CN113731433B - Trace molybdenum doped iron-based catalyst and preparation method and application thereof - Google Patents
Trace molybdenum doped iron-based catalyst and preparation method and application thereof Download PDFInfo
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- CN113731433B CN113731433B CN202111005279.9A CN202111005279A CN113731433B CN 113731433 B CN113731433 B CN 113731433B CN 202111005279 A CN202111005279 A CN 202111005279A CN 113731433 B CN113731433 B CN 113731433B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 32
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 11
- 239000011733 molybdenum Substances 0.000 title claims abstract description 7
- 239000002109 single walled nanotube Substances 0.000 claims abstract description 94
- 238000000034 method Methods 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 239000011609 ammonium molybdate Substances 0.000 claims description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 9
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 9
- 229940010552 ammonium molybdate Drugs 0.000 claims description 9
- 159000000003 magnesium salts Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 150000002751 molybdenum Chemical class 0.000 claims description 9
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims 3
- 238000010304 firing Methods 0.000 claims 2
- 239000006260 foam Substances 0.000 abstract description 5
- 238000005530 etching Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 31
- 239000000463 material Substances 0.000 description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 16
- 239000002041 carbon nanotube Substances 0.000 description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 description 11
- 239000000395 magnesium oxide Substances 0.000 description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 7
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 7
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 101150116295 CAT2 gene Proteins 0.000 description 2
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 2
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910017116 Fe—Mo Inorganic materials 0.000 description 2
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 2
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002079 double walled nanotube Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance 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
- B01J23/76—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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
-
- B01J35/40—
-
- B01J35/618—
-
- 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
- C01B32/159—Carbon nanotubes single-walled
-
- 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
-
- 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
- C01B2202/02—Single-walled nanotubes
-
- 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
- C01B2202/30—Purity
-
- 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
- C01B2202/32—Specific surface area
Abstract
The invention provides a trace molybdenum doped iron-based catalyst and a preparation method and application thereof. The catalyst prepared by the method has a loose porous foam structure, adopts low-temperature roasting and micro Mo doping to form a special iron molybdate structure, further adopts water for etching, avoids damaging the structure, and can realize large-scale preparation of high-quality SWNTs.
Description
Technical Field
The invention relates to the technical field of single-wall carbon nanotube preparation, in particular to a trace molybdenum doped iron-based catalyst and a preparation method and application thereof.
Background
Carbon nanotubes, which are a novel carbon material, have many excellent properties such as mechanical properties, electrical conductivity, thermal conductivity, etc., due to their special structure. The carbon nanotubes can be roughly classified into single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, and the like according to the number of layers of the wall, and single-walled carbon nanotubes are one-dimensional carbon nanotube hollow tubular structures composed of carbon atoms, and can be regarded as seamless carbon tubes formed by crimping single-layered graphene.
Among them, single-walled carbon nanotubes (SWNTs), which have a high aspect ratio, are typical one-dimensional nanomaterials, and their special tubular structures determine that carbon nanotubes have excellent physical, chemical, electrical and mechanical properties, so that they have extremely important application values in many fields, especially in the fields of energy storage, environmental protection, electronics, composite materials, medical fields, etc., are increasingly highlighted. At present, the methods for growing single-wall carbon nanotubes mainly comprise an arc discharge method, a laser evaporation catalytic precipitation technology, a Chemical Vapor Deposition (CVD) method and the like, the former two methods are very complex to operate, solid carbon sources are required to be evaporated into carbon atoms at a high temperature of more than 3000 ℃, the number of synthesizable carbon nanotubes is severely limited, and in addition, the carbon nanotubes grown by evaporating the carbon atoms are highly entangled in morphology, and are mixed with other carbon impurities and metal catalysts, so that the application range of the method is severely limited. The chemical vapor deposition method is the most important method for preparing single-wall carbon nanotubes, but the chemical vapor deposition method still has very serious problems such as low SWNTs yield, high catalyst preparation cost and the like.
The Fe group metal has higher SWNTs growth activity and is widely used for industrially producing the carbon nano tube, but the service life of the catalyst is shorter, and the satisfactory SWNTs yield is difficult to obtain. To increase the yield of SWNTs, other metals may be added to achieve the high activity, long life requirements of the catalyst. The metal Mo does not have the high activity characteristic of SWNTs growth, but has larger binding force between Mo and C and higher carbon dissolving capacity, and can improve the carbon yield of the catalyst, so that the single-wall carbon nano tube CVD growth based on the Fe-Mo bimetallic catalyst can realize the mass preparation of the single-wall carbon nano tube. However, based on the effect of Mo, the Mo consumption in the prior art is relatively high, the Fe to Mo atomic ratio is usually about 0.5-10, for example, the beijing university application CN201911006484 discloses a CVD preparation method of single-walled carbon nanotubes, by optimizing the catalyst formulation, reducing the Mg content in the catalyst, optimizing the flux of carbon-containing gas, hydrogen and inert gas, and enabling macro-scale preparation of carbon nanotubes, while the carbon yield in the grown product is approximately 2 times, wherein the molar ratio of Mo to Fe in the catalyst formulation is 0.1, the Mo consumption is relatively high, and few researchers recognize that the relatively low Mo addition can not only maintain the activity of the catalyst, but also can significantly improve the stability of the catalyst.
Disclosure of Invention
In order to solve the problems, the invention provides the molybdenum-doped iron-based catalyst, and the preparation method and the application thereof, wherein the molybdenum-doped iron-based catalyst is baked at a low temperature, is doped with a trace amount of Mo to form a special iron molybdate structure, and is further etched by water to avoid damaging the structure. Can realize the large-scale preparation of SWNTs and trace H 2 The quality and the property of SWNTs can be regulated and controlled by O, so that the quality of the product is effectively improved.
The first aspect of the invention provides a method for preparing a molybdenum-doped iron-based catalyst, the method comprising the steps of:
s1: mixing soluble molybdenum salt and an initiator and dissolving the mixture in water to obtain a precursor solution;
s2: adding soluble ferric salt, soluble magnesium salt and an auxiliary agent into the precursor solution obtained in the step S1, stirring and dissolving, then adding silicon oxide and an alumina carrier under intense stirring, and uniformly stirring to obtain uniform and viscous slurry;
s3: and (3) drying the uniform and sticky slurry obtained in the step (S2), grinding, and finally roasting at a low temperature to obtain the molybdenum-doped iron-based catalyst.
Further, the molar ratio of the iron atoms in the soluble iron salt to the molybdenum atoms in the soluble molybdenum salt is (25-60): 1.
Further, the molar ratio of the iron atom in the soluble iron salt to the magnesium atom in the soluble magnesium salt is (20-30): 1.
Further, the carrier is weighed according to 2-10wt% of the iron content in the catalyst.
Further, the soluble ferric salt is selected from at least one of ferric chloride, ferric nitrate and ferric sulfate.
Further, the soluble molybdenum salt is at least one selected from ammonium molybdate and sodium molybdate.
Further, the soluble magnesium salt is at least one selected from magnesium chloride, magnesium nitrate and magnesium sulfate.
Further, the initiator is selected from urea.
Further, the auxiliary agent is at least one selected from citric acid and sodium citrate.
Further, the mass ratio of the silicon oxide to the aluminum oxide carrier is 3-9:1, preferably 4:1.
Further, the drying temperature is 80-160 ℃, and the drying time is 6-48h.
Further, the roasting temperature is 300-400 ℃ and the roasting time is 2-6h.
The second aspect of the invention provides a molybdenum-doped iron-based catalyst, which comprises an active component and a carrier, wherein the active component comprises a main active component and a secondary active component, the main active component is iron, the secondary active component is molybdenum, and the carrier is silicon oxide or aluminum oxide.
Further, the iron content of the catalyst is 2 to 10wt%, preferably 4 to 6wt%.
Further, the molar ratio of iron atoms to molybdenum atoms in the catalyst is (25-60): 1, preferably 30:1.
Further, the particle size of the active component FeMo in the catalyst is 15-25nm.
Further, the mass ratio of the carrier silicon oxide to the carrier aluminum oxide is 3-9:1, preferably 4:1.
Further, the iron and molybdenum form iron molybdate.
The third aspect of the present invention provides a method for preparing single-walled carbon nanotubes, the method comprising the steps of:
s1: placing the catalyst provided by the invention or the catalyst prepared by the preparation method provided by the invention into a reaction device, and heating to the reaction temperature;
s2: introducing methane containing water vapor and inert gas for reaction;
s3: purifying the product obtained in the step S2 to obtain the single-walled carbon nanotube.
Further, the reaction temperature is 600 to 900 ℃, preferably 700 to 800 ℃.
Further, the concentration of the water vapor is 100-1000ppm.
Further, the inert gas is one of helium and argon.
Further, the concentration of methane is 20-50%.
Compared with the prior art, the invention has at least the following technical effects:
(1) The invention adopts low-concentration Mo doping and low-temperature roasting to form FeMo alloy, effectively improves the carbon yield and the purity of SWNTs, and simultaneously selects a proper amount of H 2 O is used as an etchant, does not damage the microstructure of FeMo, can ensure that the catalyst has better anti-sintering performance, prolongs the service life of the catalyst, and simultaneously has trace H 2 The quality and the property of SWNTs can be regulated and controlled by O, so that the quality of the product is effectively improved.
(2) The FeMo in the catalyst prepared by the invention has small particle size and average particle size of 15-25nm, and meanwhile, the catalyst prepared by the invention has a porous foam structure, has the advantages of high porosity (mesoporous is concentrated on microcosmic scale to form a mesoporous-macroporous loose structure), high metal dispersity and high activity, improves sufficient active sites and growth space for mass growth of SWNTs, and can realize large-scale preparation of the SWNTs.
(3) The invention adopts the silicon oxide and the aluminum oxide carrier, overcomes the defect that the magnesium oxide carrier is difficult to form, effectively improves the fluidity of the catalyst in a fluidized bed, and simultaneously optimizes the proper conditions for obtaining the Fe-Mo catalyst reaction. The catalyst used is at a higher CH 4 Concentration and lower reactionThe temperature reaction is favorable for growing SWNTs with high quality and high yield. I of SWNTs produced by the method of the present invention G /I D All exceed 13, and the specific surface area is as high as 1053.3m 2 The carbon yield per gram can reach 33.5%, and the purity of SWNTs reaches 98.7%.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate and together with the embodiments of the invention serve to explain the invention and do not limit the invention.
FIG. 1 is an SEM image of the catalyst Cat-1 prepared in example 1;
FIG. 2 is a TEM image of the catalyst Cat-1 prepared in example 1;
FIG. 3 is an SEM image of the product SWNTs-1 of example 1;
FIG. 4 is an SEM image of the product SWNTs-7 of comparative example 4;
FIG. 5 is an SEM image of the product SWNTs-10 of comparative example 7.
Detailed Description
The invention provides a preparation method of a molybdenum-doped iron-based catalyst, which comprises the following steps:
s1: mixing soluble molybdenum salt and an initiator and dissolving the mixture in water to obtain a precursor solution; according to an embodiment of the invention, the soluble molybdenum salt is selected from at least one of ammonium molybdate and sodium molybdate, and the initiator is selected from urea.
S2: adding soluble ferric salt, soluble magnesium salt and an auxiliary agent into the obtained precursor solution, stirring and dissolving, then adding silicon oxide and an alumina carrier under intense stirring, and uniformly stirring to obtain uniform and sticky slurry; according to the embodiment of the invention, the soluble ferric salt is selected from at least one of ferric chloride, ferric nitrate and ferric sulfate, the soluble magnesium salt is selected from at least one of magnesium chloride, magnesium nitrate and magnesium sulfate, the auxiliary agent is selected from at least one of citric acid and sodium citrate, and the mass ratio of the silicon oxide to the aluminum oxide is 3-9: 1.
s3: and drying the obtained uniform and viscous slurry, grinding, and finally roasting at a low temperature of 300-400 ℃ to obtain the molybdenum-doped iron-based catalyst.
According to an embodiment of the present invention, the molar ratio of the iron atoms in the soluble iron salt to the molybdenum atoms in the soluble molybdenum salt is (25-60): 1. The low-concentration Mo doping is adopted, so that the carbon yield and the purity of SWNTs are effectively improved.
According to the examples of the present invention, the molar ratio of the iron atom in the soluble iron salt to the magnesium atom in the soluble magnesium salt was (20-30): 1.
According to an embodiment of the present invention, the support is weighed according to 2-10wt% of the iron content in the catalyst.
According to the embodiment of the invention, the drying temperature is 80-160 ℃, and the drying time is 6-48h.
According to the embodiment of the invention, the roasting temperature is 300-400 ℃ and the roasting time is 2-6h.
The invention also provides a preparation method of the single-walled carbon nanotube, which comprises the following steps:
s1: placing the catalyst prepared by the preparation method or the catalyst provided by the invention into a reaction device, and heating to the reaction temperature; the reaction temperature according to the embodiments of the present invention is 600 to 900 c, preferably 700 to 800 c.
S2: methane containing water vapor and inert gas is added to carry out the reaction.
S3: purifying the product obtained in the step S2 to obtain the single-walled carbon nanotube.
According to an embodiment of the invention, the concentration of water vapour is 100-1000ppm, the concentration of methane is 20-50%, and the inert gas is preferably argon. The invention utilizes H 2 O is used as an etchant, does not damage the microstructure of FeMo, can ensure that the catalyst has better anti-sintering performance, prolongs the service life of the catalyst, and simultaneously has trace H 2 The quality and the property of SWNTs can be regulated and controlled by O, so that the quality of the product is effectively improved.
The following examples illustrate the detailed preparation procedures and conditions of the preparation methods provided by the present invention.
Example 1
(1) Preparation of the catalyst: weighing 0.196g of ammonium molybdate and 1g of urea, mixing and dissolving in 20mL of deionized water, and uniformly stirring; 8.2g of ferric nitrate and 0.148g of nitrate are addedStirring and dissolving magnesium carbonate and 2g of citric acid, after stirring until the magnesium carbonate and the citric acid are completely dissolved, adding 43.2g of fumed silica and 10.8g of gamma-alumina (more than 200 meshes) under vigorous stirring, and stirring until uniform and sticky slurry is formed; drying overnight in a baking oven at 120 ℃, grinding into powder after complete drying, heating to 350 ℃ at 2 ℃ per minute, and roasting for 240min to obtain the catalyst Fe 30 Mo 1 MgO, designated Cat-1, wherein the content of Fe is about 3wt%.
(2) SWNTs preparation: placing 0.5g Cat-1 catalyst in a quartz reaction tube with the inner diameter of 16mm, introducing 100sccm argon, and heating to the reaction temperature of 800 ℃ for 60 min; introducing 500sccm methane, water vapor and argon gas mixture, wherein the concentration of methane is 30%, the concentration of water vapor is 200ppm, and starting SWNTs growth reaction; after 60min, the reaction gas is closed, heating is stopped, and 100sccm Ar is kept to be cooled to room temperature; the product was removed and then purified to give single walled carbon nanotubes, designated SWNTs-1.
Fig. 1 is an SEM image of the catalyst prepared in example 1, and it can be seen that the catalyst prepared in the invention has a porous foam structure, and the porous foam structure provides a growth support and a wide space for SWNTs, so that the growth direction of SWNTs is expanded from two dimensions to three dimensions, and the catalyst can meet the requirements of high metal load and high dispersion, can form a blocking space, reduces the interaction between pipes, and is beneficial to the mass growth of SWNTs just by forming a loose foam space structure composed of macropores and mesopores.
FIG. 2 is a TEM image of the catalyst prepared in example 1, showing that FFT transforms show the addition of MgO (200) and Fe 3 The C (301) crystal face, also Fe 2 MoO 4 The crystal planes (211), (432) and (223) indicate that Fe and Mo form a specific structure.
Example 2
The procedure and materials used in the preparation of the catalyst in this example were the same as those in example 1, except that the amount of ammonium molybdate used in this example was 0.098g, and the remaining procedure and materials used in the preparation of the catalyst were the same as those in example 1. The catalyst prepared in this example was Fe 60 Mo 1 MgO, designated Cat-2.
SWNTs preparation: the steps and materials for preparing SWNTs in this example are the same as those in example 1, except that Cat-2 is used as the catalyst in this example, and the steps and materials for preparing SWNTs are the same as those in example 1. SWNTs prepared in this example were designated SWNTs-2.
Example 3
The procedure and materials for preparing the catalyst in this example were the same as in example 1, except that the amount of ammonium molybdate in this example was 0.0235g, and the procedure and materials for preparing the catalyst were the same as in example 1. The catalyst prepared in this example was Fe 25 Mo 1 MgO, designated Cat-3.
SWNTs preparation: the steps and materials for preparing SWNTs in this example are the same as those in example 1, except that Cat-3 is used as the catalyst in this example, and the steps and materials for preparing SWNTs are the same as those in example 1. SWNTs prepared in this example were designated SWNTs-3.
The SWNTs-1, SWNTs-2 and SWNTs-3 prepared in examples 1 to 3 were subjected to performance test to obtain I G /I D The specific results are shown in Table 1:
TABLE 1 SWNTs obtained in examples 1-3 are I G /I D Value of
| Sample of | SWNTs | I G /I D |
| Example 1 | SWNTs-1 | 15.5 |
| Example 2 | SWNTs-2 | 14.3 |
| Example 3 | SWNTs-3 | 14.7 |
As can be seen from the above table, the catalyst of the present invention is used for preparing single-walled carbon nanotubes G /I D All exceed 13, and the SWNTs have good graphitization degree, and the more complete the pipe wall structure of the obtained SWNTs.
Comparative example 1
Comparative example 1 the procedure and materials used for preparing the catalyst were the same as in example 1, except that the amount of ammonium molybdate used in comparative example 1 was 0.588g, and the procedure and materials used for preparing the catalyst were the same as in example 1. Comparative example 1 the catalyst prepared was Fe 10 Mo 1 MgO, designated Cat-4.
SWNTs preparation: comparative example 1 the SWNTs preparation procedure and materials were the same as in example 1 except that Cat-4 was used as catalyst in comparative example 1 and the remaining SWNTs preparation procedure and materials were the same as in example 1. SWNTs prepared in comparative example 1 were designated SWNTs-4.
Comparative example 2
Comparative example 2 the procedure and materials used for preparing the catalyst were the same as in example 1, except that the amount of ammonium molybdate used in comparative example 2 was 2.94g, and the procedure and materials used for preparing the catalyst were the same as in example 1. The catalyst prepared in this comparative example is Fe 2 Mo 1 MgO, designated Cat-5.
SWNTs preparation: comparative example 2 the SWNTs preparation procedure and materials were the same as in example 1 except that Cat-5 was used as catalyst in comparative example 2 and the remaining SWNTs preparation procedure and materials were the same as in example 1. SWNTs prepared in comparative example 2 were designated SWNTs-5.
Comparative example 3
Weighing 8.2g of ferric nitrate and 0.196g of ammonium molybdate, and dissolving in a proper amount of absolute ethyl alcoholAdding 54g of light MgO under stirring, uniformly stirring, putting into a 100 ℃ oven for drying overnight, grinding into powder after complete drying, and roasting for 180min at the temperature of 2 ℃/min to 450 ℃, wherein the ethanol amount is 1.0-1.2 times of the saturated adsorption amount of the light MgO, and the catalyst is 3wt% Fe 30 Mo 1 MgO-IM, designated Cat-6.
SWNTs preparation: comparative example 3 the SWNTs preparation procedure and materials were the same as in example 1 except that comparative example 3 used Cat-6 as the catalyst and the remaining SWNTs preparation procedure and materials were the same as in example 1. SWNTs prepared in comparative example 3 were designated SWNTs-6.
The structural data of the catalysts obtained in example 1 and comparative example 3 are detailed in Table 2
Table 2N 2 desorption standard data for the catalyst obtained in example 1
| BET(m 2 g) | Kong Gu (cm) 3 /g) | Average pore diameter (nm) | |
| Cat-1 | 93.1 | 0.39 | 17.2 |
| Cat-6 | 62.9 | 0.208 | 13.9 |
As can be seen from Table 2, compared with the conventional impregnation method, the catalyst prepared by the preparation method provided by the invention has higher specific surface area and better pore structure, and can provide more growth sites for the preparation of single carbon nanotubes.
Comparative example 4
SWNTs preparation: placing 0.5g Cat-1 catalyst in a quartz reaction tube with the inner diameter of 16mm, introducing 100sccm argon, and heating to the reaction temperature of 800 ℃ for 60 min; introducing H 2 Mixed with Ar, wherein H 2 The concentration is 10%, the mixture is kept for 30min, and 500sccm methane and H are introduced 2 Argon gas mixture, wherein the concentration of methane is 30%, H 2 The concentration is 10%, and the SWNTs growth reaction is started; after 60min, the reaction gas is closed, heating is stopped, and 100sccm Ar is kept to be cooled to room temperature; the product was removed and then purified to give single walled carbon nanotubes, designated SWNTs-7.
Comparative example 5
Comparative example 5 the procedure and materials used for preparing the catalyst were the same as in example 1, except that the catalyst calcination temperature in comparative example 5 was 450 c and the remaining procedure and materials used for preparing the catalyst were the same as in example 1. The catalyst prepared in comparative example 5 was designated Cat-8.
SWNTs preparation: comparative example 5 the SWNTs preparation procedure and materials were the same as in example 1 except that Cat-8 was used as catalyst in comparative example 5 and the remaining SWNTs preparation procedure and materials were the same as in example 1. SWNTs prepared in comparative example 5 were designated SWNTs-8.
Comparative example 6
Comparative example 6 the procedure and materials used for preparing the catalyst were the same as in example 1, except that comparative example 6 was calcined at 500 c and the remaining procedure and materials used for preparing the catalyst were the same as in example 1. The catalyst prepared in comparative example 6 was designated Cat-9.
SWNTs preparation: comparative example 6 the SWNTs preparation procedure and materials were the same as in example 1 except that Cat-9 was used as catalyst in comparative example 6 and the remaining SWNTs preparation procedure and materials were the same as in example 1. SWNTs prepared in comparative example 6 were designated SWNTs-9.
Comparative example 7
SWNTs preparation: comparative example 7 the SWNTs preparation procedure and materials were selected as in example 1 except that the water vapor concentration was 2000ppm and the remaining SWNTs preparation procedure and materials were selected as in example 1. SWNTs prepared in comparative example 7 were designated SWNTs-10.
Comparative example 8
SWNTs preparation: placing 0.5g Cat-1 catalyst in a quartz reaction tube with the inner diameter of 16mm, introducing 100sccm argon, and heating to the reaction temperature of 800 ℃ for 60 min; introducing 500sccm methane and argon gas mixture, wherein the methane concentration is 30%, and starting SWNTs growth reaction; after 60min, the reaction gas is closed, heating is stopped, and 100sccmAr is kept to be cooled to room temperature; the product was removed and then purified to give single walled carbon nanotubes, designated SWNTs-11.
Performance tests are carried out on SWNTs-1, SWNTs-2, SWNTs-3, SWNTs-4, SWNTs-5, SWNTs-6, SWNTs-7, SWNTs-8, SWNTs-9, SWNTs-10 and SWNTs-11 prepared in examples 1 to 3, so as to obtain the carbon yield and the purity of SWNTs respectively, wherein the specific results are shown in Table 3:
TABLE 3 results for SWNTs obtained in examples 1-3, comparative examples 1-8
| Sample of | SWNTs | SWNTs carbon yield (%) | SWNTs purity (%) |
| Example 1 | SWNTs-1 | 33.5 | 98.7 |
| Example 2 | SWNTs-2 | 32.9 | 97.4 |
| Example 3 | SWNTs-3 | 31.2 | 95.5 |
| Comparative example 1 | SWNTs-4 | 30.5 | 89.1 |
| Comparative example 2 | SWNTs-5 | 28.8 | 80.6 |
| Comparative example 3 | SWNTs-6 | 20.8 | 85.7 |
| Comparative example 4 | SWNTs-7 | 9.8 | 59.7 |
| Comparative example 5 | SWNTs-8 | 25.9 | 91.3 |
| Comparative example6 | SWNTs-9 | 12.6 | 84.6 |
| Comparative example 7 | SWNTs-10 | 17.1 | 76.6 |
| Comparative example 8 | SWNTs-11 | 29.4 | 63.4 |
As shown in Table 3, the carbon yield of SWNTs prepared by the method of the present invention can reach 33.5%, and the purity of SWNTs can reach 98.7%, so that the method provided by the present invention is favorable for growing SWNTs with high quality and high yield. While comparing the catalyst of example 1 with the results of other examples or comparative examples, the following conclusions can be drawn: (1) Comparing example 1 with comparative examples 1-2, it can be seen that a better carbon yield and purity can be obtained by the micro Mo doping, because Mo and Fe at low concentrations form an iron molybdate structure, are more stable at high temperature and become structure aids between Fe, avoiding the growth and aggregation of Fe, resulting in better SWNTs quality, whereas when Mo content is too high, fe and Mo are present separately, respectively, the active component particles tend to become larger at high temperature, yielding more MWNTs. (2) Compared with comparative example 3, the catalyst prepared by the method of the invention has better microstructure, improves sufficient active sites and growth space for mass growth of SWNTs, and can realize large-scale preparation of SWNTs. (3) Comparative example 4 uses H 2 As an etchant, it can be seen from FIG. 4 that the bundles of the obtained carbon nanotubes are fewer, and the productivity is low because of H 2 Not only can play a role in etching, but also can destroy the original catalysisA reagent structure; comparative example 7 with 2000ppm of etchant H 2 O, it can be seen from FIG. 5 that the morphology of the resulting carbon nanotubes is not uniform due to the low concentration of H 2 O acts on the catalytic interface to directly influence the growth of SWNTs, thereby being beneficial to etching disordered carbon. However, higher concentrations of H 2 O can functionalize SWNTs, preferentially etch small pipe diameter SWNTs, gradually etch MWNTs, and form more defects and impurities. Comparative example 8 no etchant was added and the presence of a large amount of amorphous carbon resulted in a significant decrease in purity. (4) It is apparent from the products obtained in comparative examples 5 to 6 that the catalyst obtained by increasing the calcination temperature is significantly reduced in catalytic performance, which may be disadvantageous in that the high-temperature calcination is disadvantageous in forming the iron molybdate structure.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications to the above would be obvious to those of ordinary skill in the art, without departing from the spirit and scope of the present invention. The scope of the invention is therefore intended to be indicated by the appended claims.
Claims (11)
1. A method for preparing a trace molybdenum doped iron-based catalyst, which is characterized by comprising the following steps:
s1: mixing soluble molybdenum salt and an initiator and dissolving the mixture in water to obtain a precursor solution;
s2: adding soluble ferric salt, soluble magnesium salt and an auxiliary agent into the precursor solution obtained in the step S1, stirring and dissolving, adding a silicon oxide carrier and an aluminum oxide carrier, and stirring uniformly to obtain uniform and sticky slurry;
s3: drying, grinding and roasting the uniform and sticky slurry obtained in the step S2 at 300-400 ℃ to obtain the molybdenum-doped iron-based catalyst;
the molar ratio of the iron atoms in the soluble ferric salt to the molybdenum atoms in the soluble molybdenum salt is (25-60): 1; the initiator is selected from urea; the auxiliary agent is at least one selected from citric acid and sodium citrate.
2. The method according to claim 1, wherein the molar ratio of the iron atoms in the soluble iron salt to the magnesium atoms in the soluble magnesium salt is (20-30): 1.
3. The preparation method according to claim 1, wherein the soluble iron salt is at least one selected from the group consisting of ferric chloride, ferric nitrate and ferric sulfate, the soluble molybdenum salt is at least one selected from the group consisting of ammonium molybdate and sodium molybdate, and the soluble magnesium salt is at least one selected from the group consisting of magnesium chloride, magnesium nitrate and magnesium sulfate.
4. The preparation method according to claim 1, wherein the mass ratio of the silica to the alumina carrier is 3-9:1.
5. The preparation method according to claim 4, wherein the mass ratio of the silica to the alumina carrier is 4:1.
6. The method according to claim 1, wherein the firing temperature is 300 to 400 ℃ and the firing time is 2 to 6 hours.
7. A molybdenum-doped iron-based catalyst obtainable by the process according to claim 1, characterized in that the catalyst comprises an active component and a support, the active component comprising a main active component and a co-active component, the main active component being iron and the co-active component being molybdenum, wherein the iron content of the catalyst is 2-10wt%, and the molar ratio of iron atoms to molybdenum atoms in the catalyst is (25-60): 1, the carrier is silicon oxide and aluminum oxide.
8. The catalyst of claim 7, wherein the iron content of the catalyst is 4-6wt%.
9. The catalyst according to claim 7, characterized in that the particle size of the active component FeMo in the catalyst is 15-25nm.
10. The catalyst according to claim 7, wherein the mass ratio of the carrier silica to alumina is 3 to 9:1.
11. A method for preparing single-walled carbon nanotubes, the method comprising the steps of:
s1: placing the catalyst prepared by the preparation method of any one of claims 1 to 6 or the catalyst of any one of claims 7 to 10 in a reaction device, and heating;
s2: adding methane containing water vapor and inert gas for reaction, and purifying to obtain the single-walled carbon nanotube.
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