WO2006005234A1 - Catalyst for growth of carbon nanotubes and the preparing method of same - Google Patents
Catalyst for growth of carbon nanotubes and the preparing method of same Download PDFInfo
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- WO2006005234A1 WO2006005234A1 PCT/CN2004/001112 CN2004001112W WO2006005234A1 WO 2006005234 A1 WO2006005234 A1 WO 2006005234A1 CN 2004001112 W CN2004001112 W CN 2004001112W WO 2006005234 A1 WO2006005234 A1 WO 2006005234A1
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- catalyst
- carbon nanotubes
- carbon nanotube
- sodium
- preparing
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 44
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 13
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [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 claims abstract description 10
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 10
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 7
- 150000004706 metal oxides Chemical class 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 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000002923 metal particle Substances 0.000 claims description 9
- 235000002639 sodium chloride Nutrition 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 159000000000 sodium salts Chemical class 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 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
- 238000001354 calcination Methods 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000011259 mixed solution 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
- 238000005406 washing Methods 0.000 claims description 2
- 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 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000002048 multi walled nanotube Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000009499 grossing Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004627 transmission electron microscopy Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 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
- 239000003245 coal Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- -1 45% of A1 2 0 3 Inorganic materials 0.000 description 1
- 229910003321 CoFe Inorganic materials 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 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
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect 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
- 238000001914 filtration Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011068 loading method Methods 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
- 238000002156 mixing Methods 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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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
- B01J23/74—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)
Definitions
- the invention relates to a catalyst for carbon nanotube growth and a preparation method thereof.
- Carbon nanotubes are a new functional material of one-dimensional tubular molecular structure. Their special structure shows extremely strong quantum effects and singular physicochemical properties in catalysis, composite materials, energy storage materials and microelectronic devices. Many areas have shown a potential application prospect. Carbon nanotubes are seamless nano-scale tubes in which single-layer or multi-layer graphite sheets are curled around a central axis at a certain helix angle. According to different preparation methods and conditions, carbon nanotubes have multi-walled carbon nanotubes ( ⁇ and Ts). ) and single-walled carbon nanotubes (SWNTs) in two forms.
- ⁇ and Ts multi-walled carbon nanotubes
- SWNTs single-walled carbon nanotubes
- methods for preparing carbon nanotubes include graphite arc method, laser evaporating graphite rod method, flame method, catalytic cracking method (CVD), etc., wherein the first three methods have the disadvantages of low yield and difficult industrialized production; The advantages of simple equipment, low cost, easy control of the reaction process, and high yield have become the mainstream of the current preparation of carbon nanotubes.
- the active components of the catalyst are mostly the transition metal Fe, Co and Ni, or alloys thereof. Different catalysts directly affect the quality and yield of the carbon nanotubes; therefore, people actively explore different catalysts for carbon nanometers. The influence of tube growth has led to many reports on the growth of carbon nanotubes by different catalysts.
- the present invention provides a novel carbon nanotube growth catalyst.
- Another object of the invention is to provide a process for the preparation of the catalyst. - The invention combines the characteristics of microscopic tunability of the composition and structure of the LDHs laminate, and can introduce the active species into the laminate by design, and prepare the hydrotalcite precursor containing the active component in the laminate, which is obtained by calcining the precursor A catalyst for preparing carbon nanotubes.
- the specific preparation method of the catalyst is as follows:
- A. preparing a mixed salt solution containing a divalent metal ion M 2+ and a trivalent metal ion M 3+ , wherein 01 2+ ] / [3 ⁇ 41 3+ ] 1.2 to 5.0, and the total molar concentration of each metal ion is 0.4-1.2 M; wherein M 2+ is one or more of Mg 2+ , Fe 2+ , Ni 2+ , Co 2+ , Cu 2+ , and M 3+ is Co 3+ , Al 3+ , Fe One or more of 3+ , the acid ion in the salt mixed solution may be any one or more of C1—, C0 3 2 —, N0 3 — or S0 4 2 ⁇ ;
- the above LDHs are placed in a high temperature furnace, heated to 500 ⁇ 900 ° C at a rate of 2 ⁇ 15 ° C / min, and calcined for 2 ⁇ 7h to obtain a catalyst for preparing carbon nanotubes.
- the water used is deionized water.
- the soluble sodium salt is any one of sodium sulfate, sodium nitrate or sodium chloride, nitrogen protection is required.
- the catalyst is a kind of (0H) 2 ] x+ (A n — ) ⁇ / ⁇ ⁇ mH 2 0 mixed formation of precursors
- the main component is a metal oxide of M 2+ , M 3+ and a composite oxide of a spinel structure. 4 ⁇
- the average pore size is 0. 4 ⁇ 2. Onm, the average pore diameter is 20 - lOOnm, the total pore volume is 0. 4 ⁇ 1. OcmVg, specific surface area is 50 ⁇ 300m7go
- the active elemental metal is one or more of Fe, Wi Co and Cu; the metal oxide exists in three types of M 2 O 3 , M0 or M 3 0 4 , wherein M in M 2 0 3 is Al 3+ Or one or more of Co 3+ and Fe 3+ , M in M0 is one or more of Mg 2+ , M 2+ , Co 2+ , and M in M 3 0 4 is Co 3 + or one of Fe 3+ ; the spinel-type composite oxide exists in the form of M 2+ M 3+ 2 0 4 , wherein M 2+ is Co 2+ , Ni 2+ , Fe 2+ , One or more of Mg 2+ and Cu 2+ , and M 3+ is one or more of Co 3+ , Fe 3+ , and Al 3+ .
- the average metal particle size was determined by high-resolution transmission electron microscopy to be 15 ⁇ 35 nm.
- the final product was confirmed by transmission electron microscopy to have carbon nanotubes formed in the product.
- the average diameter of the carbon nanotubes produced was 20 ⁇ 40 nm, the average length was 4 ⁇ 15 ⁇ , and the tube diameter was uniform and the tube wall was smooth.
- High-power transmission electron microscopy showed that the carbon nanotubes produced were 16 to 28 layers of multi-walled tubes, and the yield (percentage of carbon produced per gram of catalyst) reached 200 - 400%.
- the LDHs precursor is reduced by calcination, it is possible to obtain gold which is microscopically composed and structurally uniform. It is a catalyst particle, so that a novel catalyst having a small metal particle, a dispersed active component, and a narrow particle size distribution can be obtained.
- the growth of the carbon nanotubes by using the catalyst can improve the growth efficiency, and the prepared carbon nanotubes have small and uniform diameters, and the tube diameter distribution range is narrow.
- the reduced solution was slowly added dropwise to the salt solution until 10 stops, crystallization in a 50 ° C water bath, 12 h, after the reaction was filtered, washed twice with deionized water, air Dry in the middle.
- the hydrotalcite precursor prepared above was placed in a muffle furnace, heated to 60 CTC at a rate of 5 ° C /min, held for 4 h, and finally cooled to room temperature with a furnace to obtain a catalyst sample.
- the singularity of the pores is 1. 5 nm, the average pore diameter is 1.5 nm, the total pore volume is 0. 605 cm 3 /g, and the specific surface area is 131. 3 m 2 /g.
- elemental analysis and X-ray photoelectron spectroscopy showed that 8% of metal cobalt, 55% of A1 2 0 3 and Co 3 0 4 , and 37% of CoAl 2 0 4 were obtained by high-resolution transmission electron microscopy.
- the average metal particle size was observed to be 15 nm.
- the final product confirmed the formation of carbon nanotubes by transmission electron microscopy, with an average diameter of 20 ⁇ 30nm.
- the tube diameter is uniform, the tube wall is smooth, and the average length is 12 ⁇ ; the high-power transmission electron microscope shows that the carbon nanotubes produced are 18-layer multi-wall tubes with a yield of 220 1 ⁇ .
- Example 2
- A1 (N0 3 ) 3 - 9H 2 0 is added to 50 ml of deionized water to prepare a salt solution; 2.83 g of NaC0 3 , 3. 42 g
- NaOH is combined with 5 Oral deionized water to make an alkaline solution.
- the lye was slowly added dropwise to the salt solution under stirring at 25 ° C until the pH was 9 and crystallization was carried out in a 40 ° C water bath for 8 hours. After the reaction was completed, it was suction filtered and washed twice with deionized water. Dry in the air.
- the hydrotalcite precursor prepared above was placed in a muffle furnace, heated to 700 ° C at a rate of 3 ° C / min, kept for 5 h, and finally cooled to room temperature with a furnace to obtain a catalyst sample.
- the low-temperature nitrogen absorption and desorption test has a mesoporous average pore diameter of 3. 5 nm, and the average pore diameter of the f-perforation is
- the growth test of carbon nanotubes was carried out in the same manner as in Example 1.
- the final product confirmed the formation of carbon nanotubes by transmission electron microscopy, and the tube diameter was uniform, the tube wall was smooth, and the average tube diameter was 20 ⁇
- the osmotic volume is 0. 685cmVg, the specific surface area is 105. 3m 2 /g; the specific pore diameter is 0. 685cmVg, the specific surface area is 105. 3m 2 /g;
- elemental analysis and X-photoelectron spectroscopy showed that 10% of elemental Ni and Fe, 45% of A1 2 0 3 , NiO and Fe 3 0 4 , 45% of NiAl 2 0 4 and NiFe 2 0 were obtained. 4.
- the average metal particle size was 17 nm observed by high resolution transmission electron microscopy.
- Example 4 The growth test of carbon nanotubes was carried out in the same manner as in Example 1. The final product confirmed the formation of carbon nanotubes by transmission electron microscopy, and the tube diameter was uniform, the tube wall was smooth, the average diameter was 25 ⁇ 35nm, and the average length was 8 ⁇ . The high-power transmission electron microscope showed that the carbon nanotubes produced were 21-layer multi-wall. Tube, the yield reached 290%.
- Example 4 The high-power transmission electron microscope showed that the carbon nanotubes produced were 21-layer multi-wall. Tube, the yield reached 290%.
- the surface area is 0. 735cm 3 /g, the specific surface area is 56. 3mVg; After catalyst reduction, elemental analysis and X-ray photoelectron spectroscopy showed 12% single Ni and Fe, 58% of NiO and Fe 3 0 4 , and 30% of NiFe 2 0 4 were observed by high-resolution transmission electron microscopy to have an average metal particle size of 22 nm.
- Example 5 The growth test of carbon nanotubes was carried out in the same manner as in Example 1. The final product confirmed the formation of carbon nanotubes by transmission electron microscopy, and the tube diameter was uniform, the tube wall was smooth, the average diameter was 35 ⁇ 40 nm, and the average length was about 8 jn. The high-power transmission electron microscope showed that the carbon nanotubes were 24 layers. The multi-wall tube has a yield of 250%.
- the lye was slowly added dropwise to the salt solution under stirring at 25 ° C until the pH was 11 and crystallization was carried out in a 40 ° C water bath for 8 hours. After the reaction was completed, suction filtration was carried out. Wash twice with deionized water and dry in air.
- the hydrotalcite precursor prepared above was placed in a muffle furnace and heated to 700 ° C at a rate of 3 ° C / min; held for 5 h, and finally cooled to room temperature with a furnace to obtain a catalyst sample.
- the growth test of carbon nanotubes was carried out in the same manner as in Example 1.
- the final product was confirmed by transmission electron microscopy, and the diameter of the carbon nanotubes was relatively uniform.
- the average diameter was 35 ⁇ 40 nm, and the average length was about 5. 5 ⁇ .
- the high-power transmission electron microscope showed that the carbon nanotubes produced were 23 layers.
- the wall tube has a yield of 270%.
Abstract
The present invention relates to a catalyst for growth of carbon nanotubes and the preparing method of the catalyst. The preparing method of the catalyst comprises: at first, a hydrotalcite precursor with the formula of [M2+1-XM3+ x (OH)2]x+ (An-)x/n.mH2O which contains active component is prepared by introducing the active component into lamellated plate of the hydrotalcite, then the precursor is calcinate to obtain a compound oxide catalyst which contains metal oxides of M2+ and M3+ and contains spinel thereof. The granular catalyst containing the active metal may be obtained by reducing the catalyst before using. The multi-walled carbon nanotubes which have an average tube diameter of 20~40nm, an average length of 4~15µm, and 16~18 layers, and the tube diameter thereof is even, and the tube wall thereof is smoothing, may obtained by conducting carbon nanotubes growth using this catalyst.
Description
一种碳纳来管生长用催化剂及其制备方法 技术领域 Catalyst for carbon nano tube growth and preparation method thereof
本发明涉及一种碳纳米管生长用催化剂及其制备方法。 技术背景 The invention relates to a catalyst for carbon nanotube growth and a preparation method thereof. technical background
碳纳米管是一种一维管状分子结构的新型功能材料， 以其特殊的结 构显示出了极强的量子效应和奇异的物理化学性能， 在催化、 复合材料、 储能材料和微电子器件等诸多领域表现出了^ ί艮大的潜在应用前景。 碳纳 米管是单层或多层石墨片围绕中心轴按一定的螺旋角卷曲而成的无缝纳米 级管， 根据制备方法和条件的不同，碳纳米管存在多壁碳纳米管（Μ而 Ts) 和单壁碳纳米管（SWNTs)两种形式。 Carbon nanotubes are a new functional material of one-dimensional tubular molecular structure. Their special structure shows extremely strong quantum effects and singular physicochemical properties in catalysis, composite materials, energy storage materials and microelectronic devices. Many areas have shown a potential application prospect. Carbon nanotubes are seamless nano-scale tubes in which single-layer or multi-layer graphite sheets are curled around a central axis at a certain helix angle. According to different preparation methods and conditions, carbon nanotubes have multi-walled carbon nanotubes (Μ and Ts). ) and single-walled carbon nanotubes (SWNTs) in two forms.
目前制备碳纳米管的方法有石墨电弧法、 激光蒸发石墨棒法、 火焰 法、 催化裂解法 ( CVD )等， 其中前三种方法存在产量少 , 不易实现工业 化生产的缺点； 而 CVD 法以其设备简单， 成本低， 反应过程容易控制， 产量高等优点成为目前制备碳纳米管的主流。 在 CVD 法中， 所用的催化 剂活性组分多为第 Vin族过渡金属 Fe，Co 和 Ni，或其合金， 不同催化剂直 接影响碳纳米管的质量和产量； 因此， 人们积极探索不同催化剂对碳纳 米管生长的影响， 出现了许多关于不同催化剂生长碳纳米管的报道。 At present, methods for preparing carbon nanotubes include graphite arc method, laser evaporating graphite rod method, flame method, catalytic cracking method (CVD), etc., wherein the first three methods have the disadvantages of low yield and difficult industrialized production; The advantages of simple equipment, low cost, easy control of the reaction process, and high yield have become the mainstream of the current preparation of carbon nanotubes. In the CVD method, the active components of the catalyst are mostly the transition metal Fe, Co and Ni, or alloys thereof. Different catalysts directly affect the quality and yield of the carbon nanotubes; therefore, people actively explore different catalysts for carbon nanometers. The influence of tube growth has led to many reports on the growth of carbon nanotubes by different catalysts.
文献 [1] A. Thaib, G. A. Martin, P. Pinheiro, M. C. Schouler and P. Gadel le, Catalys is Letters 63 (1999) 135和文献 [2] L P. Pinheiro, M. C. Schouler, P. Gadel le, Carbon 41 (2003) 2949 均以过渡金属元素 Co为活性组分制备了不同的负载型金属催化剂 Co/Al203和 Co/Mg0, 合成 出了长度、 管径不同， 结晶程度各异的碳纳米管， 但是由于负载时活性 组分的分散以及最终金属颗粒的粒径分布和大小难以控制， 存在合成出 的碳纳米管产量较低且粗细分布不均的缺陷。
发明内容 [1] A. Thaib, GA Martin, P. Pinheiro, MC Schouler and P. Gadel le, Catalys is Letters 63 (1999) 135 and literature [2] L P. Pinheiro, MC Schouler, P. Gadel le, Carbon 41 (2003) 2949 Different supported metal catalysts Co/Al 2 0 3 and Co/Mg0 were prepared by using transition metal element Co as active component, and carbon nanometers with different lengths, different pipe diameters and different degrees of crystallinity were synthesized. Tube, but due to the dispersion of the active component at the time of loading and the particle size distribution and size of the final metal particles are difficult to control, there is a defect that the synthesized carbon nanotubes have a low yield and an uneven thickness distribution. Summary of the invention
本发明为了克服传统的负载型金属催化剂的缺点， 提供一种新型碳 纳米管生长催化剂。 本发明的另一个目的是提供该催化剂的制备方法。 - 本发明结合 LDHs 层板组成和结构微观可调变的特点， 通过设计可以 向其层板引入活性物种， 制备得到层板含活性组分的水滑石前体， 以其 为前体焙烧后得到制备碳纳米管的催化剂。 In order to overcome the shortcomings of conventional supported metal catalysts, the present invention provides a novel carbon nanotube growth catalyst. Another object of the invention is to provide a process for the preparation of the catalyst. - The invention combines the characteristics of microscopic tunability of the composition and structure of the LDHs laminate, and can introduce the active species into the laminate by design, and prepare the hydrotalcite precursor containing the active component in the laminate, which is obtained by calcining the precursor A catalyst for preparing carbon nanotubes.
该催化剂的具体制备方法如下： The specific preparation method of the catalyst is as follows:
A. 配制含有二价金属离子 M2+和三价金属离子 M3+的混合盐溶液， 其 中012+]/[¾13+]=1.2~5.0,且各种金属离子的总摩尔浓度为 0.4-1.2 M; 其 中 M2+是 Mg2+、 Fe2+、 Ni2+、 Co2+、 Cu2+中的一种或多种， M3+是 Co3+、 Al3+、 Fe3+ 中的一种或多种， 盐混合溶液中的的酸根离子可以是 C1—、C03 2-、N03—或 S04 2- 中的任意一种或多种； A. preparing a mixed salt solution containing a divalent metal ion M 2+ and a trivalent metal ion M 3+ , wherein 01 2+ ] / [3⁄41 3+ ] = 1.2 to 5.0, and the total molar concentration of each metal ion is 0.4-1.2 M; wherein M 2+ is one or more of Mg 2+ , Fe 2+ , Ni 2+ , Co 2+ , Cu 2+ , and M 3+ is Co 3+ , Al 3+ , Fe One or more of 3+ , the acid ion in the salt mixed solution may be any one or more of C1—, C0 3 2 —, N0 3 — or S0 4 2 − ;
用氢氧化钠和可溶性无机钠盐 NaCl、 Na2C03、 NaN03或 Na2S04配制混 合碱性溶液， 其中氢氧化钠浓度为 0.8 ~ 2.5M, 钠盐浓度为 0.3 ~ 3.0 M; Mixing alkaline solution with sodium hydroxide and soluble inorganic sodium salt NaCl, Na 2 C0 3 , NaN0 3 or Na 2 SO 4 , wherein the sodium hydroxide concentration is 0.8 ~ 2.5M, and the sodium salt concentration is 0.3 ~ 3.0 M;
B. 将混合碱性溶液緩慢滴加到混合盐溶液中， 当体系中的 pH值 达到 7 ~ 12 时， 停止滴加， 在 20~ 70°C水浴中， 晶化 5 ~ 25h， 经过 滤， 洗涤， 干燥， 得到层状水滑石 LDHs前体， 该前体的结构通式为： [Μ2+ Χ_ΧΜ3+ Χ (OH)2]x+(An-)x/n-mH20, 其中 M2+、 M3+与步骤 A 中的相同； An_为 步骤 A 中混合盐和碱溶液中的阴离子， 是 C03 2-、 N03-、 Cl-、 OH -、 S04 2 -中 的一种或多种； B. Slowly add the mixed alkaline solution to the mixed salt solution. When the pH value in the system reaches 7 ~ 12, stop the dropwise addition. In the water bath of 20~70 °C, crystallization for 5 ~ 25h, after filtration, Washing and drying to obtain a layered hydrotalcite LDHs precursor having the structural formula: [Μ 2+ Χ _ Χ Μ 3+ Χ (OH) 2 ] x+ (A n -) x/n -mH 2 0, wherein M 2+ and M 3+ are the same as in step A; A n _ is an anion in the mixed salt and alkali solution in step A, which is C0 3 2 -, N0 3 -, Cl-, OH -, S0 One or more of 4 2 -
C. 将上述 LDHs置于高温炉中， 以 2~15°C/min的速率升温至 500 ~ 900°C, 焙烧 2~7h, 得到制备碳纳米管的催化剂。 C. The above LDHs are placed in a high temperature furnace, heated to 500 ~ 900 ° C at a rate of 2 ~ 15 ° C / min, and calcined for 2 ~ 7h to obtain a catalyst for preparing carbon nanotubes.
步骤 A和 B 中， 所用的水均为去离子水， 当可溶性钠盐为硫酸钠、 硝酸钠或氯化钠的任意一种时， 需采用氮气保护。 In steps A and B, the water used is deionized water. When the soluble sodium salt is any one of sodium sulfate, sodium nitrate or sodium chloride, nitrogen protection is required.
该催化剂是一种由
(0H)2]x+(An— )χ/η · mH20前体焙烧形成的混
合物， 主要成份是 M2+、 M3+的金属氧化物及其尖晶石结构的复合氧化物。 经低温氮气吸脱附测试出该催化剂的介孔平均孔径为 2. 3 ~ 30nm, 微 孔平均孔径为 0. 4 ~ 2. Onm ,平均孔径为 20 - lOOnm, 总孔体积为 0. 4 ~ 1. OcmVg, 比表面积为 50 ~ 300m7go The catalyst is a kind of (0H) 2 ] x+ (A n — ) χ/η · mH 2 0 mixed formation of precursors The main component is a metal oxide of M 2+ , M 3+ and a composite oxide of a spinel structure. 4 ~ The average pore size is 0. 4 ~ 2. Onm, the average pore diameter is 20 - lOOnm, the total pore volume is 0. 4 ~ 1. OcmVg, specific surface area is 50 ~ 300m7go
将此催化剂按使用前的还原条件进行还原后， 用元素分析和 X-光电 子能谱测试得出产物各组分的质量百分含量分别是： 活性单质金属 5 ~ 1 %、 金属氧化物 40 ~ 60%， 尖晶石结构的复合氧化物 15 ~ 55%。 活性单 质金属为 Fe、 Wi Co和 Cu中的一种或几种； 金属氧化物以 M203、 M0或 M304三种类型存在， 其中 M203中的 M为 Al3+、 Co3+、 Fe3+中的一种或多种, M0中的 M为 Mg2+、 M2+、 Co2+中的一种或多种， M304中的 M为 Co3+ 、 Fe3+ 中的一种或两种； 尖晶石型复合氧化物以 M2+M3+ 204形式存在， 其中 M2+为 Co2+、 Ni2+ 、 Fe2+、 Mg2+和 Cu2+中的一种或几种， M3+为 Co3+、 Fe3+ 、 Al3+中 的一种或几种。用高分辨透射电镜观察测算出其平均金属颗粒大小为 15 ~ 35nm。 After the catalyst was reduced according to the reducing conditions before use, elemental analysis and X-ray photoelectron spectroscopy showed that the mass percentages of the components of the product were: active elemental metal 5 ~ 1 %, metal oxide 40 ~ 60%, a composite oxide of spinel structure 15 to 55%. The active elemental metal is one or more of Fe, Wi Co and Cu; the metal oxide exists in three types of M 2 O 3 , M0 or M 3 0 4 , wherein M in M 2 0 3 is Al 3+ Or one or more of Co 3+ and Fe 3+ , M in M0 is one or more of Mg 2+ , M 2+ , Co 2+ , and M in M 3 0 4 is Co 3 + or one of Fe 3+ ; the spinel-type composite oxide exists in the form of M 2+ M 3+ 2 0 4 , wherein M 2+ is Co 2+ , Ni 2+ , Fe 2+ , One or more of Mg 2+ and Cu 2+ , and M 3+ is one or more of Co 3+ , Fe 3+ , and Al 3+ . The average metal particle size was determined by high-resolution transmission electron microscopy to be 15 ~ 35 nm.
取上述步骤 C得到的催化剂 30mg放入石英固定床中， 以流速为 15 ~ Take 30mg of the catalyst obtained in the above step C into a quartz fixed bed at a flow rate of 15 ~
50 ml/min, H2/N2体积比为 1: 10 ~ 1： 40的混合气体作为还原气， 以 2 ~ 20°C /min的速率升温至 450 ~ 700°C还原 0. 5 ~ 3h ； 随后在还原条件下， 将 切换成原料气 C2H2 , C2H2和 N2体积比为 1 : 20, 混合气流速 30ml/min, 并继续以 5 °C /min的速率升温至裂解温度 70(TC进行碳纳米管的生长， 反 应 2h后降至室温。 5〜3小时。 The mixture of 50 m / min, H 2 / N 2 volume ratio of 1: 10 ~ 1: 40 as a reducing gas, at a rate of 2 ~ 20 ° C / min to 450 ~ 700 ° C to restore 0. 5 ~ 3h Subsequently, under reducing conditions, it will switch to the feed gas C 2 H 2 , C 2 H 2 and N 2 volume ratio of 1: 20, the mixed gas flow rate of 30 ml / min, and continue to heat up to 5 ° C / min to The cracking temperature was 70 (TC was carried out for the growth of carbon nanotubes, and the reaction was allowed to fall to room temperature after 2 hours.
最终产品通过透射电镜证实了产物中有碳纳米管生成， 生成的碳纳 米管平均管径为 20 ~ 40nm， 平均长度为 4 ~ 15μώ, 且管径均匀， 管壁光 滑。 高倍透射电镜显示生成的碳纳米管为 16 ~ 28 层的多壁管， 产率（每 克催化剂生成的碳的质量百分数）达到 200 - 400 %。 The final product was confirmed by transmission electron microscopy to have carbon nanotubes formed in the product. The average diameter of the carbon nanotubes produced was 20 ~ 40 nm, the average length was 4 ~ 15 μώ, and the tube diameter was uniform and the tube wall was smooth. High-power transmission electron microscopy showed that the carbon nanotubes produced were 16 to 28 layers of multi-walled tubes, and the yield (percentage of carbon produced per gram of catalyst) reached 200 - 400%.
本发明具有如下显著效果： The present invention has the following remarkable effects:
由于 LDHs 前体经焙烧还原后能够得到在微观上组成和结构均匀的金
属催化剂颗粒， 从而可获得金属颗粒较小、 活性組分分散均勾、 粒径分 布窄的新型催化剂。 利用这种催化剂进行碳纳米管的生长， 可以在提高 生长效能的同时， 使得制备得到的碳纳米管管径小且均匀， 管径分布范 围较窄。 具体实施方式 Since the LDHs precursor is reduced by calcination, it is possible to obtain gold which is microscopically composed and structurally uniform. It is a catalyst particle, so that a novel catalyst having a small metal particle, a dispersed active component, and a narrow particle size distribution can be obtained. The growth of the carbon nanotubes by using the catalyst can improve the growth efficiency, and the prepared carbon nanotubes have small and uniform diameters, and the tube diameter distribution range is narrow. detailed description
实施例 1 Example 1
将 11. 29g Co (N03) 2 · 6H20和 8. 478g Al (N03) 3 · 9H20加入 50ml去离 子水中配制盐溶液； 将 4. 79g NaC03和 3. 93g NaOH加入 50ml去离子水中 配制碱溶液。 11.29g Co (N0 3 ) 2 · 6H 2 0 and 8.478g Al (N0 3 ) 3 · 9H 2 0 were added to 50ml of deionized water to prepare a salt solution; 4.79g of NaCO 3 and 3.93g of NaOH were added to 50ml The alkaline solution is prepared in deionized water.
在 25 °C搅拌条件下， 将减溶液緩慢滴加到盐溶液中， 至 为 10停 止， 于 50°C水浴中， 晶化 12h,反应结束后抽滤， 用去离子水洗涤两次， 空 气中干燥。 Under agitation at 25 °C, the reduced solution was slowly added dropwise to the salt solution until 10 stops, crystallization in a 50 ° C water bath, 12 h, after the reaction was filtered, washed twice with deionized water, air Dry in the middle.
将上述制备得到的水滑石前体放于马弗炉中， 以 5 °C /min 的速率升 温至 60CTC , 保温 4h, 最后随炉冷却至室温得到催化剂样品。 The hydrotalcite precursor prepared above was placed in a muffle furnace, heated to 60 CTC at a rate of 5 ° C /min, held for 4 h, and finally cooled to room temperature with a furnace to obtain a catalyst sample.
低温氮气吸脱附测试其介孔平均孔径为 2. 3mn , 微孔平均孔径为 1. 5nm，平均孔径为 43nm ,总孔体积为 0. 605cm3/g,比表面积为 131. 3m2/g; 催化剂还原后经元素分析和 X-光电子能谱表征得出， 含有 8%的金属钴， 55%的 A1203和 Co304， 37%的 CoAl204, 经高分辨透射电镜观察其平均金属 颗粒大小为 15nm。 The singularity of the pores is 1. 5 nm, the average pore diameter is 1.5 nm, the total pore volume is 0. 605 cm 3 /g, and the specific surface area is 131. 3 m 2 /g. After catalyst reduction, elemental analysis and X-ray photoelectron spectroscopy showed that 8% of metal cobalt, 55% of A1 2 0 3 and Co 3 0 4 , and 37% of CoAl 2 0 4 were obtained by high-resolution transmission electron microscopy. The average metal particle size was observed to be 15 nm.
然后将 30mg 上述制备'所得的催化剂放入石英固定床中， 以流速为 30ml/min, H2/N2体积比为 1: 20的混合气体作为还原气， 以 5 °C /min的 速率升温至 50Q°C还原 2h；随后在 500°C条件下，将112切换成原料气 C2H2, C2H2和！^体积比为 1 : 20， 混合气流速 30ml/min, 继续以 5°C /min的速率 升温至裂解温度 700 °C进行碳纳米管的生长， 反应 2h后降至室温。 Then, 30 mg of the above-prepared catalyst was placed in a quartz fixed bed, and a mixed gas having a flow rate of 30 ml/min and a H 2 /N 2 volume ratio of 1:20 was used as a reducing gas, and the temperature was raised at a rate of 5 ° C /min. Reduction to 50h °C for 2h; then at 1100 °C, switch 11 2 into the feed gas C 2 H 2 , C 2 H 2 and! The volume ratio was 1:20, the mixed gas flow rate was 30 ml/min, and the growth of the carbon nanotubes was continued at a rate of 5 ° C /min to a cracking temperature of 700 ° C, and the reaction was allowed to fall to room temperature after 2 hours.
最终产品通过透射电镜证实了碳纳米管的生成， 平均管径 20 ~ 30nm,
管径均匀， 管壁光滑， 平均长度为 12μπι; 高倍透射电镜显示生成的碳纳 米管为 18层的多壁管， 产率达到 220 1κ 实施例 2 The final product confirmed the formation of carbon nanotubes by transmission electron microscopy, with an average diameter of 20 ~ 30nm. The tube diameter is uniform, the tube wall is smooth, and the average length is 12μπι; the high-power transmission electron microscope shows that the carbon nanotubes produced are 18-layer multi-wall tubes with a yield of 220 1κ. Example 2
称取 11. 64g Co (N03) 2 · 6H20、 2. 69g Fe (N03) 3 · 9H20 和 2. 50gWeigh 11.64g Co (N0 3 ) 2 · 6H 2 0, 2. 69g Fe (N0 3 ) 3 · 9H 2 0 and 2. 50g
A1 (N03) 3 - 9H20加入 50ml去离子水中配制盐溶液； 用 2. 83g NaC03、 3. 42gA1 (N0 3 ) 3 - 9H 2 0 is added to 50 ml of deionized water to prepare a salt solution; 2.83 g of NaC0 3 , 3. 42 g
NaOH与 5 Oral去离子水配制成碱溶液。 NaOH is combined with 5 Oral deionized water to make an alkaline solution.
在 25 °C搅拌条件下， 将碱液緩慢滴加到盐溶液中， 至 pH为 9停止， 于 40°C水浴中， 晶化 8h, 反应结束后抽滤， 用去离子水洗涤两次， 空气 中干燥。 将上述制备所得水滑石前体放于马弗炉中， 以 3 °C /min 的速率 升温至 700°C , 保温 5h， 最后随炉冷却至室温得到催化剂样品。 The lye was slowly added dropwise to the salt solution under stirring at 25 ° C until the pH was 9 and crystallization was carried out in a 40 ° C water bath for 8 hours. After the reaction was completed, it was suction filtered and washed twice with deionized water. Dry in the air. The hydrotalcite precursor prepared above was placed in a muffle furnace, heated to 700 ° C at a rate of 3 ° C / min, kept for 5 h, and finally cooled to room temperature with a furnace to obtain a catalyst sample.
低温氮气吸脱附测试其介孔平均孔径为 3. 5nm , f敖孔平均孔径为 The low-temperature nitrogen absorption and desorption test has a mesoporous average pore diameter of 3. 5 nm, and the average pore diameter of the f-perforation is
1. 7nm ,平均孔径为 51nm， 总孔体积为 0. 632cm3/g , 比表面积为 63. 3m2/g; 催化剂还原后经元素分析和 X-光电子能 i普表征得出， 含 17°/。的单质 Co和 Fe, 48%的 A1203、 Fe304 ^ Co304, 35%的 CoAl204和 CoFe204, 经高分辨透射 电镜观察其平均金属颗粒大小为 18nm。 1. 7nm, average pore diameter is 51nm, total pore volume is 0. 632cm 3 /g, specific surface area is 63. 3m 2 /g; after catalyst reduction, elemental analysis and X-photoelectron energy characterization, including 17° /. The elemental masses of Co and Fe, 48% of A1 2 0 3 , Fe 3 0 4 ^ Co 3 0 4 , 35% of CoAl 2 0 4 and CoFe 2 0 4 were observed by high-resolution transmission electron microscopy to an average metal particle size of 18 nm. .
再按实施例 1 的步驟进行碳纳米管的生长试验。 最终产品通过透射 电镜证实了碳纳米管的生成， 且管径均匀， 管壁光滑， 平均管径为 20 ~The growth test of carbon nanotubes was carried out in the same manner as in Example 1. The final product confirmed the formation of carbon nanotubes by transmission electron microscopy, and the tube diameter was uniform, the tube wall was smooth, and the average tube diameter was 20 ~
30nm, 平均长度为 6μιη, 高倍透射电镜显示生成的碳纳米管为 20 层的多 壁管， 产率达到 280 。 实施例 3 At 30 nm, the average length is 6 μm, and high-power transmission electron microscopy shows that the carbon nanotubes produced are 20-layer multi-walled tubes with a yield of 280. Example 3
将 10. 51g NiS04 · 6H20、 3. 71g FeS04■ 7H20和 8. 88g Al2 (S04) 3 · 18H20 加入 100ml 去离子水中配制盐溶液; 将 14. 20g Na2S04和 6. 00g NaOH加 入 lOOffll通过 N2去离子水中配制碱溶液。 10. 51g NiS0 4 · 6H 2 0, 3. 71g FeS0 4 ■ 7H 2 0 and 8. 88g Al 2 (S0 4 ) 3 · 18H 2 0 is added to 100ml of deionized water to prepare a salt solution; 14.20g Na 2 S0 4 and 6. 00 g NaOH was added to lOOffll to prepare an alkali solution in N 2 deionized water.
在氮气保护、 25 °C带搅拌条件下， 将碱液緩慢滴加到盐溶液中， 至 pH
为 8停止； 在！^保护的条件下， 于 20Ό水浴中， 晶化 24h, 反应结束后 抽滤， 用通过 N2的冰水洗涤， 最后再用乙醇洗涤两次， 空气中干燥。 将 上述制备所得水滑石前体放于马弗炉中，以 10°C/min的速率升温至 800°C , 保温 5h, 最后随炉冷却至室温得到催化剂样品。 Slowly add the lye to the salt solution under nitrogen atmosphere at 25 °C with stirring to pH Stop for 8; at! Under the conditions of protection, crystallization was carried out for 24 hours in a 20 Torr water bath. After the reaction was completed, it was suction filtered, washed with ice water of N 2 and finally twice with ethanol, and dried in air. The hydrotalcite precursor prepared above was placed in a muffle furnace, heated to 800 ° C at a rate of 10 ° C / min, held for 5 h, and finally cooled to room temperature with a furnace to obtain a catalyst sample.
低温氮气吸脱附测试该催化剂的介孔平均孔径为 6. lnm, 微孔平均孔 径为 1. 9nm ，平均孔径为 45nm , 总孔体积为 0. 685cmVg , 比表面积为 105. 3m2/g; 该催化剂还原后经元素分析和 X-光电子能侮测得含有 10%的 单质 Ni和 Fe， 45%的 A1203、 NiO和 Fe304, 45%的 NiAl204和 NiFe204, 经 高分辨透射电镜观察其平均金属颗粒大小为 17nm。 The osmotic volume is 0. 685cmVg, the specific surface area is 105. 3m 2 /g; the specific pore diameter is 0. 685cmVg, the specific surface area is 105. 3m 2 /g; After reduction of the catalyst, elemental analysis and X-photoelectron spectroscopy showed that 10% of elemental Ni and Fe, 45% of A1 2 0 3 , NiO and Fe 3 0 4 , 45% of NiAl 2 0 4 and NiFe 2 0 were obtained. 4. The average metal particle size was 17 nm observed by high resolution transmission electron microscopy.
再按实施例 1 的步骤进行碳纳米管的生长试^ r。 最终产品通过透射 电镜证实了碳纳米管的生成， 且管径均匀， 管壁光滑， 平均管径为 25 ~ 35nm, 平均长度为 8μπι， 高倍透射电镜显示生成的碳纳米管为 21 层的多 壁管， 产率达到 290%。 实施例 4 The growth test of carbon nanotubes was carried out in the same manner as in Example 1. The final product confirmed the formation of carbon nanotubes by transmission electron microscopy, and the tube diameter was uniform, the tube wall was smooth, the average diameter was 25 ~ 35nm, and the average length was 8μπι. The high-power transmission electron microscope showed that the carbon nanotubes produced were 21-layer multi-wall. Tube, the yield reached 290%. Example 4
称取 11. 89g Ni (N03) 2 · 6H20和 3. 67g Fe (N03) 3 · 9H20加入 100ml 去 离子水中配制成盐溶液； 用 100ml去离子水、 14. 61g NaCl和 4. 00g NaOH 配制碱溶液。 Weigh 11.89g Ni (N0 3 ) 2 · 6H 2 0 and 3. 67g Fe (N0 3 ) 3 · 9H 2 0 into 100ml deionized water to make a salt solution; use 100ml deionized water, 14. 61g NaCl and 4. 00g NaOH to prepare an alkaline solution.
在氮气保护、 25°C带搅拌条件下， 将碱液緩慢滴加到盐溶液中， 至 pH 为 9. 5停止； 在 N2保护的条件下， 于 7(TC 7j浴中， 晶化 5h, 反应结束后 抽滤。 用通过 N2的水水洗涤， 最后再用乙醇洗涤两次， 空气中干燥。 将上 述制备所得水滑石前体放于马弗炉中， 以 lOO/min的速率升温至 850°C , 保温 5h, 最后随炉冷却至室温得到催化剂样品。 Under a nitrogen atmosphere, stirring at 25 ° C, the lye was slowly added dropwise to the salt solution until the pH was 9.5. Stop; under N 2 protection, in 7 (TC 7j bath, crystallization for 5 h) After the reaction, the mixture was filtered, washed with water of N 2 , and finally washed twice with ethanol, and dried in air. The hydrotalcite precursor prepared above was placed in a muffle furnace and heated at a rate of 100/min. The catalyst sample was obtained by heating to 850 ° C for 5 h and finally cooling to room temperature with the furnace.
低温氮气吸脱附测试该催化剂的介孔平均孔径为 10. Onm, 孔平均 孔径为 0. 8nm，平均孔径为 63nm , 总孔体积为 0. 735cm3/g, 比表面积为 56. 3mVg; 该催化剂还原后经元素分析和 X-光电子能谱测得含有 12%的单
质 Ni和 Fe, 58%的 NiO和 Fe304， 30%的 NiFe204， 经高分辨透射电镜观察 其平均金属颗粒大小为 22nm。 The surface area is 0. 735cm 3 /g, the specific surface area is 56. 3mVg; After catalyst reduction, elemental analysis and X-ray photoelectron spectroscopy showed 12% single Ni and Fe, 58% of NiO and Fe 3 0 4 , and 30% of NiFe 2 0 4 were observed by high-resolution transmission electron microscopy to have an average metal particle size of 22 nm.
再按实施例 1 的步骤进行碳纳米管的生长试验。 最终产品通过透射电 镜证实了碳纳米管的生成， 且管径均匀， 管壁光滑， 平均管径为 35 ~ 40 nm, 平均长度大约为 8 jn, 高倍透射电镜显示生成的碳纳米管为 24层的多壁管， 产率达到 250%。 实施例 5 The growth test of carbon nanotubes was carried out in the same manner as in Example 1. The final product confirmed the formation of carbon nanotubes by transmission electron microscopy, and the tube diameter was uniform, the tube wall was smooth, the average diameter was 35 ~ 40 nm, and the average length was about 8 jn. The high-power transmission electron microscope showed that the carbon nanotubes were 24 layers. The multi-wall tube has a yield of 250%. Example 5
将 11. 17g Ni (N03) 2 · 6H20、 2. 46g Mg (N03) 2 · 6H20 和 10. 66g A12 (S04) 3 · 18H20加入 100ml去离子水中配制成盐溶液； 将 19. 08g Na2C03 和 8. 8g NaOH加入 100ml 去离子水配制成碱溶液。 11.17g Ni (N0 3 ) 2 · 6H 2 0, 2. 46g Mg (N0 3 ) 2 · 6H 2 0 and 10.66g A1 2 (S0 4 ) 3 · 18H 2 0 are added to 100ml of deionized water. Salt solution; 19.08 g of Na 2 CO 3 and 8.8 g of NaOH were added to 100 ml of deionized water to prepare an alkali solution.
在 25 °C搅拌条件下， 将碱液緩慢滴加到盐溶液中， 至 pH为 11停止， 于 40°C水浴中， 晶化 8h, 反应结束后抽滤。 用去离子水洗涤两次， 空气 中干燥。 将上述制备所得水滑石前体放于马弗炉中， 以 3 °C /min 的速率 升温至 700°C；， 保温 5h, 最后随炉冷却至室温得到催化剂样品。 The lye was slowly added dropwise to the salt solution under stirring at 25 ° C until the pH was 11 and crystallization was carried out in a 40 ° C water bath for 8 hours. After the reaction was completed, suction filtration was carried out. Wash twice with deionized water and dry in air. The hydrotalcite precursor prepared above was placed in a muffle furnace and heated to 700 ° C at a rate of 3 ° C / min; held for 5 h, and finally cooled to room temperature with a furnace to obtain a catalyst sample.
4氐温氮气吸脱附测试该催化剂的介孔平均孔径为 18nm, 孔平均孔 径为 1. 2nm ,平均孔径为 65nm , 总孔体积为 0. 585cm3/g， 比表面积为 42. 5m2/g; 该催化剂还原后经元素分析和 X-光电子能谱测得含有 13%的单 质 Ni， 49%的 A1203、 NiO和 MgO, 38°/。的 NiAl204和 MgAl204, 经高分辨透射 电镜观察其平均金属颗粒大小为 25mn。 4 Di nitrogen desorption temperature of the catalyst test mesopores an average pore diameter 18nm, average pore diameter of the hole 1. 2nm, average pore diameter of 65nm, a total pore volume of 0. 585cm 3 / g, a specific surface area of 42. 5m 2 / g; After reduction of the catalyst, elemental analysis and X-ray photoelectron spectroscopy showed that 13% of elemental Ni, 49% of A1 2 0 3 , NiO and MgO, 38°/. NiAl 2 0 4 and MgAl 2 0 4 were observed by high-resolution transmission electron microscopy to have an average metal particle size of 25 nm.
再按实施例 1 的步骤进行碳纳米管的生长试验。 最终产品通过透射 电镜证实了碳纳米管的生成， 且管径较为均匀， 平均管径为 35 ~ 40 nm, 平均长度大约为 5. 5μ ， 高倍透射电镜显示生成的碳纳米管为 23 层的多 壁管， 产率达到 270 %。
The growth test of carbon nanotubes was carried out in the same manner as in Example 1. The final product was confirmed by transmission electron microscopy, and the diameter of the carbon nanotubes was relatively uniform. The average diameter was 35 ~ 40 nm, and the average length was about 5. 5μ. The high-power transmission electron microscope showed that the carbon nanotubes produced were 23 layers. The wall tube has a yield of 270%.
Claims
1、 一种碳纳米管生长用催化剂的制备方法， 具体步骤如下： 1. A method for preparing a catalyst for carbon nanotube growth, the specific steps are as follows:
A. 用去离子水配制含有二价金属离子 M2+和三价金属离子 M3+的混合 盐溶液,其中 [M2+] I [M3+] =1.2-5.0,且各种金属离子的总摩尔浓度为 0.4 ~ 1.2M; 其中 M2+是 Mg2+、 Fe2\ Ni2+、 Co2+、 Cu2+中的一种或多种， M3+是 Co3+、 Al3+、 Fe3+中的一种或多种， 盐混合溶液中的的酸根离子可以是 Cl—、 C03 2一、 N03-或 S04 2-中的任意一种或多种； - 用氢氧化钠、 可溶性无机钠盐和去离子水配制混合碱性溶液， 其中 氢氧化钠浓度为 0.8 ~ 2.5 , 钠盐浓度为 0.3 ~ 3.0 M; A. Preparing a mixed salt solution containing a divalent metal ion M 2+ and a trivalent metal ion M 3+ with deionized water, wherein [M 2+ ] I [M 3+ ] = 1.2-5.0, and various metal ions The total molar concentration is 0.4 ~ 1.2M; wherein M 2+ is one or more of Mg 2+ , Fe 2 \ Ni 2+ , Co 2+ , Cu 2+ , M 3+ is Co 3+ , Al One or more of 3+ and Fe 3+ , the acid ion in the salt mixed solution may be any one or more of Cl—, C0 3 2 —, N0 3 — or S0 4 2 −; Preparing a mixed alkaline solution with sodium hydroxide, soluble inorganic sodium salt and deionized water, wherein the sodium hydroxide concentration is 0.8 ~ 2.5, and the sodium salt concentration is 0.3 ~ 3.0 M;
B. 将混合碱性溶液緩慢滴加到混合盐溶液中， 当体系中的 pH值 达到 7 ~ 12时， 停止滴加， 在 20~ 70°C水浴中， 晶化 5 ~ 25h, 经过 滤， 洗涤，干燥， 得到层状水滑石 LDHs 前体， 该前体的结构通式为: [Μ2+ Χ_ΧΜ3+ Χ (0Η)2]χ+(Απ— )x/n · m 0,其中 M2+、 M3+与步骤 A 中的相同； An一为 步骤 A中混合盐和碱溶液中的阴离子中的一种或多种； B. Slowly add the mixed alkaline solution to the mixed salt solution. When the pH value in the system reaches 7 ~ 12, stop the dropwise addition, crystallize in the water bath at 20~70 °C for 5 ~ 25h, and filter. Washing and drying to obtain a layered hydrotalcite LDHs precursor having a structural formula of: [Μ 2+ Χ _ Χ Μ 3+ Χ (0Η) 2 ] χ+ (Α π — ) x/n · m 0, wherein M 2+ , M 3+ are the same as in step A; A n is one or more of the anions in the mixed salt and alkali solution in step A;
C. 将上述 LDHs置于高温炉中， 以 2~15°C/min的速率升温至 500 ~ C. Place the above LDHs in a high temperature furnace and heat up to 500 ~ at a rate of 2~15 °C/min.
900°C, 焙烧 2~7h, 得到制备碳纳米管的催化剂。 At 900 ° C, calcination for 2-7 h, a catalyst for preparing carbon nanotubes is obtained.
2、 权利要求 1 所述的碳纳米管生长用催化剂的制备方法： 其特征是 可溶性无机钠益是 NaCl、 Na2C03、 NaN03或 Na2S04, 当可溶性无机钠盐为 硫酸钠、 硝酸钠或氯化钠时， 步驟 A和 B需在氮气保护下进行。 The method for preparing a catalyst for carbon nanotube growth according to claim 1, wherein the soluble inorganic sodium is NaCl, Na 2 C0 3 , NaN0 3 or Na 2 S0 4 , and the soluble inorganic sodium salt is sodium sulfate. In the case of sodium nitrate or sodium chloride, steps A and B are carried out under nitrogen.
3、 一种碳纳米管生长用催化剂， 其特征是该催化剂是用权利要求 1 的方法制备得到的。 A catalyst for carbon nanotube growth characterized in that the catalyst is produced by the method of claim 1.
4、 权利要求 3 所述的碳纳米管生长用催化剂， 其特征是该催化剂是 多孔性的， 其介孔平均孔径为 2.3 - 30nm, 微孔平均孔径为 0.4 ~ 2. Onm, 平均孔径为 20~ 100nra, 总孔体积为 0, 4 ~ 1. OcmVg, 比表面积为 50 - 300mVgo
The catalyst for carbon nanotube growth according to claim 3, wherein the catalyst is porous, having a mesoporous average pore diameter of 2.3 to 30 nm, a micropore average pore diameter of 0.4 to 2. Onm, and an average pore diameter of 20 ~ 100nra, total pore volume 0, 4 ~ 1. OcmVg, specific surface area 50 - 300mVg o
5、 权利要求 3 所述的碳纳米管生长用催化剂， 其特征是该催化剂按 使用前的还原条件进行还原后， 各组分的质量百分含量分别是： The catalyst for carbon nanotube growth according to claim 3, characterized in that the mass percentage of each component after the reduction of the catalyst according to the reducing conditions before use is:
活性单质金属： 5 - 25% Active elemental metal: 5 - 25%
金属氧化物： 40 ~ 60% Metal oxide: 40 ~ 60%
尖晶石结构的复合氧化物： 15 ~ 55%； Composite oxide of spinel structure: 15 ~ 55%;
其中金属氧化物以 M203、 MO或 M304形式存在； 活性单质金属颗粒大 小为 15 ~ 35nm。 The metal oxide is present in the form of M 2 O 3 , MO or M 3 0 4 ; the active elemental metal particles are 15 to 35 nm in size.
6、 权利要求 5 所述的碳纳米管生长用催化剂， 其特征是该催化剂还 原后， 活性单质金属为 Fe、 Ni、 Co和 Cu中的一种或多种； 金属氧化物 是 A1203 、 Co203、 Fe203、 Mg0、 Ni0、 Co0、 Co304、 Fe304中的一种或多种； 尖晶石型复合氧化物以 M2+M3+ 204形式存在， 其中 M2+为 Co2+、 Ni2+ 、 Fe2+、 Mg2+和 Cu2+中的一种或多种, M3+为 Co3+、 Fe3+ 、 Al3+中的一种或多种。
The catalyst for carbon nanotube growth according to claim 5, wherein after the catalyst is reduced, the active elemental metal is one or more of Fe, Ni, Co and Cu; and the metal oxide is A1 2 0 3 One or more of Co 2 0 3 , Fe 2 0 3 , Mg0, Ni0, Co0, Co 3 0 4 , Fe 3 0 4 ; spinel-type composite oxide with M 2+ M 3+ 2 0 Form 4 exists, wherein M 2+ is one or more of Co 2+ , Ni 2+ , Fe 2+ , Mg 2+ and Cu 2+ , and M 3+ is Co 3+ , Fe 3+ , Al 3 One or more of + .
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| CN102068991B (en) * | 2010-11-26 | 2012-07-04 | 北京化工大学 | High dispersed loaded nano-metal Ni catalyst and preparation method thereof |
| CN102502584A (en) * | 2011-11-01 | 2012-06-20 | 南京大学 | Method for controllably synthesizing carbon nano-fiber, carbon nanotube and carbon nanospring |
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| CN111135788A (en) * | 2019-09-18 | 2020-05-12 | 青岛农业大学 | Magnetic nitrogen-doped carbon nanotube water treatment adsorbent and preparation method thereof |
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