CN110339842A - A kind of composite catalyst and preparation method thereof growing carbon nanotube - Google Patents
A kind of composite catalyst and preparation method thereof growing carbon nanotube Download PDFInfo
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- CN110339842A CN110339842A CN201910563543.7A CN201910563543A CN110339842A CN 110339842 A CN110339842 A CN 110339842A CN 201910563543 A CN201910563543 A CN 201910563543A CN 110339842 A CN110339842 A CN 110339842A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
Abstract
The invention belongs to carbon nanomaterial preparation process and applied technical fields, more particularly to a kind of composite catalyst and preparation method thereof for growing carbon nanotube, the composite catalyst is made of transition metal major catalyst and oxide carrier co-catalyst, by regulating and controlling stoichiometric ratio, it is uniformly distributed in major catalyst in co-catalyst and size tunable, with efficient catalytic synthesizing carbon nanotubes and the diameter and pattern of carbon nanotube can be regulated and controled；Presoma is made via chemical complexometry in the composite catalyst, two steps are calcined in air to be made, it is simple for process, low energy consumption and at low cost, can largely synthesize and realize technical grade production, there is huge application value to the carbon nanotube of the long different-diameter of Follow-up Industry metaplasia and pattern.
Description
Technical field
The present invention relates to belong to carbon nanomaterial preparation process and applied technical field.More specifically, it is related to one kind
Grow the composite catalyst and preparation method thereof of carbon nanotube.
Background technique
Carbon nanotube was found by Japanese scholars Sumio Iijima in 1991, belonged to one-dimensional carbon nano material, i.e. diameter is to receive
The shape of small of meter level scale.Carbon nanotube has high-termal conductivity, chemical stability and thermal stability, and different helical angle curlings
Formed carbon nanotube is respectively provided with semiconductive and metallicity attribute；On the other hand, this tubular structure and same diameter steel
Iron phase ratio can be bent with up to 100 times or more of tensile strengths and nondestructively to 90 °；Carbon nanotube is hollow simultaneously, the original of carbon
Son amount is small, so that carbon nanotube density very little, is considered as high-strength light raw material and attracts attention.It is divided by microstructure, carbon
Nanotube includes single-walled carbon nanotube and multi-walled carbon nanotube；It is divided by macro morphology, carbon nanotube dust, carbon can be divided into again
Nanotube fibers and carbon nano-tube film etc.；Microstructure abundant has further expanded carbon nanotube with macro morphology many
The application in field.
Currently, carbon nanotube is mainly prepared by arc discharge method, laser ablation method, chemical vapour deposition technique (CVD).Its
In, CVD method is most popular because of its economy, industrial scale production capacity.And should during catalyst partial size, pattern, crystal form pair
Diameter, pattern and the length of synthesized carbon nanotube play conclusive effect.As being directed to carbon nanotube and be used to prepare
Existing KR published patent the 2010/0042765th carbon nanotube synthesis loaded catalyst of its catalyst, its system
Preparation Method and using its carbon nanotube and No. 2012/0093458 binding structure with vertical orientation high conductivity
Carbon nanotube and the high conductivity high molecule nano composite material composition for utilizing it, and it is directed to broken spherical form respectively
Catalyst and sheet type catalyst carry out disclosure, but the catalyst invented of these patents be only used for growing it is previously described
A kind of carbon nanotube, that is, making it all be not widely practiced in growth various types of due to the fixed mixing ratio of catalyst
Carbon nanotube, and in the application of the practical commercialization of carbon nanotube, it needs for different application direction using different types of carbon
Nanotube could generate greatest benefit, thus the product that these catalyst are grown is utilizing the excellent of different type carbon nanotube
There are in place of wretched insufficiency in terms of elegant characteristic.
Summary of the invention
The main object of the present invention is to provide a kind of composite catalyst and preparation method thereof for growing carbon nanotube, to solve
Any problem in above-mentioned and other potential problems of the prior art.
In order to achieve the above object, the embodiment of the present disclosure discloses a kind of composite catalyst for growing carbon nanotube, described multiple
Closing catalyst includes transition metal major catalyst and oxide carrier co-catalyst, by adjusting transition metal major catalyst and oxygen
The stoichiometric ratio of compound carrier co-catalyst is distributed in adjusting transition metal primary catalyst particles in co-catalyst.
According to the embodiment of the present disclosure, the mass ratio of the transition metal major catalyst and oxide carrier co-catalyst is
0.05~0.55:0.95~0.45.
According to the embodiment of the present disclosure, the transition metal major catalyst is one or more of in iron, cobalt, nickel or molybdenum, grain
Diameter is between 0.5~50nm.
According to the embodiment of the present disclosure, the oxide carrier co-catalyst is one in aluminium oxide, yttrium oxide or lanthana
Kind is several.
According to the embodiment of the present disclosure, the specific surface area of the composite catalyst is between 5~200cm2Between/g.
The embodiment of the present disclosure another object is that disclosing a kind of method for preparing above-mentioned composite catalyst, the method packet
Include following steps:
S1 colloid is made after) mixing according to the weighed each raw material of stoichiometric ratio using chemical complexometry, adopts in air
AB is made with two steps annealing methodxC1-xO3Perovskite type catalyst presoma, wherein 0≤x≤1；
S2 S1)) is obtained into ABxC1-xO3Perovskite type catalyst presoma is restored in a hydrogen atmosphere, obtains composite catalyzing
Agent.
According to the embodiment of the present disclosure, the S1) specifically includes the following steps:
S1.1) stoichiometrically weigh respectively the soluble-salt of element A, the soluble-salt of B element, C element soluble-salt
It is dissolved in deionized water, complexing agent is then added and stirs evenly, is heated to 80-120 DEG C, the solution evaporation after making complexing becomes glue
Body；
S1.2) then colloid described in S1.1) is warming up to 700~1100 DEG C of roastings in 350-500 DEG C of air calcination 1-24h again
Fire to obtain ABxC1-xO3Perovskite type catalyst presoma；
According to the embodiment of the present disclosure, the S2) specifically comprises the processes of:
S2.1 AB will) be obtainedxC1-xO3Perovskite type catalyst presoma is placed in horizontal pipe furnace high temperature section, vacuumizes；
S2.2 it) is first passed through inert gas and is warming up to 800~1100 DEG C, then be passed through hydrogen, the recovery time is 0.1~1h, is restored
The velocity ratio of hydrogen and inert gas is 1:1 in journey, and between 10~200sccm.
According to the embodiment of the present disclosure, the ABxC1-xO3Element A in perovskite type catalyst presoma is aluminium, yttrium or lanthanum,
B element is aluminium, yttrium or lanthanum, and C element is one of iron, cobalt, nickel, molybdenum or a variety of.
According to the embodiment of the present disclosure, the S1.1) in complexing agent be citric acid or oxalic acid；The complexing agent additional amount is rubbed
Your number is greater than or equal to two times of soluble-salt total amount；The soluble-salt is nitrate.
A method of using above-mentioned composite catalyst prepare carbon nanotube, this method specifically includes the following steps:
Composite catalyst is heated to 800~1100 DEG C, is passed through carbon-source gas reaction 0.5h, gained black powder is collected and is received for carbon
Mitron, the carbon nanotube include single-walled carbon nanotube, free property multi-walled carbon nanotube, Bamboo-shaped multi-walled carbon nanotube or multi wall
Carbon nano-tube fibre.
The carbon-source gas is methane, coal bed gas, natural gas, biogas, ethylene, acetylene, propylene or the gas being atomized in advance
One or more of state ethyl alcohol, acetone, thiacyclohexane, benzene or toluene.Compared with prior art, the present invention possessed by the present invention
It has the beneficial effect that
1, the partial size of carbon nano-tube catalyst, pattern, crystal form play decision to the diameter, pattern and length of synthesized carbon nanotube
The effect of property.This method uses chemical complexometry that major catalyst precursor is uniformly distributed in promoter precursor in the solution first
In, then calcine to obtain monocrystalline ABxC1-xO3Perovskite type catalyst presoma controls main catalytic by adjusting stoichiometric ratio perfection
Distribution sites of the agent in lattice regulate and control the content and particle diameter of major catalyst in final catalyst in turn, and can realize industry
Change large-scale production；
2, by adjusting stoichiometric ratio, obtained monocrystalline ABxC1-xO3Perovskite type catalyst presoma is passing through hydrogen reducing
Afterwards, it carries out chemical vapor deposition growth and goes out the carbon nanotube that pattern is abundant, partial size is different, including single-walled carbon nanotube, free property
Multi-walled carbon nanotube, Bamboo-shaped multi-walled carbon nanotube, multi-walled carbon nanotube fiber etc. have substantially expanded grown carbon nanotube and have existed
Range and dimension are applied in different field.
Detailed description of the invention
Fig. 1 is catalyst precursor LaFeO of the invention3XRD spectra.
Fig. 2 is to use catalyst precursor LaFeO of the present invention3What CVD was grown after reduction does not purify Bamboo-shaped carbon nanometer
Pipe schematic diagram.
Fig. 3 is to use catalyst precursor LaFeO of the present invention3The Bamboo-shaped carbon nanometer of purifying that CVD is grown after reduction
Pipe schematic diagram.
Fig. 4 is to use catalyst precursor LaFeO of the present invention3The grown carbon nano-tube fibre of CVD after reduction, (a figure is mark
50 microns of electron-microscope scanning figures of ruler；B figure is 5 microns of electron-microscope scanning figures of scale).
Fig. 5 catalyst precursor YAl0.5Fe0.5O3(a figure is that scale 2 is micro- to the carbon nano-tube fibre that CVD is grown after reduction
Rice electron-microscope scanning figure；B figure is 250 nanometers of electron-microscope scanning figures of scale).
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention is protected
It encloses.
A kind of composite catalyst for growing carbon nanotube of the present invention, the composite catalyst includes transition metal major catalyst
With oxide carrier co-catalyst, pass through the stoichiometry of adjusting transition metal major catalyst and oxide carrier co-catalyst
Than being distributed in adjusting transition metal primary catalyst particles in co-catalyst.
According to the embodiment of the present disclosure, the mass ratio of the transition metal major catalyst and oxide carrier co-catalyst is
0.05~0.55:0.95~0.45.
According to the embodiment of the present disclosure, the transition metal major catalyst is one or more of in iron, cobalt, nickel or molybdenum, grain
Diameter is between 0.5~50nm.
According to the embodiment of the present disclosure, the oxide carrier co-catalyst is one in aluminium oxide, yttrium oxide or lanthana
Kind is several.
According to the embodiment of the present disclosure, the specific surface area of the composite catalyst is between 5~200cm2Between/g.
The embodiment of the present disclosure another object is that disclosing a kind of method for preparing above-mentioned composite catalyst, the method packet
Include following steps:
S1 colloid is made after) mixing according to the weighed each raw material of stoichiometric ratio using chemical complexometry, adopts in air
AB is made with two steps annealing methodxC1-xO3Perovskite type catalyst presoma, wherein 0≤x≤1；
S2 S1)) is obtained into ABxC1-xO3Perovskite type catalyst presoma is restored in a hydrogen atmosphere, obtains composite catalyzing
Agent.
According to the embodiment of the present disclosure, the S1) specifically includes the following steps:
S1.1) stoichiometrically weigh respectively the soluble-salt of element A, the soluble-salt of B element, C element soluble-salt
It is dissolved in deionized water, complexing agent is then added and stirs evenly, is heated to 80-120 DEG C, the solution evaporation after making complexing becomes glue
Body；
S1.2) then colloid described in S1.1) is warming up to 700~1100 DEG C of roastings in 350-500 DEG C of air calcination 1-24h again
Fire to obtain ABxC1-xO3Perovskite type catalyst presoma；
According to the embodiment of the present disclosure, the S2) specifically comprises the processes of:
S2.1 AB will) be obtainedxC1-xO3Perovskite type catalyst presoma is placed in horizontal pipe furnace high temperature section, vacuumizes；
S2.2 it) is first passed through inert gas and is warming up to 800~1100 DEG C, then be passed through hydrogen, the recovery time is 0.1~1h, is restored
The velocity ratio of hydrogen and inert gas is 1:1 in journey, and between 10~200sccm.
According to the embodiment of the present disclosure, the ABxC1-xO3Element A in perovskite type catalyst presoma is aluminium, yttrium or lanthanum,
B element is aluminium, yttrium or lanthanum, and C element is one of iron, cobalt, nickel, molybdenum or a variety of.
According to the embodiment of the present disclosure, the S1.1) in complexing agent be citric acid or oxalic acid；The complexing agent additional amount is rubbed
Your number is greater than or equal to two times of soluble-salt total amount；The soluble-salt is nitrate.
A method of using above-mentioned composite catalyst prepare carbon nanotube, this method specifically includes the following steps:
Composite catalyst is heated to 800~1100 DEG C, is passed through carbon-source gas reaction 0.5h, gained black powder is collected and is received for carbon
Mitron, the carbon nanotube include single-walled carbon nanotube, free property multi-walled carbon nanotube, Bamboo-shaped multi-walled carbon nanotube or multi wall
Carbon nano-tube fibre.
The carbon-source gas is methane, coal bed gas, natural gas, biogas, ethylene, acetylene, propylene or the gas being atomized in advance
One or more of state ethyl alcohol, acetone, thiacyclohexane, benzene or toluene.
Embodiment:
ABxC1-xO3Perovskite type catalyst precursor preparation embodiment:
| A | B | x | C | 1-x | ABxC1-xO3 | |
| 1 | La | / | 0 | Fe | 1 | LaFeO3 |
| 2 | Y | / | 0 | Fe | 1 | YFeO3 |
| 3 | Al | / | 0 | Fe | 1 | AlFeO3 |
| 4 | La | / | 0 | Ni | 1 | LaNiO3 |
| 5 | Y | / | 0 | Ni | 1 | YNiO3 |
| 6 | Al | / | 0 | Ni | 1 | AlNiO3 |
| 7 | La | / | 0 | Co | 1 | LaCoO3 |
| 8 | Y | / | 0 | Co | 1 | YCoO3 |
| 9 | Al | / | 0 | Co | 1 | AlCoO3 |
| 10 | La | Al | 0<x≤0.9 | Fe | 0.1≤1-x<1 | LaAlxFe1-xO3 |
| 11 | La | Al | 0<x≤0.9 | Ni | 0.1≤1-x<1 | LaAlxNi1-xO3 |
| 12 | La | Al | 0<x≤0.9 | Co | 0.1≤1-x<1 | LaAlxCo1-xO3 |
| 13 | La | Y | 0<x≤0.9 | Fe | 0.1≤1-x<1 | LaYxFe1-xO3 |
| 14 | La | Y | 0<x≤0.9 | Ni | 0.1≤1-x<1 | LaYxNi1-xO3 |
| 15 | La | Y | 0<x≤0.9 | Co | 0.1≤1-x<1 | LaYxCo1-xO3 |
| 16 | Al | La | 0<x≤0.9 | Fe | 0.1≤1-x<1 | AlLaxFe1-xO3 |
| 17 | Al | La | 0<x≤0.9 | Ni | 0.1≤1-x<1 | AlLaxNi1-xO3 |
| 18 | Al | La | 0<x≤0.9 | Co | 0.1≤1-x<1 | AlLaxCo1-xO3 |
| 19 | Al | Y | 0<x≤0.9 | Fe | 0.1≤1-x<1 | AlYxFe1-xO3 |
| 20 | Al | Y | 0<x≤0.9 | Ni | 0.1≤1-x<1 | AlYxNi1-xO3 |
| 21 | Al | Y | 0<x≤0.9 | Co | 0.1≤1-x<1 | AlYxCo1-xO3 |
| 22 | Y | La | 0<x≤0.9 | Fe | 0.1≤1-x<1 | YLaxFe1-xO3 |
| 23 | Y | La | 0<x≤0.9 | Ni | 0.1≤1-x<1 | YLaxNi1-xO3 |
| 24 | Y | La | 0<x≤0.9 | Co | 0.1≤1-x<1 | YLaxCo1-xO3 |
| 25 | Y | Al | 0<x≤0.9 | Fe | 0.1≤1-x<1 | YAlxFe1-xO3 |
| 26 | Y | Al | 0<x≤0.9 | Ni | 0.1≤1-x<1 | YAlxNi1-xO3 |
| 27 | Y | Al | 0<x≤0.9 | Co | 0.1≤1-x<1 | YAlxCo1-xO3 |
Remarks:
1) in major catalyst usually also there is divalent stable state, such as La in Ni2NiO4；
2) component C also can be two or more in iron-cobalt-nickel molybdenum, not itemize mix proportion scheme herein.
Test 1:
LaFeO in embodiment 13The specific preparation process of catalyst precursor:
1) 1:1:4 weighs ferric nitrate, lanthanum nitrate and citric acid in molar ratio, is add to deionized water stirring to being completely dissolved network
Orange solution is formed after conjunction, 100 DEG C are then heated in convection oven, until being evaporated to orange-yellow sticky glue
Object；This jelly is transferred to quartz boat and is placed on progress first step air calcination in horizontal pipe furnace, then firing product is ground
Mill carries out second of calcination and obtains LaFeO3, calcination parameter is as follows:
| It is empty for the first time to burn | 25-200℃ | 200℃ | 200-500℃ | 500℃ |
| Time (min) | 60 | 60 | 60 | 240 |
| Second of empty burning | 25-200℃ | 200-800℃ | 800℃ | |
| Time (min) | 35 | 60 | 360 |
It is primary to repeat test 1, and XRD characterizations are carried out to two groups of products of gained, as a result prepared LaFeO as shown in Figure 1:3Spy
Sign spectral line shows it as pbnm space group, and crystallinity is very high.Test result is identical twice, and reproducibility is good.Implement
AB in example 2-27xC1-xO3Synthesis referring to embodiment 1, the precursor raw material of each metal is corresponding nitrate, and molybdenum is then molybdenum
Sour ammonium；A, the molar ratio of the corresponding nitrate of B, C and citric acid is 1:x:1-x:4.
Test 2:
LaFeO prepared by 1 being tested3It is placed in horizontal pipe furnace, is evacuated to 0~2Pa, be passed through inert gas Ar and add to normal pressure
Heat then passes to H to 800 DEG C2CVD test is carried out after restoring 30min, specific experiment parameter is as follows:
The product SEM that CVD reaction generates is characterized as shown in Fig. 2, the spheroidal particle in background is LaFeO3Catalyst precursor
Through H2Reduction gained Fe/La2O3Catalyst particle, diameter are evenly distributed, about 25nm.High brightness tube is institute in figure
It is raw carbon nanotube, Bamboo-shaped is presented；The CVD product is placed in 4M HCl vacuum filtration after pickling 12h and distillation will be used
Water washing, until purifying CVD product is made close to neutral in filtrate, SEM characterization as shown in figure 3, in Fig. 3 catalyst particle by
Completely remove, only high-purity caliber be 25~60nm bamboo-like carbon nano tubes.
Test 3:
LaFeO prepared by 1 being tested3It is placed in horizontal pipe furnace, is evacuated to 0~2Pa, be passed through inert gas Ar and add to normal pressure
Heat then passes to H to 850 DEG C2CVD test is carried out after restoring 30min, specific experiment parameter is as follows:
The product that CVD reaction generates is filtered by vacuum and will be washed with distilled water using after pickling 12h in 4M HCl, until filtrate connects
Purifying CVD product is made in weakly acidic pH, as shown in figure 4, Fig. 4 a shows that purifying CVD product is presented threadiness, width is SEM characterization
0.1~50 μm, length is limited to 100~250 μm by the SEM ken, and longest is up to 5mm；Fig. 4 b then shows observed fiber
It is made of the tube bank of 30~100nm carbon nanotube of same orientation.
Test 4
YAl is prepared according to 25 stoichiometric ratio of embodiment and the specific method of test 10.5Fe0.5O3Catalyst precursor is set
In horizontal pipe furnace, it is evacuated to 0~2Pa, inert gas Ar is passed through to normal heating to 900 DEG C, then passes to H2Reduction
CVD test is carried out after 30min, specific experiment parameter is as follows:
The product that CVD reaction generates is filtered by vacuum and will be washed with distilled water using after pickling 12h in 4M HCl, until filtrate connects
Purifying CVD product is made in weakly acidic pH, and SEM characterization is as shown in figure 5, Fig. 5 a shows that purifying CVD product is presented cotton-shaped membrane structure；
Cotton-shaped membrane structure observed by Fig. 5 b then shows is made of the single-walled carbon nanotube that 1nm of different orientation or so dissociates.
Only presently preferred embodiments of the present invention is explained in detail above, but the present invention is not limited to above-described embodiment,
Within the knowledge of a person skilled in the art, it can also make without departing from the purpose of the present invention each
Kind variation, various change should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of composite catalyst for growing carbon nanotube, which is characterized in that the composite catalyst includes transition metal main reminder
Agent and oxide carrier co-catalyst, the chemistry by adjusting transition metal major catalyst and oxide carrier co-catalyst are counted
Ratio is measured, is distributed in adjusting transition metal primary catalyst particles in co-catalyst.
2. composite catalyst according to claim 1, which is characterized in that the transition metal major catalyst and oxide carry
The mass ratio of body co-catalyst is 0.05~0.55:0.95~0.45.
3. composite catalyst according to claim 1, which is characterized in that the transition metal major catalyst is iron, cobalt, nickel
Or it is one or more of in molybdenum, partial size is between 0.5~50nm.
4. composite catalyst according to claim 1, which is characterized in that the oxide carrier co-catalyst is oxidation
One or more of aluminium, yttrium oxide or lanthana.
5. composite catalyst according to claim 1, which is characterized in that the specific surface area of the composite catalyst is between 5
~200cm2Between/g.
6. a kind of method for preparing the composite catalyst as described in claim 1-5 any one, which is characterized in that the method
The following steps are included:
S1 colloid is made after) mixing according to the weighed each raw material of stoichiometric ratio using chemical complexometry, adopts in air
AB is made with two steps annealing methodxC1-xO3Perovskite type catalyst presoma, wherein 0≤x≤1；
S2 S1)) is obtained into ABxC1-xO3Perovskite type catalyst presoma is restored in a hydrogen atmosphere, obtains composite catalyzing
Agent.
7. according to the method described in claim 6, the it is characterized in that, S1) specifically includes the following steps:
S1.1) stoichiometrically weigh respectively the soluble-salt of element A, the soluble-salt of B element, C element soluble-salt
It is dissolved in deionized water, complexing agent is then added and is uniformly mixing to obtain solution, is heated to 80-120 DEG C, the solution after making complexing steams
Hair becomes colloid；
S1.2) then colloid described in S1.1) is warming up to 700~1100 DEG C of roastings in 350-500 DEG C of air calcination 1-24h again
Fire to obtain ABxC1-xO3Perovskite type catalyst presoma.
8. according to the method described in claim 6, the it is characterized in that, S2) specifically comprises the processes of:
S2.1 AB will) be obtainedxC1-xO3Perovskite type catalyst presoma is placed in horizontal pipe furnace high temperature section, vacuumizes；
S2.2 it) is first passed through inert gas and is warming up to 800~1100 DEG C, then be passed through hydrogen, the recovery time is 0.1~1h, is restored
The velocity ratio of hydrogen and inert gas is 1:1 in journey, and between 10~200sccm.
9. according to the method described in claim 6, it is characterized in that, the ABxC1-xO3A in perovskite type catalyst presoma
Element is aluminium, yttrium or lanthanum, and B element is aluminium, yttrium or lanthanum, and C element is one of iron, cobalt, nickel, molybdenum or a variety of.
10. the method according to the description of claim 7 is characterized in that the S1.1) in complexing agent be citric acid or oxalic acid；Institute
The molfraction for stating complexing agent additional amount is greater than or equal to two times of soluble-salt total amount；The soluble-salt is nitrate.
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| CN110801843A (en) * | 2019-11-11 | 2020-02-18 | 内蒙古骏成新能源科技有限公司 | Two-stage method for preparing high-magnification carbon nano tube with superfine tube diameter, catalyst and preparation method thereof |
| 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 |
| CN112871181A (en) * | 2019-11-29 | 2021-06-01 | 新奥石墨烯技术有限公司 | Carbon nanotube catalyst, preparation method thereof and preparation method of carbon nanotube |
| CN114797864A (en) * | 2021-01-21 | 2022-07-29 | 北京大学深圳研究院 | Preparation method of catalyst for growth of small-diameter bulk-phase single-walled carbon nanotube |
| WO2023159700A1 (en) * | 2022-02-23 | 2023-08-31 | 无锡东恒新能源科技有限公司 | Synthesis method for superfine catalyst powder |
| WO2023159698A1 (en) * | 2022-02-24 | 2023-08-31 | 无锡东恒新能源科技有限公司 | Method for synthesizing highly active catalyst |
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