CN1718278A - Catalyst for growth of carbon nano-tube, and its prepn. method - Google Patents
Catalyst for growth of carbon nano-tube, and its prepn. method Download PDFInfo
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- CN1718278A CN1718278A CNA2004100627495A CN200410062749A CN1718278A CN 1718278 A CN1718278 A CN 1718278A CN A2004100627495 A CNA2004100627495 A CN A2004100627495A CN 200410062749 A CN200410062749 A CN 200410062749A CN 1718278 A CN1718278 A CN 1718278A
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- carbon nano
- sodium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 13
- 230000012010 growth Effects 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 8
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 4
- 239000011029 spinel Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 31
- 239000011148 porous material Substances 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 239000013528 metallic particle Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 235000002639 sodium chloride Nutrition 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011833 salt mixture Substances 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 235000012222 talc Nutrition 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 abstract description 7
- 238000001354 calcination Methods 0.000 abstract 1
- 230000005540 biological transmission Effects 0.000 description 18
- 239000007788 liquid Substances 0.000 description 10
- 238000009938 salting Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 6
- 229910001701 hydrotalcite Inorganic materials 0.000 description 6
- 229960001545 hydrotalcite Drugs 0.000 description 6
- 238000001420 photoelectron spectroscopy Methods 0.000 description 6
- 238000002336 sorption--desorption measurement Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000007605 air drying Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 229910002515 CoAl Inorganic materials 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- 229910000943 NiAl Inorganic materials 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910003321 CoFe Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
Classifications
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/007—Mixed salts
-
- 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
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
-
- B01J35/393—
-
- B01J35/635—
-
- B01J35/643—
-
- B01J35/647—
-
- B01J35/651—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/34—Length
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
Abstract
A catalyst for growing the carbon nanotubes with 16-28 layers of smooth wall, 20-40 nm in diameter and 4-15 microns in average length is prepared through introducing its active component to the laminated hydrotalcite to obtain the precursor, calcining to obtain the composite oxide with spinel structure, and reducing before it is used to obtain granular catalyst.
Description
Technical field:
The present invention relates to a kind of catalyst for growth of carbon nano-tube and preparation method thereof.
Technical background:
CNT is a kind of new function material of one dimension tracheary element structure, demonstrated extremely strong quantum effect and unusual physical and chemical performance with its special structure, shown very big potential application foreground at numerous areas such as catalysis, composite, energy storage material and microelectronic components.CNT is the seamless nanoscale pipe that the single or multiple lift graphite flake curls and forms by certain helical angle around central shaft, different according to preparation method and condition, CNT exists multi-walled carbon nano-tubes (MWNTs) and two kinds of forms of SWCN (SWNTs).
The method for preparing at present CNT has graphite arc method, laser evaporation graphite rod method, flame method, catalystic pyrolysis (CVD) etc., and wherein first three methods exists output few, is difficult for realizing the shortcoming of suitability for industrialized production; And the CVD method is simple with its equipment, and cost is low, and course of reaction is controlled easily, and the output advantages of higher becomes the main flow of present preparation CNT.In the CVD method, used catalyst activity component mostly is group VIII transition metal Fe, Co and Ni, or its alloy, and different catalysts directly influences the quality and the output of CNT; Therefore, people try to explore the influence of different catalysts to carbon nano tube growth, many reports about the different catalysts carbon nano-tube occurred.
Document [1] A.Thaib, G.A.Martin, P.Pinheiro, M.C.Schouler andP.Gadelle, Catalysis Letters 63 (1999) 135 and document [2] J.P.Pinheiro, M.C.Schouler, P.Gadelle, Carbon 41 (2003) 2949 are that active component has prepared different load type metal catalyst Co/Al with transition metal Co all
2O
3And Co/MgO, length, caliber difference have been synthesized, the CNT that crystallization degree is different, but since during load the particle diameter of the dispersion of active component and final metallic particles distribute and size is difficult to control the defective of the lower and thickness skewness of the CNT output that existence synthesizes.
Summary of the invention:
The present invention provides a kind of novel appropriate carbon nanotube growth catalysts in order to overcome the shortcoming of traditional load type metal catalyst.Another object of the present invention provides this Preparation of catalysts method.
But the present invention is in conjunction with the characteristics of LDHs laminate The Nomenclature Composition and Structure of Complexes microcosmic modulation, can introduce active specy to its laminate by design, prepare the hydrotalcite precursor that laminate contains active component, is the catalyst that obtains preparing CNT after the precursor roasting with it.
The concrete preparation method of this catalyst is as follows:
A. preparation contains bivalent metal ion M
2+With trivalent metal ion M
3+Mixing salt solution, [M wherein
2+]/[M
3+]=1.2～5.0, and the total mol concentration of each metal ion species is 0.4～1.2M; M wherein
2+Be Mg
2+, Fe
2+, Ni
2+, Co
2+, Cu
2+In one or more, M
3+Be Co
3+, Al
3+, Fe
3+In one or more, in the mixed salt solution acid ion can be Cl
-, CO
3 2-, NO
3 -Or SO
4 2-In any one or multiple;
With NaOH and solubility inorganic sodium NaCl, Na
2CO
3, NaNO
3Or Na
2SO
4Preparation mixed-alkali solution, wherein naoh concentration is 0.8～2.5M, sodium salt concentration is 0.3～3.0M;
B. mixed-alkali solution slowly is added drop-wise in the mixing salt solution, when the pH value in the system reaches 7～12, stops to drip, in 20～70 ℃ of water-baths, crystallization 5～25h, after filtration, washing, drying obtains stratum water talcum LDHs precursor, and the general structure of this precursor is: [M
2+ 1-XM
3+ X(OH)
2]
X+(A
N-)
X/nMH
2O, wherein M
2+, M
3+Identical with in the steps A; A
N-Being the anion in salt-mixture in the steps A and the aqueous slkali, is CO
3 2-, NO
3 -, Cl
-, OH
-, SO
4 2-In one or more;
C. above-mentioned LDHs is placed high temperature furnace, be warming up to 500～900 ℃ with the speed of 2～15 ℃/min, roasting 2～7h obtains preparing the catalyst of CNT.
Among steps A and the B, used water is deionized water, when soluble sodium salt is any one of sodium sulphate, sodium nitrate or sodium chloride, needs to adopt nitrogen protection.
This catalyst is a kind of by [M
2+ 1-XM
3+ X(OH)
2]
X+(A
N-)
X/nMH
2The mixture that the roasting of O precursor forms, Main Ingredients and Appearance is M
2+, M
3+Metal oxide and the composite oxides of spinel structure.
The mesoporous average pore size that tests out this catalyst through the low temperature nitrogen adsorption desorption is 2.3～30nm, and the micropore average pore size is 0.4～2.0nm, and average pore size is 20～100nm, and total pore volume is 0.4～1.0cm
3/ g, specific area is 50～300m
2/ g.
After this catalyst reduced by the reducing condition before using, the quality percentage composition that draws each component of product with elementary analysis and the test of X-photoelectron spectroscopy is respectively: active elemental metal 5～25%, metal oxide 40～60%, the composite oxides 15～55% of spinel structure.The active elemental metal is one or more among Fe, Ni, Co and the Cu; Metal oxide is with M
2O
3, MO or M
3O
4Three types of existence, M wherein is Al
3+, Co
3+, Fe
3+In one or more, the M among the MO is Mg
2+, Ni
2+, Co
2+In one or more, M
3O
4In M be Co
3+, Fe
3+In one or both; Spinelle type composite oxides is with M
2+M
3+ 2O
4Form exists, wherein M
2+Be Co
2+, Ni
2+, Fe
2+, Mg
2+And Cu
2+In one or more, M
3+Be Co
3+, Fe
3+, Al
3+In one or more.Calculating its average metallic particles size with the high-resolution-ration transmission electric-lens observation is 15～35nm.
Getting the catalyst 30mg that above-mentioned steps C obtains and put into quartzy fixed bed, is 15～50ml/min with flow velocity, H
2/ N
2Volume ratio be 1: 10～1: 40 mist as reducing gases, be warming up to 450～700 ℃ of reduction 0.5～3h with the speed of 2～20 ℃/min; Subsequently under reducing condition, with H
2Switch to unstripped gas C
2H
2, C
2H
2And N
2Volume ratio is 1: 20, gaseous mixture flow velocity 30ml/min, and continue to be warming up to 700 ℃ of growths of carrying out CNT of cracking temperature with the speed of 5 ℃/min, reduce to room temperature behind the reaction 2h.
Final products have confirmed to have in the product CNT to generate by transmission electron microscope, and the average caliber of the CNT of generation is 20～40nm, and average length is 4～15 μ m, and uniform diameter, and tube wall is smooth.The high power transmission electron microscope shows that the CNT that generates is 16～28 layers a multi-walled pipes, and productive rate (mass percent of the carbon that every gram catalyst generates) reaches 200～400%.
The present invention has following remarkable result:
Because the LDHs precursor be through accessing The Nomenclature Composition and Structure of Complexes even metal catalyst granules on microcosmic behind the roasting reduction, thereby can obtain that metallic particles is less, active component is uniformly dispersed, the new catalyst of narrow diameter distribution.Utilize this catalyst to carry out the growth of CNT, can make that the CNT caliber for preparing is little and even when improving growth usefulness, the caliber distribution is narrower.
The specific embodiment:
Embodiment 1:
With 11.29g Co (NO
3)
26H
2O and 8.478g Al (NO
3)
39H
2Prepare salting liquid in the O adding 50ml deionized water; With 4.79g NaCO
3Add in the 50ml deionized water with 3.93g NaOH and to prepare aqueous slkali.
Under 25 ℃ of stirring conditions, aqueous slkali slowly is added drop-wise in the salting liquid, be 10 to stop to pH, in 50 ℃ of water-baths, crystallization 12h, reaction finishes the back suction filtration, spends deionised water twice, air drying.
The above-mentioned hydrotalcite precursor for preparing is put in the Muffle furnace, is warming up to 600 ℃ with the speed of 5 ℃/min, insulation 4h cools to room temperature at last with the furnace and obtains catalyst sample.
It is 2.3nm that the low temperature nitrogen adsorption desorption is tested its mesoporous average pore size, and the micropore average pore size is 1.5nm, and average pore size is 43nm, and total pore volume is 0.605cm
3/ g, specific area is 131.3m
2/ g; Catalyst reduction contains 8% metallic cobalt, 55% Al after elementary analysis and X-photoelectron spectroscopy sign draw
2O
3And Co
3O
4, 37% CoAl
2O
4, observe its average metallic particles size through high-resolution-ration transmission electric-lens and be 15nm.
Then the catalyst of the above-mentioned preparation gained of 30mg being put into quartzy fixed bed, is 30ml/min with the flow velocity, H
2/ N
2Volume ratio be 1: 20 mist as reducing gases, be warming up to 500 ℃ of reductase 12 h with the speed of 5 ℃/min; Subsequently under 500 ℃ of conditions, with H
2Switch to unstripped gas C
2H
2, C
2H
2And N
2Volume ratio is 1: 20, and gaseous mixture flow velocity 30ml/min continues to be warming up to 700 ℃ of growths of carrying out CNT of cracking temperature with the speed of 5 ℃/min, reduces to room temperature behind the reaction 2h.
Final products have confirmed the generation of CNT by transmission electron microscope, average caliber 20～30nm, and uniform diameter, tube wall is smooth, and average length is 12 μ m; The high power transmission electron microscope shows that the CNT that generates is 18 layers a multi-walled pipes, and productive rate reaches 220%.
Embodiment 2:
Take by weighing 11.64g Co (NO
3)
26H
2O, 2.69g Fe (NO
3)
39H
2O and 2.50g Al (NO
3)
39H
2Prepare salting liquid in the O adding 50ml deionized water; Use 2.83g NaCO
3, 3.42g NaOH and 50ml deionized water be mixed with aqueous slkali.
Under 25 ℃ of stirring conditions, slowly alkali lye is gone into slowly to be added drop-wise in the salting liquid, be 9 to stop to pH, in 40 ℃ of water-baths, crystallization 8h, reaction finishes the back suction filtration, spends deionised water twice, air drying.Above-mentioned preparation gained hydrotalcite precursor is put in the Muffle furnace, is warming up to 700 ℃ with the speed of 3 ℃/min, insulation 5h cools to room temperature at last with the furnace and obtains catalyst sample.
It is 3.5nm that the low temperature nitrogen adsorption desorption is tested its mesoporous average pore size, and the micropore average pore size is 1.7nm, and average pore size is 51nm, and total pore volume is 0.632cm
3/ g, specific area is 63.3m
2/ g; Catalyst reduction contains 17% simple substance Co and Fe, 48% Al after elementary analysis and X-photoelectron spectroscopy sign draw
2O
3, Fe
3O
4And Co
3O
4, 35% CoAl
2O
4And CoFe
2O
4, observe its average metallic particles size through high-resolution-ration transmission electric-lens and be 18nm.
Carry out the growth test of CNT again by the step of embodiment 1.Final products have confirmed the generation of CNT by transmission electron microscope, and uniform diameter, and tube wall is smooth, and average caliber is 20～30nm, and average length is 6 μ m, and the high power transmission electron microscope shows that the CNT that generates is 20 layers a multi-walled pipes, and productive rate reaches 280%.
Embodiment 3:
With 10.51g NiSO
46H
2O, 3.71g FeSO
47H
2O and 8.88g Al
2(SO
4)
318H
2Prepare salting liquid in the O adding 100ml deionized water; With 14.20g Na
2SO
4Add 100ml with 6.00g NaOH and pass through N
2Prepare aqueous slkali in the deionized water.
Under nitrogen protection, 25 ℃ of band stirring conditions, stir down in 25 ℃ of bands, slowly alkali lye is gone into slowly to be added drop-wise in the salting liquid, be 8 to stop to pH; At N
2Under the condition of protection, in 20 ℃ of water-baths, crystallization 24h, reaction finishes the back suction filtration, with passing through N
2Frozen water washing, use ethanol washed twice, air drying at last again.Above-mentioned preparation gained hydrotalcite precursor is put in the Muffle furnace, is warming up to 800 ℃ with the speed of 10 ℃/min, insulation 5h cools to room temperature at last with the furnace and obtains catalyst sample.
The mesoporous average pore size that the low temperature nitrogen adsorption desorption is tested this catalyst is 6.1nm, and the micropore average pore size is 1.9nm, and average pore size is 45nm, and total pore volume is 0.685cm
3/ g, specific area is 105.3m
2/ g; This catalyst reduction contains 10% simple substance Ni and Fe, 45% Al after elementary analysis and X-photoelectron spectroscopy record
2O
3, NiO and Fe
3O
4, 45% NiAl
2O
4And NiFe
2O
4, observe its average metallic particles size through high-resolution-ration transmission electric-lens and be 17nm.
Carry out the growth test of CNT again by the step of embodiment 1.Final products have confirmed the generation of CNT by transmission electron microscope, and uniform diameter, and tube wall is smooth, and average caliber is 25～35nm, and average length is 8 μ m, and the high power transmission electron microscope shows that the CNT that generates is 21 layers a multi-walled pipes, and productive rate reaches 290%.
Embodiment 4:
Take by weighing 11.89g Ni (NO
3)
26H
2O and 3.67g Fe (NO
3)
39H
2Be mixed with salting liquid in the O adding 100ml deionized water; With 100ml deionized water, 14.61g NaCl and 4.00g NaOH preparation aqueous slkali.
Under nitrogen protection, 25 ℃ of band stirring conditions, slowly alkali lye is gone into slowly to be added drop-wise in the salting liquid, be 9.5 to stop to pH; At N
2Under the condition of protection, in 70 ℃ of water-baths, crystallization 5h, reaction finishes the back suction filtration.With passing through N
2Frozen water washing, use ethanol washed twice, air drying at last again.Above-mentioned preparation gained hydrotalcite precursor is put in the Muffle furnace, is warming up to 850 ℃ with the speed of 10 ℃/min, insulation 5h cools to room temperature at last with the furnace and obtains catalyst sample.
The mesoporous average pore size that the low temperature nitrogen adsorption desorption is tested this catalyst is 10.0nm, and the micropore average pore size is 0.8nm, and average pore size is 63nm, and total pore volume is 0.735cm
3/ g, specific area is 56.3m
2/ g; This catalyst reduction contains 12% simple substance Ni and Fe, 58% NiO and Fe after elementary analysis and X-photoelectron spectroscopy record
3O
4, 30% NiFe
2O
4, observe its average metallic particles size through high-resolution-ration transmission electric-lens and be 22nm.
Carry out the growth test of CNT again by the step of embodiment 1.Final products have confirmed the generation of CNT by transmission electron microscope, and uniform diameter, and tube wall is smooth, and average caliber is 35～40nm, and average length is approximately 8 μ m, and the high power transmission electron microscope shows that the CNT that generates is 24 layers a multi-walled pipes, and productive rate reaches 250%.
Embodiment 5:
With 11.17g Ni (NO
3)
26H
2O, 2.46g Mg (NO
3)
26H
2O and 10.66g Al
2(SO
4)
318H
2Be mixed with salting liquid in the O adding 100ml deionized water; With 19.08g Na
2CO
3Add the 100ml deionized water with 8.8g NaOH and be mixed with aqueous slkali.
Under 25 ℃ of stirring conditions, slowly alkali lye is gone into slowly to be added drop-wise in the salting liquid, be 11 to stop to pH, in 40 ℃ of water-baths, crystallization 8h, reaction finishes the back suction filtration.Spend deionised water twice, air drying.Above-mentioned preparation gained hydrotalcite precursor is put in the Muffle furnace, is warming up to 700 ℃ with the speed of 3 ℃/min, insulation 5h cools to room temperature at last with the furnace and obtains catalyst sample.
The mesoporous average pore size that the low temperature nitrogen adsorption desorption is tested this catalyst is 18nm, and the micropore average pore size is 1.2nm, and average pore size is 65nm, and total pore volume is 0.585cm
3/ g, specific area is 42.5m
2/ g; This catalyst reduction contains 13% simple substance Ni, 49% Al after elementary analysis and X-photoelectron spectroscopy record
2O
3, NiO and MgO, 38% NiAl
2O
4And MgAl
2O
4, observe its average metallic particles size through high-resolution-ration transmission electric-lens and be 25nm.
Carry out the growth test of CNT again by the step of embodiment 1.Final products have confirmed the generation of CNT by transmission electron microscope, and caliber is comparatively even, and average caliber is 35～40nm, and average length is approximately 5.5 μ m, and the high power transmission electron microscope shows that the CNT that generates is 23 layers a multi-walled pipes, and productive rate reaches 270%.
Claims (6)
1. the preparation method of a catalyst for growth of carbon nano-tube, concrete steps are as follows:
A. contain bivalent metal ion M with the deionized water preparation
2+With trivalent metal ion M
3+Mixing salt solution, [M wherein
2+]/[M
3+]=1.2～5.0, and the total mol concentration of each metal ion species is 0.4～1.2M; M wherein
2+Be Mg
2+, Fe
2+, Ni
2+, Co
2+, Cu
2+In one or more, M
3+Be Co
3+, Al
3+, Fe
3+In one or more, in the mixed salt solution acid ion can be Cl
-, CO
3 2-, NO
3 -Or SO
4 2-In any one or multiple;
With NaOH, solubility inorganic sodium and deionized water preparation mixed-alkali solution, wherein naoh concentration is 0.8～2.5M, and sodium salt concentration is 0.3～3.0M;
B. mixed-alkali solution slowly is added drop-wise in the mixing salt solution, when the pH value in the system reaches 7～12, stops to drip, in 20～70 ℃ of water-baths, crystallization 5～25h, after filtration, washing, drying obtains stratum water talcum LDHs precursor, and the general structure of this precursor is: [M
2+ 1-XM
3+ X(OH)
2]
X+(A
N-)
X/nMH
2O, wherein M
2+, M
3+Identical with in the steps A; A
N-Be in the anion in salt-mixture in the steps A and the aqueous slkali one or more, A
N-Be;
C. above-mentioned LDHs is placed high temperature furnace, be warming up to 500～900 ℃ with the speed of 2～15 ℃/min, roasting 2～7h obtains preparing the catalyst of CNT.
2. the preparation method of the described catalyst for growth of carbon nano-tube of claim 1: it is characterized in that the solubility inorganic sodium is NaCl, Na
2CO
3, NaNO
3Or Na
2SO
4, when the solubility inorganic sodium was sodium sulphate, sodium nitrate or sodium chloride, steps A and B needed carry out under nitrogen protection.
3. catalyst for growth of carbon nano-tube is characterized in that this catalyst is that method with claim 1 prepares.
4. the described catalyst for growth of carbon nano-tube of claim 3 is characterized in that this catalyst is porous, and its mesoporous average pore size is 2.3～30nm, and the micropore average pore size is 0.4～2.0nm, and average pore size is 20～100nm, and total pore volume is 0.4～1.0cm
3/ g, specific area is 50～300m
2/ g.
5. the described catalyst for growth of carbon nano-tube of claim 3 is characterized in that this catalyst by after using preceding reducing condition to reduce, and the quality percentage composition of each component is respectively:
Active elemental metal: 5～25%
Metal oxide: 40～60%
The composite oxides of spinel structure: 15～55%;
Wherein metal oxide is with M
2O
3, MO or M
3O
4Form exists; Active elemental metallic particles size is 15～35nm.
6. the described catalyst for growth of carbon nano-tube of claim 5, it is characterized in that this catalyst reduction after, the active elemental metal is one or more among Fe, Ni, Co and the Cu; Metal oxide is Al
2O
3, Co
2O
3, Fe
2O
3, MgO, NiO, CoO, Co
3O
4, Fe
3O
4In one or more; Spinelle type composite oxides is with M
2+M
3+ 2O
4Form exists, wherein M
2+Be Co
2+, Ni
2+, Fe
2+, Mg
2+And Cu
2+In one or more, M
3+Be Co
3+, Fe
3+, Al
3+In one or more.
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| CNA2004100627495A CN1718278A (en) | 2004-07-09 | 2004-07-09 | Catalyst for growth of carbon nano-tube, and its prepn. method |
| PCT/CN2004/001112 WO2006005234A1 (en) | 2004-07-09 | 2004-09-28 | Catalyst for growth of carbon nanotubes and the preparing method of same |
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|---|---|---|---|
| CNA2004100627495A CN1718278A (en) | 2004-07-09 | 2004-07-09 | Catalyst for growth of carbon nano-tube, and its prepn. method |
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| WO (1) | WO2006005234A1 (en) |
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| CN1335257A (en) * | 2000-07-21 | 2002-02-13 | 中国科学院成都有机化学研究所 | Catalyst for preparing nanometer carbon tube |
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