again
2(50ml/min), N
2(140ml/min), C
2H
2Mist (16ml/min).Stop reaction after reaction is carried out 1 hour, collect product, product is purified, after the drying the CNT of 100mg. the productive rate by the CNT of this method preparation is 5g/g.catal., and the external diameter of CNT is 10-40nm.Resulting CNT transmission electron microscope photo is seen Figure 10.
Claims (10)
1. a method for preparing CNT adopts the fixed-bed process preparation, it is characterized in that comprising the steps:
(1) quartz boat that will be loaded with catalyst is placed in the quartz tube reactor, heats up while lead to nitrogen, and wherein catalyst has perovskite or perovskite-like structure, and general structure is AM
1-xL
xO
y, or A
2M
1-xL
xO
y, the A in the formula is a kind of among La, Sr, the Ce, M is a kind of among Fe, Co or the Ni, L is a kind of among Fe, Co, the Ni, and M ≠ L, x=0.01～0.50, y=2～5, this catalyst under heating condition by hydrogen reducing after, have the novel substance of the hydroxide of A to generate;
(2) when being raised to predetermined temperature 550-1000 ℃, feed hydrogen, after a period of time is carried out in reaction, feed carbon source gas, N again
2And H
2Mist, carbon source gas is methane, acetylene, acetone or carbon monoxide, the reaction certain hour can obtain the thick product of CNT;
(3) hydrochloric acid, nitric acid or its mixed acid immersion CNT with heat filtered after 5-24 hour, cleaned with distilled water again, and the CNT behind the purifying gets final product between 100-200 ℃ of dry a few hours again.
2. according to the described a kind of method for preparing CNT of claim 1, it is characterized in that described elements A is La, this catalyst is having La (OH) after by hydrogen reducing under 700 ℃
3Novel substance generates.
3. according to claim 1 or 2 described a kind of methods that prepare CNT, the general formula that it is characterized in that described catalyst is LaNi
1-xFe
xO
y, in the formula: x=0.01～0.50, y=2～3.
4. according to claim 1 or 2 described a kind of methods that prepare CNT, the general formula that it is characterized in that described catalyst is La
2Ni
1-xFe
xO
y, in the formula: x=0.01～0.40, y=3～5.
5. according to claim 1 or the 2 described methods that prepare CNT, it is characterized in that described method for preparing catalyst is as follows: the catalyst chemical formula by required preparation is formed AM
1-xL
xO
yOr A
2M
1-xL
xO
yThe proportionate relationship of middle A, M, L, be raw material with salt or the oxide that contains A, M, L three dvielements respectively, at least a as complexing agent and incendiary agent with in citric acid, tartaric acid, glycine, the ethylenediamine tetra-acetic acid in the aqueous solution of water or ethanol, prepares by the gel combustion synthetic method.
6. according to the described method for preparing CNT of claim 5, it is characterized in that in catalyst preparation process, also adding pore creating material is arranged.
7. the method for preparing CNT according to claim 6 is characterized in that described pore creating material is at least a in ammonium carbonate, carbonic hydroammonium, ammonium nitrate, ammoniacal liquor, the ammonium acetate.
8. the method for preparing CNT according to claim 5 is characterized in that catalyst calcination preparation in oxidizing atmosphere, and calcination temperature is 500-1000 ℃.
9. the method for preparing CNT according to claim 6 is characterized in that catalyst calcination preparation in oxidizing atmosphere, and calcination temperature is 500-1000 ℃.
10. the method for preparing CNT according to claim 7 is characterized in that catalyst calcination preparation in oxidizing atmosphere, and calcination temperature is 500-1000 ℃.
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| CN107010663B (en) * | 2017-04-11 | 2018-06-19 | 陕西科技大学 | The method that a kind of tartaric acid-nitrate combustion method prepares zirconic acid yttrium |
| CN107500268A (en) * | 2017-10-19 | 2017-12-22 | 焦作集越纳米材料技术有限公司 | A kind of preparation method of CNT |
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| CN111514903A (en) * | 2019-12-25 | 2020-08-11 | 江西悦安新材料股份有限公司 | Method for preparing iron-based array carbon tube catalyst in large scale |
| CN111841561A (en) * | 2020-07-09 | 2020-10-30 | 江西铜业技术研究院有限公司 | High-efficiency catalyst for growing carbon nano tube and preparation and use methods thereof |
| CN112962116B (en) * | 2021-02-09 | 2022-05-24 | 江南大学 | ABO3Type double perovskite LaCoyNi1-yO3Nano-rod electrocatalytic material and preparation method thereof |
| CN114570354B (en) * | 2022-03-11 | 2023-08-15 | 清华大学 | Perovskite catalyst and preparation method thereof |
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