CN112958126B - Iron-cobalt catalyst for preparing carbon nano tube and preparation method and application thereof - Google Patents
Iron-cobalt catalyst for preparing carbon nano tube and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 59
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 title claims abstract description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- 229910052742 iron Inorganic materials 0.000 claims abstract description 30
- 239000010941 cobalt Substances 0.000 claims abstract description 29
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 23
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001567 cementite Inorganic materials 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims description 35
- 238000010438 heat treatment Methods 0.000 claims description 34
- 239000000843 powder Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 20
- 239000008103 glucose Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 239000012065 filter cake Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 10
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 10
- 239000012141 concentrate Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 10
- 238000001914 filtration 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000011852 carbon nanoparticle Substances 0.000 abstract 1
- 239000002109 single walled nanotube Substances 0.000 description 5
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000001241 arc-discharge method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/51—
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- 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
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- 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
- C01B2202/22—Electronic properties
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The application discloses an iron-cobalt catalyst for preparing carbon nanotubes, a preparation method and application thereof, wherein the catalyst comprises the following components: iron source in parts by weight: cobalt source= (2-8): 10; the iron source is iron carbide; the cobalt source is spherical carbon-loaded cobalt oxide; the catalyst is prepared by mechanically mixing an iron source with a cobalt source. The iron carbide in the catalyst component has high dispersibility and rich pore structure, and the surface of the catalyst component has more N, O functional groups, so that the carbon nano-particles can be effectively prevented from generating Wen Tuanju in the process of generating the carbon nano-tubes in a specific environment; the catalyst spherical carbon loaded cobalt oxide is highly dispersed on the spherical carbon matrix, and the particles are controllable, so that the problem of agglomeration of carbon particles in the growth process can be avoided in the preparation process of the carbon nano tube, and the catalyst spherical carbon loaded cobalt oxide is suitable for preparing the carbon nano tube with thin wall and small particle size; the iron-cobalt based catalyst helps to increase the electrical and mechanical properties of the carbon nanotubes.
Description
Technical Field
The application relates to the technical field of catalyst synthesis, in particular to an iron-cobalt catalyst for preparing carbon nanotubes, a preparation method and application thereof.
Background
The preparation method of the carbon nano tube is reported, thereby causing the hot trend of the carbon nano tube research and promoting the rapid development of nano technology. The carbon nanotubes are divided into single-walled carbon nanotubes and multi-walled carbon nanotubes by the structural characteristics, wherein the single-walled carbon nanotubes have various potential application values, have unique structural characteristics, such as large length-diameter ratio, few structural defects, small end curvature radius and the like, so that the single-walled carbon nanotubes show excellent mechanical, electrical and magnetic properties and are widely applied to electron field emission, microfluidic films, nano-electronic devices and the like. The array type carbon nano tube is formed by the arrangement mode of the carbon nano tube monomers, has the characteristics of good orientation performance, large growth density, regular orientation, arrangement and the like, and is suitable for various high and new technical fields such as field emission, electrode materials, radiating fins, nano sensors and the like.
Currently, methods for preparing carbon nanotubes mainly include an arc discharge method, a laser evaporation method and a chemical vapor deposition method. The method for preparing the carbon nano tube by arc discharge or laser evaporation has higher reaction temperature and relatively high process requirement. The chemical vapor deposition method has the advantages of lower working temperature (less than 800 ℃), simpler process and equipment, lower cost, controllable growth of carbon tubes and the like, thereby replacing the methods of an arc discharge method, a laser evaporation method and the like, being used for semi-industrialized and industrialized production and meeting the industrial requirements on carbon nano tube composite materials.
The key point of the method for synthesizing the carbon nano tube by adopting the chemical vapor deposition method is that the preparation and selection of the catalyst can influence the structure and the property of the finally obtained carbon nano tube to different degrees, the selectivity and the dispersion performance of the catalyst are particularly important for controlling the growth morphology of the carbon nano tube, the diameter and the chirality of the single-wall carbon nano tube are greatly influenced, the chiral control of the carbon nano tube is generally realized at about 600 ℃ at present, the growth temperature is improved, the growth speed of the carbon nano tube is forceful, and when the growth temperature is improved, the chiral distribution of the carbon nano tube is widened by the agglomeration of catalyst particles. Therefore, the catalyst is important to prepare small-diameter single-wall carbon nanotubes with consistent structure and narrow chiral distribution under the condition of higher temperature; and is beneficial to the formation of the array type carbon nano tube structure.
Therefore, it is desirable to provide an iron-cobalt-based catalyst for preparing carbon nanotubes, a preparation method and use thereof, so as to obtain a catalyst having stability and dispersity under higher temperature conditions, and preventing high-temperature agglomeration during the growth of carbon nanotubes, so as to overcome the above problems.
Disclosure of Invention
In order to solve the problems, the embodiment of the application provides an iron-cobalt catalyst for preparing carbon nanotubes, and a preparation method and application thereof, and the aim of the application is realized by the following technical scheme:
an iron-cobalt-based catalyst for preparing carbon nanotubes, the catalyst comprising: iron source in parts by weight: cobalt source= (2-8): 10;
the iron source is iron carbide prepared by a melting method;
the cobalt source is spherical carbon-supported cobalt oxide.
The preparation method of the iron-cobalt catalyst for preparing the carbon nano tubes is characterized in that the catalyst is prepared by mechanically mixing an iron source and a cobalt source.
The preparation method of the iron-cobalt catalyst for preparing the carbon nano tube comprises the following steps of:
step S 1 : firstly, glucose, urea and distilled water are mixed according to the solid-to-liquid ratio of 1-4:2-6:100 g/ml, and under the conditions that the reaction temperature is 145-165 ℃ and the stirring speed is 500-1200 rpm, the completely clarified mixed solution M is obtained 1 ；
Step S 2 : go to step S 1 Mixed solution M 1 Adding ferric nitrate with the concentration of 0.05-0.15 mol/l, stirring at the stirring speed of 400-800 rpm until the mixed solution does not have obvious bubbles, thus obtaining the mixed solution M 2 ；
Step S 3 : step S is carried out 2 The mixed solution M obtained in (3) 2 Transferring into a baking oven, drying at 135-185 ℃ for 12-24 h to obtain black powder, ball milling the black powder to 220-360 meshes to obtain powder M 3 ；
Step S 4 : step S is carried out 3 Powder M obtained in (3) 3 Transferring the mixture into a tubular roasting furnace, and carrying out two-stage heating roasting under the atmosphere of high-purity nitrogen bubbling to obtain an iron source of the iron carbide.
The preparation method of the iron-cobalt catalyst for preparing the carbon nano tubes comprises the following steps of 4 Heating up in the first stage: heating from room temperature to 380-420 ℃ at a heating rate of 1-3 ℃/min, and then keeping the roasting temperature for roasting for 30-60 min; and (3) two-stage heating: after rising to 745-755 ℃ at a heating rate of 2-5 ℃/min, the roasting is kept at the roasting temperature for 1.5-2.5 h.
The preparation method of the iron-cobalt catalyst for preparing the carbon nano tube comprises the following steps of:
step L 1 : preparing spherical carbon;
step L 2 : in step L 1 The spherical carbon obtained in the step (a) is oxidized by being carried thereonCobalt prepares the cobalt source.
The preparation method of the iron-cobalt catalyst for preparing the carbon nano tube comprises the step L 1 The preparation process of the medium spherical carbon comprises the following steps:
step P 1 : glucose and distilled water are dissolved for 10 to 30 minutes under the action of ultrasonic wave according to the solid-to-liquid ratio of 0.2 to 0.3:1g/ml, and the glucose solution N is obtained 1 ；
Step P 2 : step P 1 Glucose solution N obtained in (a) 1 Transferring into a concentration reaction kettle, crystallizing and concentrating for 8-12 h at 175-190 ℃ to obtain colloidal concentrate N 2 ；
Step P 3 : step P 2 The gel-like concentrate N is obtained 2 Washing with 15-30% concentration alcohol solution, suction filtering to obtain filter cake N 3 ；
Step P 4 : filter cake N 3 Transferring into a baking oven, baking at 105-115 ℃ for 8-12 h, ball milling to 200-240 meshes to obtain powder N 4 ；
Step P 5 : step P 4 Powder N obtained in (3) 4 Transferring into a tube roasting furnace, and roasting at a temperature increased under the atmosphere of high-purity nitrogen to obtain spherical carbon N 5 。
The preparation method of the iron-cobalt catalyst for preparing the carbon nano tube comprises the step P 5 Middle powder N 4 Roasting at 750-820 deg.c for 1.5-2.5 hr.
The preparation method of the iron-cobalt catalyst for preparing the carbon nano tube comprises the step L 2 The preparation process of the medium spherical carbon-supported cobalt oxide comprises the following steps:
step Q 1 : cobalt acetylacetonate and spherical carbon N 5 The mixture is mixed with the kamine according to the solid-to-liquid ratio of (0.005-0.015) to (0.01-0.02) 1, and the mixture is placed in a flask and dispersed for 10-30 min under the action of ultrasonic wave to obtain clear mixed solution W 1 ；
Step Q 2 : step Q 1 Is filled with mixed solution W 1 The flask of (2) is placed in an oil bath pot, and the temperature is raised to 185-195 ℃ under the conditions of reflux stirring and heating rate of 2-10 ℃/min, and the reaction temperature is kept for 0.5-1.0h; cooling to room temperature under reflux stirring to obtain solid powder W 2 ；
Step Q 3 : step Q 2 The fixed powder W obtained in (a) 2 Washing with 15-30% concentration ethanol solution for 5-8 times, suction filtering to obtain filter cake W 3 ；
Step Q 4 : step Q 3 The filter cake W obtained in (3) 3 Transferring the mixture into an oven, and drying the mixture at the drying temperature of 55-75 ℃ for 6-12 hours to obtain the cobalt source of the spherical carbon supported cobalt oxide.
The preparation method of the iron-cobalt catalyst for preparing the carbon nano tube comprises the step P 1 Or step Q 1 The working frequency of the medium ultrasonic wave is 15-30 kHz, and the working density is 0.2-1.5 Wcm -2 。
The application of the iron-cobalt catalyst for preparing the carbon nano tube is that the iron-cobalt catalyst is used for preparing the array type thin-walled carbon nano tube.
Compared with the prior art, the embodiment of the application at least has the following beneficial effects:
1. in the cementite iron carbide catalyst prepared by adopting the melting method, the iron carbide particles have high dispersibility, the iron carbide catalyst has rich pore structures, and the surface of the iron carbide catalyst has more N, O functional groups, so that the problem of agglomeration of nano carbon particles in the process of generating carbon nano tubes can be effectively prevented in a specific environment, and the catalytic performance of the catalyst is improved;
2. the application adopts the spherical carbon to load the cobalt oxide to realize the high dispersion on the spherical carbon matrix, the particles are controllable, the particle size of the growth of the cobalt oxide particles is controlled by improving the temperature rising rate, and the agglomeration problem of the carbon particles in the growth process can be avoided by controlling the reduction process in the preparation process of the carbon nano tube, so that the application is suitable for the preparation of the carbon nano tube with thin wall and small particle size.
3. When the iron-cobalt catalyst is used for preparing the array type thin-walled carbon nanotubes, part of catalyst particles can be used for filling the iron atom carbon nanotubes by controlling the growth conditions of the carbon nanotubes, so that the conductive performance and the mechanical performance of the carbon nanotubes can be improved.
Drawings
FIG. 1 is an XRD pattern of a sample of iron carbide catalyst of varying supported iron content (25-0.05 mol/l iron nitrate; 35-0.075mol/l iron nitrate; 45-0.1mlo/l;55-0.125mol/l;65-0.15 mol/l) in an embodiment of the application;
FIG. 2 shows XRD patterns (2-2 ℃/min;5-5 ℃/min;8-8 ℃/min;10-10 ℃/min) of cobalt oxide samples under different heating rates in the embodiment of the application;
FIG. 3 is an SEM image of iron carbide catalysts of samples of different supported iron content in examples of the present application (a and b:0.05mol/l iron nitrate; c:0.075mol/l iron nitrate; d:0.1mlo/l; e:0.125mol/l; f:0.15 mol/l);
FIG. 4 is an SEM image of samples of spherical carbon-supported cobalt oxide at different heating rates (a: 2 ℃/min; b:5 ℃/min; c:8 ℃/min; d:10 ℃/min) in an embodiment of the application.
Detailed Description
The application is further described in connection with the following detailed description. It should be understood by those skilled in the art that these embodiments are merely for explaining the technical principles of the present application, and are not intended to limit the scope of the present application.
Example 1:
an iron-cobalt-based catalyst for preparing carbon nanotubes, the catalyst comprising: iron source in parts by weight: cobalt source = 2:10; the iron source is iron carbide prepared by a melting method; the cobalt source is spherical carbon-supported cobalt oxide. The iron-cobalt catalyst is used for preparing the array type thin-walled carbon nanotube.
Example 2:
an iron-cobalt-based catalyst for preparing carbon nanotubes, the catalyst comprising: iron source in parts by weight: cobalt source = 8:10; the iron source is iron carbide prepared by a melting method; the cobalt source is spherical carbon-supported cobalt oxide. The iron-cobalt catalyst is used for preparing the array type thin-walled carbon nanotube.
Example 3:
an iron-cobalt-based catalyst for preparing carbon nanotubes, the catalyst comprising: iron source in parts by weight: cobalt source = 5:10; the iron source is iron carbide prepared by a melting method; the cobalt source is spherical carbon-supported cobalt oxide. The iron-cobalt catalyst is used for preparing the array type thin-walled carbon nanotube.
Example 4:
a preparation method of an iron-cobalt catalyst for preparing carbon nanotubes, wherein the catalyst is prepared by mechanically mixing an iron source and a cobalt source in a proportioning amount:
wherein, the preparation of the iron source comprises the following steps:
step S 1 : glucose, urea and distilled water are firstly mixed according to the solid-to-liquid ratio of 1:2:100g/ml, and under the conditions that the reaction temperature is 145 ℃ and the stirring speed is 800rpm, the completely clarified mixed solution M is obtained 1 ；
Step S 2 : go to step S 1 Mixed solution M 1 Adding ferric nitrate with the concentration of 0.05mol/l, and stirring at the stirring speed of 600rpm until no obvious bubbles appear in the mixed solution to obtain a mixed solution M 2 ；
Step S 3 : step S is carried out 2 The mixed solution M obtained in (3) 2 Transferring into an oven, drying at 160deg.C for 12 hr to obtain black powder, ball milling to 220 mesh to obtain powder M 3 ；
Step S 4 : step S is carried out 3 Powder M obtained in (3) 3 Transferring to a tube roasting furnace, and carrying out two-stage heating roasting under the atmosphere of high-purity nitrogen; wherein, one section heats up: heating from room temperature to 380 ℃ at a heating rate of 1 ℃/min, and then keeping the roasting temperature for 30min; and (3) two-stage heating: after the temperature rising rate of 2 ℃/min is increased to 750 ℃, the roasting temperature is kept for roasting for 1.5 hours, and then the iron source of the iron carbide can be obtained.
Wherein, the preparation of the cobalt source comprises the following steps:
step L 1 : the preparation process of the spherical carbon comprises the following steps:
step P 1 : glucose and distilled water are mixed according to the solid-to-liquid ratio of 0.2:1g/ml, and the working density is 0.2Wcm at the ultrasonic working frequency of 20kHz -2 Dissolving under the condition for 10min to obtain glucose solution N 1 ；
Step P 2 : step P 1 Glucose solution N obtained in (a) 1 Transferring into a concentration reaction kettle, crystallizing and concentrating for 8h at 175 ℃ to obtain colloidal concentrate N 2 ；
Step P 3 : step P 2 The gel-like concentrate N is obtained 2 Washing with 15% ethanol solution, and suction filtering to obtain filter cake N 3 ；
Step P 4 : filter cake N 3 Transferring into an oven, drying at 105deg.C for 8 hr, ball milling to 200 mesh to obtain powder N 4 ；
Step P 5 : step P 4 Powder N obtained in (3) 4 Transferring into a tube roasting furnace, heating and roasting under the atmosphere of high-purity nitrogen, wherein the roasting temperature is 750 ℃, and roasting for 1.5h at the roasting temperature to obtain spherical carbon N 5 。
Step L 2 : the preparation process of the spherical carbon-supported cobalt oxide comprises the following steps:
step Q 1 : cobalt acetylacetonate and spherical carbon N 5 The mixture and the kamine are placed in a flask according to the solid-to-liquid ratio of 0.005:0.01:1, and the working density is 0.2Wcm at the ultrasonic working frequency of 20kHz -2 Dispersing for 10min to obtain clear mixed solution W 1 ；
Step Q 2 : step Q 1 Is filled with mixed solution W 1 The flask of (2) is placed in an oil bath pot, and the temperature is raised to 185 ℃ under the conditions of reflux stirring and 2 ℃/min heating rate, and the reaction temperature is kept for 0.5h; cooling to room temperature under reflux stirring to obtain solid powder W 2 ；
Step Q 3 : step Q 2 The fixed powder W obtained in (a) 2 Washing with 15% ethanol solution for 5 times, and suction filtering to obtain filter cake W 3 ；
Step Q 4 : step Q 3 The filter cake W obtained in (3) 3 Transferring into an oven, and drying under the conditions that the drying temperature is 55 ℃ and the drying time is 6 hours to obtain the cobalt source of the spherical carbon loaded cobalt oxide.
Example 5:
a preparation method of an iron-cobalt catalyst for preparing carbon nanotubes, wherein the catalyst is prepared by mechanically mixing an iron source and a cobalt source in a proportioning amount:
wherein, the preparation of the iron source comprises the following steps:
step S 1 : glucose, urea and distilled water are firstly mixed according to the solid-to-liquid ratio of 4:6:100g/ml, and the completely clarified mixed solution M is obtained under the conditions that the reaction temperature is 165 ℃ and the stirring speed is 1200rpm 1 ；
Step S 2 : go to step S 1 Mixed solution M 1 Adding ferric nitrate with the concentration of 0.15mol/l, and stirring at the stirring speed of 800rpm until no obvious bubbles appear in the mixed solution to obtain a mixed solution M 2 ；
Step S 3 : step S is carried out 2 The mixed solution M obtained in (3) 2 Transferring into an oven, drying at 185 deg.C for 24 hr to obtain black powder, ball milling to 360 mesh to obtain powder M 3 ；
Step S 4 : step S is carried out 3 Powder M obtained in (3) 3 Transferring to a tube roasting furnace, and carrying out two-stage heating roasting under the atmosphere of high-purity nitrogen; wherein, one section heats up: heating from room temperature to 420 ℃ at a heating rate of 3 ℃/min, and then keeping a roasting temperature for roasting for 60min; and (3) two-stage heating: after the temperature rise rate of 5 ℃/min is increased to 755 ℃, the roasting temperature is kept for 2.5 hours, and then the iron source of the iron carbide can be obtained.
Wherein, the preparation of the cobalt source comprises the following steps:
step L 1 : the spherical carbon preparation process comprises the following stepsThe method comprises the following steps:
step P 1 : glucose and distilled water are mixed according to the solid-to-liquid ratio of 0.3:1g/ml, and the working density is 1.5Wcm at the ultrasonic working frequency of 30kHz -2 Dissolving under the condition for 30min to obtain glucose solution N 1 ；
Step P 2 : step P 1 Glucose solution N obtained in (a) 1 Transferring into a concentration reaction kettle, crystallizing and concentrating for 12h at 190 ℃ to obtain colloidal concentrate N 2 ；
Step P 3 : step P 2 The gel-like concentrate N is obtained 2 Washing with 30% ethanol solution, and vacuum filtering to obtain filter cake N 3 ；
Step P 4 : filter cake N 3 Transferring into an oven, drying at 115deg.C for 12 hr, ball milling to 240 mesh to obtain powder N 4 ；
Step P 5 : step P 4 Powder N obtained in (3) 4 Transferring into a tube roasting furnace, heating and roasting under the atmosphere of high-purity nitrogen, wherein the roasting temperature is 820 ℃, and roasting for 2.5h at the roasting temperature to obtain spherical carbon N 5 。
Step L 2 : the preparation process of the spherical carbon-supported cobalt oxide comprises the following steps:
step Q 1 : cobalt acetylacetonate and spherical carbon N 5 The mixture and the kamine are placed in a flask according to the solid-to-liquid ratio of 0.015:0.02:1, and the working density is 1.5Wcm at the ultrasonic working frequency of 30kHz -2 Dispersing for 30min to obtain clear mixed solution W 1 ；
Step Q 2 : step Q 1 Is filled with mixed solution W 1 Placing the flask in an oil bath pot, heating to 195 ℃ under the conditions of reflux stirring and heating rate of 10 ℃/min, and keeping the reaction temperature for 1.0h; cooling to room temperature under reflux stirring to obtain solid powder W 2 ；
Step Q 3 : step Q 2 The fixed powder W obtained in (a) 2 Adopting 30% concentrationWashing the ethanol solution with the concentration for 8 times, and filtering to obtain a filter cake W 3 ；
Step Q 4 : step Q 3 The filter cake W obtained in (3) 3 Transferring into an oven, and drying under the conditions that the drying temperature is 75 ℃ and the drying time is 12 hours to obtain the cobalt source of the spherical carbon loaded cobalt oxide.
Example 6:
a preparation method of an iron-cobalt catalyst for preparing carbon nanotubes, wherein the catalyst is prepared by mechanically mixing an iron source and a cobalt source in a proportioning amount:
wherein, the preparation of the iron source comprises the following steps:
step S 1 : glucose, urea and distilled water are firstly mixed according to the solid-to-liquid ratio of 2.5:4:100g/ml, and the completely clarified mixed solution M is obtained under the conditions that the reaction temperature is 155 ℃ and the stirring speed is 800rpm 1 ；
Step S 2 : go to step S 1 Mixed solution M 1 Adding ferric nitrate with the concentration of 0.1mol/l, and stirring at the stirring speed of 600rpm until no obvious bubbles appear in the mixed solution to obtain a mixed solution M 2 ；
Step S 3 : step S is carried out 2 The mixed solution M obtained in (3) 2 Transferring into a baking oven, drying at 160deg.C for 18 hr to obtain black powder, ball milling the black powder to 260 mesh to obtain powder M 3 ；
Step S 4 : step S is carried out 3 Powder M obtained in (3) 3 Transferring to a tube roasting furnace, and carrying out two-stage heating roasting under the atmosphere of high-purity nitrogen; wherein, one section heats up: heating from room temperature to 400 ℃ at a heating rate of 2 ℃/min, and then keeping the roasting temperature for roasting for 45min; and (3) two-stage heating: after the temperature rising rate of 4 ℃/min is increased to 750 ℃, the roasting temperature is kept for 2.0h, and then the iron source of the iron carbide can be obtained.
Wherein, the preparation of the cobalt source comprises the following steps:
step L 1 : the preparation process of the spherical carbon comprises the following steps:
step P 1 : glucose and distilled water are mixed according to the solid-to-liquid ratio of 0.25:1g/ml, and the working density is 1.0Wcm at the ultrasonic working frequency of 20kHz -2 Dissolving under the condition for 20min to obtain glucose solution N 1 ；
Step P 2 : step P 1 Glucose solution N obtained in (a) 1 Transferring into a concentration reaction kettle, crystallizing and concentrating for 10h at 180 ℃ to obtain colloidal concentrate N 2 ；
Step P 3 : step P 2 The gel-like concentrate N is obtained 2 Washing with 20% ethanol solution, and suction filtering to obtain filter cake N 3 ；
Step P 4 : filter cake N 3 Transferring into a baking oven, drying at 110deg.C for 10 hr, ball milling to 220 mesh to obtain powder N 4 ；
Step P 5 : step P 4 Powder N obtained in (3) 4 Transferring into a tube roasting furnace, heating and roasting under the atmosphere of high-purity nitrogen, wherein the roasting temperature is 790 ℃, and roasting at the roasting temperature for 2.0h to obtain spherical carbon N 5 。
Step L 2 : the preparation process of the spherical carbon-supported cobalt oxide comprises the following steps:
step Q 1 : cobalt acetylacetonate and spherical carbon N 5 The mixture and the kamine are placed in a flask according to the solid-to-liquid ratio of 0.1:0.15:1, and the working density is 1.0Wcm at the ultrasonic working frequency of 20kHz -2 Dispersing for 20min to obtain clear mixed solution W 1 ；
Step Q 2 : step Q 1 Is filled with mixed solution W 1 The flask of (2) is placed in an oil bath pot, and the temperature is raised to 190 ℃ under the conditions of reflux stirring and 6 ℃/min heating rate, and the reaction temperature is kept for 1.0h; cooling to room temperature under reflux stirring to obtain solid powder W 2 ；
Step Q 3 : step Q 2 The fixed powder W obtained in (a) 2 Washing with 20% ethanol solution for 6 times, and vacuum filtering to obtainFilter cake W 3 ；
Step Q 4 : step Q 3 The filter cake W obtained in (3) 3 Transferring into an oven, and drying under the conditions that the drying temperature is 65 ℃ and the drying time is 9 hours to obtain the cobalt source of the spherical carbon loaded cobalt oxide.
The foregoing is merely a detailed description of the preferred embodiments of the application, but the scope of the application is not limited thereto, and any changes or substitutions that would be apparent to one skilled in the art within the scope of the present application should be included in the scope of the application.
Claims (6)
1. An iron-cobalt-based catalyst for preparing carbon nanotubes, characterized in that the catalyst comprises: iron source in parts by weight: cobalt source= (2-8): 10; the iron source is iron carbide prepared by a melting method; the cobalt source is spherical carbon-loaded cobalt oxide;
the preparation of the iron source comprises the following steps:
step S 1 : firstly, glucose, urea and distilled water are mixed according to the solid-to-liquid ratio of 1-4:2-6:100 g/ml, and under the conditions that the reaction temperature is 145-165 ℃ and the stirring speed is 500-1200 rpm, the completely clarified mixed solution M is obtained 1 ；
Step S 2 : go to step S 1 Mixed solution M 1 Adding ferric nitrate with the concentration of 0.05-0.15 mol/l, stirring at the stirring speed of 400-800 rpm until the mixed solution does not have obvious bubbles, thus obtaining the mixed solution M 2 ；
Step S 3 : step S is carried out 2 The mixed solution M obtained in (3) 2 Transferring into a baking oven, drying at 135-185 ℃ for 12-24 h to obtain black powder, ball milling the black powder to 220-360 meshes to obtain powder M 3 ；
Step S 4 : step S is carried out 3 Powder M obtained in (3) 3 Transferring the mixture into a tubular roasting furnace, and carrying out two-stage heating roasting under the atmosphere of high-purity nitrogen bubbling to obtain an iron source of iron carbide;
the preparation of the cobalt source comprises the following steps:
step L 1 : preparing spherical carbon;
step L 2 : in step L 1 Preparing a cobalt source by loading cobalt oxide on the spherical carbon obtained in the step (C);
said step L 1 The preparation process of the medium spherical carbon comprises the following steps:
step P 1 : glucose and distilled water are dissolved for 10 to 30 minutes under the action of ultrasonic wave according to the solid-to-liquid ratio of 0.2 to 0.3:1g/ml, and the glucose solution N is obtained 1 ；
Step P 2 : step P 1 Glucose solution N obtained in (a) 1 Transferring into a concentration reaction kettle, crystallizing and concentrating for 8-12 h at 175-190 ℃ to obtain colloidal concentrate N 2 ；
Step P 3 : step P 2 The gel-like concentrate N is obtained 2 Washing with 15-30% concentration alcohol solution, suction filtering to obtain filter cake N 3 ；
Step P 4 : filter cake N 3 Transferring into a baking oven, baking at 105-115 ℃ for 8-12 h, ball milling to 200-240 meshes to obtain powder N 4 ；
Step P 5 : step P 4 Powder N obtained in (3) 4 Transferring into a tube roasting furnace, and roasting at a temperature increased under the atmosphere of high-purity nitrogen to obtain spherical carbon N 5 ；
Said step L 2 The preparation process of the medium spherical carbon-supported cobalt oxide comprises the following steps:
step Q 1 : cobalt acetylacetonate and spherical carbon N 5 The mixture is mixed with the kamine according to the solid-to-liquid ratio of (0.005-0.015) to (0.01-0.02) 1, and the mixture is placed in a flask and dispersed for 10-30 min under the action of ultrasonic wave to obtain clear mixed solution W 1 ；
Step Q 2 : step Q 1 Is filled with mixed solution W 1 The flask of (2) is placed in an oil bath pot, and the temperature is raised to the temperature of between 2 and 10 ℃ per minute under the condition of reflux stirring and temperature rising rate185-195 ℃, and keeping the reaction temperature for 0.5-1.0h; cooling to room temperature under reflux stirring to obtain solid powder W 2 ；
Step Q 3 : step Q 2 The fixed powder W obtained in (a) 2 Washing with 15-30% concentration ethanol solution for 5-8 times, suction filtering to obtain filter cake W 3 ；
Step Q 4 : step Q 3 The filter cake W obtained in (3) 3 Transferring the mixture into an oven, and drying the mixture at the drying temperature of 55-75 ℃ for 6-12 hours to obtain the cobalt source of the spherical carbon supported cobalt oxide.
2. The method for preparing an iron-cobalt-based catalyst for preparing carbon nanotubes according to claim 1, wherein the catalyst is prepared by mechanically mixing an iron source and a cobalt source.
3. The method for preparing an iron-cobalt-based catalyst for preparing carbon nanotubes according to claim 1, wherein step S 4 Heating up in the first stage: heating from room temperature to 380-420 ℃ at a heating rate of 1-3 ℃/min, and then keeping the roasting temperature for roasting for 30-60 min; and (3) two-stage heating: after rising to 745-755 ℃ at a heating rate of 2-5 ℃/min, the roasting is kept at the roasting temperature for 1.5-2.5 h.
4. The method for preparing an iron-cobalt-based catalyst for preparing carbon nanotubes according to claim 1, wherein step P 5 Middle powder N 4 Roasting at 750-820 deg.c for 1.5-2.5 hr.
5. The method for preparing an iron-cobalt-based catalyst for preparing carbon nanotubes according to claim 1, wherein step P 1 Or step Q 1 The working frequency of the medium ultrasonic wave is 15-30 kHz, and the working density is 0.2-1.5 Wcm -2 。
6. Use of an iron-cobalt based catalyst for the preparation of carbon nanotubes according to claim 1, wherein the iron-cobalt based catalyst is used for the preparation of arrayed thin walled carbon nanotubes.
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