CN112958126A - 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
- Publication number
- CN112958126A CN112958126A CN202110217663.9A CN202110217663A CN112958126A CN 112958126 A CN112958126 A CN 112958126A CN 202110217663 A CN202110217663 A CN 202110217663A CN 112958126 A CN112958126 A CN 112958126A
- Authority
- CN
- China
- Prior art keywords
- iron
- cobalt
- temperature
- catalyst
- preparing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 57
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 title claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052742 iron Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000010941 cobalt Substances 0.000 claims abstract description 30
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 30
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
- 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 20
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims description 35
- 239000011259 mixed solution Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000012065 filter cake Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 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 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 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
- 238000010992 reflux Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 238000007664 blowing Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting 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
- CVXBEEMKQHEXEN-UHFFFAOYSA-N carbaryl Chemical compound C1=CC=C2C(OC(=O)NC)=CC=CC2=C1 CVXBEEMKQHEXEN-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 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
- 238000005406 washing Methods 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 238000007780 powder milling Methods 0.000 claims description 3
- 239000011363 dried mixture Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910017061 Fe Co Inorganic materials 0.000 claims 2
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 claims 2
- 239000002245 particle Substances 0.000 abstract description 13
- 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
- 229910021392 nanocarbon Inorganic materials 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000002109 single walled nanotube Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001241 arc-discharge method Methods 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
- 238000009776 industrial production Methods 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
Images
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
- 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
-
- B01J35/51—
-
- 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
- C01B2202/22—Electronic properties
Abstract
The invention discloses an iron-cobalt catalyst for preparing carbon nano-tubes, a preparation method and application thereof, wherein the catalyst comprises the following components in parts by weight: the iron source comprises the following components in parts by weight: 10 for cobalt source (2-8); the iron source is iron carbide; the cobalt source is spherical carbon-supported cobalt oxide; the catalyst is prepared by mechanically mixing an iron source and a cobalt source. The iron carbide in the catalyst component has high dispersibility and abundant pore structures, and the surface of the iron carbide has more N, O functional groups, so that the high-temperature agglomeration of nano carbon particles in the process of generating carbon nano tubes can be effectively prevented in a specific environment; the catalyst spherical carbon loaded cobalt oxide is highly dispersed on the spherical carbon substrate, the particles are controllable, and the problem of agglomeration of carbon particles in the growth process can be avoided in the preparation process of the carbon nano tube, so that the method is suitable for preparing the thin-wall carbon nano tube with small particle size; the iron-cobalt catalyst is helpful for increasing the electrical conductivity and mechanical properties of the carbon nano tube.
Description
Technical Field
The invention relates to the technical field of catalyst synthesis, in particular to an iron-cobalt catalyst for preparing a carbon nano tube, and a preparation method and application thereof.
Background
The preparation method of the carbon nano tube is reported, which causes the hot tide of the research of the carbon nano tube and promotes the rapid development of the nano technology. The carbon nano tube is divided into a single-walled carbon nano tube and a multi-walled carbon nano tube by the structural characteristics, wherein the single-walled carbon nano tube has multiple potential application values and 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 nano tube shows excellent mechanical, electrical and magnetic properties and is widely applied to electron field emission, microfluidic films, nano electronic devices and the like. The array carbon nano tube is formed by arranging the carbon nano tube monomers, has the characteristics of good orientation performance, large growth density, regular orientation and arrangement and the like, and is suitable for various high and new technical fields of field emission, electrode materials, radiating fins, nano sensors and the like.
At present, the methods for preparing carbon nanotubes mainly include arc discharge methods, laser evaporation methods and chemical vapor deposition methods. The method for preparing the carbon nano tube by arc discharge or laser evaporation requires higher reaction temperature and has higher process requirement. The chemical vapor deposition method has the advantages of low working temperature (less than 800 ℃), simple process and equipment, low cost, controllable growth of the carbon tube and the like, so that the method replaces methods such as an arc discharge method, a laser evaporation method and the like, is used for semi-industrial and industrial production, and meets the industrial requirement on the carbon nanotube composite material.
The key point of preparing and synthesizing the carbon nano tube by adopting the chemical vapor deposition method is the preparation and selection of the catalyst, the components, the appearance, the physicochemical properties and the like of the catalyst can influence the structure and the properties 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 appearance of the carbon nano tube, the influence on the diameter and the chirality of the single-walled carbon nano tube is huge, the chirality control of the carbon nano tube is generally realized at lower temperature of about 600 ℃, the growth speed of the carbon nano tube is powerful when the growth temperature is increased, but when the growth temperature is increased, the catalyst particles are agglomerated, so that the chirality distribution of the carbon nano tube is widened. Therefore, the catalyst is crucial to prepare the small-diameter single-walled carbon nanotube with consistent structure and narrow chiral distribution under the condition of high temperature; and is beneficial to the formation of the array carbon nanotube structure.
Therefore, it is desirable to provide an iron-cobalt based catalyst for preparing carbon nanotubes, a preparation method and a use thereof, so as to obtain a catalyst having stability and dispersity at a higher temperature, and preventing high-temperature agglomeration during the growth of the carbon nanotubes, so as to overcome the above problems.
Disclosure of Invention
In order to solve the above problems, embodiments of the present invention provide an iron-cobalt catalyst for preparing carbon nanotubes, a preparation method and a use thereof, and the purpose of the present invention is achieved by the following technical scheme:
an iron-cobalt based catalyst for the preparation of carbon nanotubes, the catalyst comprising: the iron source comprises the following components in parts by weight: 10 for cobalt source (2-8);
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 tube comprises the step of 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:
step S1: firstly, glucose, urea and distilled water are mixed according to a solid-to-liquid ratio of 1-4: 2-6: 100g/ml, and a completely clear mixed solution M is obtained under the conditions that the reaction temperature is 145-165 ℃ and the stirring speed is 500-1200 rpm1；
Step S2: to step S1Medium mixed solution M1Adding ferric nitrate with the concentration of 0.05-0.15 mol/l, stirring at the stirring speed of 400-800 rpm until no obvious bubbles emerge from the mixed solution, and obtaining a mixed solution M2；
Step S3: will step S2The mixed solution M obtained in (1)2Transferring the mixture into an oven, drying the mixture at the drying temperature of 135-185 ℃ for 12-24 h to obtain black powder, and ball-milling the black powder to 220-360 meshes to obtain powder M3；
Step S4: will step S3The powder M obtained in (1)3Transferring the mixture to a tubular roasting furnace, and carrying out secondary heating roasting under a high-purity nitrogen atmosphere to obtain the iron source of the iron carbide.
The preparation method of the iron-cobalt catalyst for preparing the carbon nano tube comprises the step S4Heating in the middle stage: heating the temperature 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) second-stage heating: after raising the temperature to 745-755 ℃ at the rate of 2-5 ℃/min, keeping the roasting temperature for roasting 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 L1: preparing spherical carbon;
step L2: in step L1And preparing a cobalt source by loading cobalt oxide on the spherical carbon obtained in the step (1).
The preparation method of the iron-cobalt catalyst for preparing the carbon nano tube comprises a step L1The preparation process of the medium spherical carbon comprises the following steps:
step P1: dissolving glucose and distilled water according to a solid-to-liquid ratio of 0.2-0.3: 1g/ml for 10-30 min under the action of ultrasonic waves to obtain a glucose solution N1；
Step P2: step P1The glucose solution N obtained in (1)1Transferring the mixture into a concentration reaction kettle, and crystallizing and concentrating for 8-12 h at the temperature of 175-190 ℃ to obtain a colloidal concentrate N2；
Step P3: step P2To obtain a colloidal concentrate N2Cleaning and suction-filtering by adopting an ethanol solution with the concentration of 15-30% to obtain a filter cake N3；
Step P4: filtering the filter cake N3Transferring the mixture into an oven, drying the mixture at the drying temperature of 105-115 ℃ for 8-12 h, and ball-milling the obtained dried mixture to 200-240 meshes to obtain powder N4；
Step P5: step P4Powder N obtained in (1)4Transferring to a tubular roasting furnace, and heating and roasting under the condition of blowing high-purity nitrogen atmosphere to obtain spherical carbon N5。
The preparation method of the iron-cobalt catalyst for preparing the carbon nano tube comprises the step P5Middle powder N4And roasting at 750-820 ℃ for 1.5-2.5 h while keeping the roasting temperature.
The preparation method of the iron-cobalt catalyst for preparing the carbon nano tube comprises a step L2The preparation process of the medium spherical carbon-supported cobalt oxide comprises the following steps:
step Q1: cobalt acetylacetonate and spherical carbon N5Placing the mixture and the Carbamine in a flask according to the solid-to-liquid ratio of (0.005-0.015): (0.01-0.02): 1, and dispersing for 10-30 min under the action of ultrasonic waves to obtain a clear mixed solution W1；
Step Q2: step Q1In which mixed solution W is contained1The flask is placed in an oil bath kettle, the temperature is raised to 185-195 ℃ under the conditions of reflux stirring and the temperature raising rate of 2-10 ℃/min, and the reaction temperature is kept for 0.5-1.0 h; cooling to room temperature under the condition of reflux stirring to obtain solid powder W2；
Step Q3: step Q2The fixed powder W obtained in (1)2Washing the filter cake for 5 to 8 times by adopting an ethanol solution with the concentration of 15 to 30 percent, and filtering the washed filter cake to obtain a filter cake W3；
Step Q4: step Q3The filter cake W obtained in (1)3And transferring the mixture into an oven, and drying the mixture at the drying temperature of 55-75 ℃ for 6-12 h 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 P1Or step Q1The medium ultrasonic wave has the working frequency of 15-30 kHz and the working density of 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-wall carbon nano tube.
Compared with the prior art, the embodiment of the invention at least comprises the following beneficial effects:
1. in the cementite iron carbide catalyst prepared by the melting method, the dispersibility of iron carbide particles is high, the iron carbide catalyst has a rich pore structure, 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 invention adopts spherical carbon loaded cobalt oxide to realize high dispersion on a spherical carbon substrate, the particles are controllable, the particle size of the cobalt oxide particles is controlled by improving the temperature rise 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 preparation method is suitable for preparing the thin-walled carbon nano tube with small particle size.
3. When the iron-cobalt catalyst is used for preparing the array thin-wall carbon nano tube, part of catalyst particles can realize the filling of the iron atom carbon nano tube by controlling the growth condition of the carbon nano tube, and the iron-cobalt catalyst is beneficial to increasing the electrical conductivity and the mechanical property of the carbon nano tube.
Drawings
FIG. 1 is an XRD (X-ray diffraction) pattern of iron carbide catalysts with different supported iron contents (25-0.05mol/l ferric nitrate; 35-0.075mol/l ferric nitrate; 45-0.1 mlo/l; 55-0.125 mol/l; 65-0.15mol/l) in the embodiment of the invention;
FIG. 2 is an XRD (X-ray diffraction) pattern of a cobalt oxide sample under different temperature rise rate conditions in the embodiment of the invention (2-2 ℃/min; 5-5 ℃/min; 8-8 ℃/min; 10-10 ℃/min);
FIG. 3 is SEM images of iron carbide catalysts of samples with different supported iron contents in the examples of the present invention (a and b:0.05mol/l ferric nitrate; c:0.075mol/l ferric nitrate; d:0.1 mlo/l; e:0.125 mol/l; f:0.15 mol/l);
FIG. 4 is SEM images (a:2 ℃/min; b:5 ℃/min; c:8 ℃/min; d:10 ℃/min) of samples of spherical carbon-supported cobalt oxide with different heating rates in the embodiment of the invention.
Detailed Description
The present invention will be further described with reference to the following embodiments. It should be understood by those skilled in the art that these embodiments are only for explaining the technical principle of the present invention, and are not intended to limit the scope of the present invention.
Example 1:
an iron-cobalt based catalyst for the preparation of carbon nanotubes, the catalyst comprising: the iron source comprises the following components 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 array thin-wall carbon nanotubes.
Example 2:
an iron-cobalt based catalyst for the preparation of carbon nanotubes, the catalyst comprising: the iron source comprises the following components 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 array thin-wall carbon nanotubes.
Example 3:
an iron-cobalt based catalyst for the preparation of carbon nanotubes, the catalyst comprising: the iron source comprises the following components 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 array thin-wall carbon nanotubes.
Example 4:
a method for preparing an iron-cobalt catalyst for preparing carbon nanotubes, the catalyst being prepared by mechanically mixing iron sources and cobalt sources in a ratio of:
wherein the preparation of the iron source comprises the following steps:
step S1: firstly, glucose, urea and distilled water are mixed according to the solid-to-liquid ratio of 1:2:100g/ml under the conditions that the reaction temperature is 145 ℃ and the stirring speed is 800rpm to obtain a completely clear mixed solution M1；
Step S2: to step S1Medium mixed solution M1Adding 0.05mol/l ferric nitrate, and stirring at 600rpm to obtain a mixed solutionNo obvious bubbles emerge to obtain a mixed solution M2；
Step S3: will step S2The mixed solution M obtained in (1)2Transferring into a drying oven, drying at 160 deg.C for 12 hr to obtain black powder, ball milling to 220 mesh to obtain powder M3；
Step S4: will step S3The powder M obtained in (1)3Transferring to a tubular roasting furnace, and carrying out secondary heating roasting under the condition of blowing high-purity nitrogen atmosphere; wherein, first-stage temperature rising: heating from room temperature to 380 ℃ at the heating rate of 1 ℃/min, and then keeping the roasting temperature for roasting for 30 min; and (3) second-stage heating: after the temperature is raised to 750 ℃ at the temperature raising rate of 2 ℃/min, the roasting temperature is kept for roasting for 1.5h, and the iron source of the iron carbide can be obtained.
Wherein the preparation of the cobalt source comprises the steps of:
step L1: the preparation process of the spherical carbon comprises the following steps:
step P1: mixing glucose and distilled water at solid-to-liquid ratio of 0.2:1g/ml, ultrasonic frequency of 20kHz, and working density of 0.2Wcm-2Dissolving for 10min under the condition to obtain glucose solution N1；
Step P2: step P1The glucose solution N obtained in (1)1Transferring to a concentration reaction kettle, crystallizing at 175 deg.C for 8 hr to obtain colloidal concentrate N2；
Step P3: step P2To obtain a colloidal concentrate N2Cleaning and filtering the mixture by adopting 15 percent ethanol solution to obtain a filter cake N3；
Step P4: filtering the filter cake N3Transferring into a drying oven, drying at 105 deg.C for 8 hr, ball milling to 200 mesh to obtain powder N4；
Step P5: step P4Powder N obtained in (1)4Transferring to a tubular roasting furnace, and roasting at high temperature under high-purity nitrogen atmosphereRoasting at 750 deg.C for 1.5 hr to obtain spherical carbon N5。
Step L2: the preparation process of the spherical carbon-supported cobalt oxide comprises the following steps:
step Q1: cobalt acetylacetonate and spherical carbon N5Placing the mixture and Carbamine in a flask according to a solid-to-liquid ratio of 0.005:0.01:1, and performing ultrasonic treatment at an ultrasonic working frequency of 20kHz and a working density of 0.2Wcm-2Dispersing for 10min under the condition to obtain clear mixed solution W1；
Step Q2: step Q1In which mixed solution W is contained1The flask is placed in an oil bath kettle, the temperature is raised to 185 ℃ under the conditions of reflux stirring and the temperature rise rate of 2 ℃/min, and the reaction temperature is kept for 0.5 h; cooling to room temperature under the condition of reflux stirring to obtain solid powder W2；
Step Q3: step Q2The fixed powder W obtained in (1)2Washing with 15% ethanol solution for 5 times, and vacuum filtering to obtain filter cake W3；
Step Q4: step Q3The filter cake W obtained in (1)3And transferring the mixture into an oven, and drying the mixture at the drying temperature of 55 ℃ for 6h to obtain the cobalt source of the spherical carbon-supported cobalt oxide.
Example 5:
a method for preparing an iron-cobalt catalyst for preparing carbon nanotubes, the catalyst being prepared by mechanically mixing iron sources and cobalt sources in a ratio of:
wherein the preparation of the iron source comprises the following steps:
step S1: firstly, glucose, urea and distilled water are mixed according to the solid-to-liquid ratio of 4:6:100g/ml under the conditions that the reaction temperature is 165 ℃ and the stirring speed is 1200rpm to obtain a completely clear mixed solution M1；
Step S2: to step S1Medium mixed solution M1Adding 0.15mol/l ferric nitrate, stirring at 800rpm until no obvious bubbles emerge to obtain mixed solution M2；
Step S3: will step S2The mixed solution M obtained in (1)2Transferring into a drying oven, drying at 185 deg.C for 24 hr to obtain black powder, ball milling to 360 mesh to obtain powder M3；
Step S4: will step S3The powder M obtained in (1)3Transferring to a tubular roasting furnace, and carrying out secondary heating roasting under the condition of blowing high-purity nitrogen atmosphere; wherein, first-stage temperature rising: heating from room temperature to 420 ℃ at a heating rate of 3 ℃/min, and keeping the roasting temperature for roasting for 60 min; and (3) second-stage heating: after the temperature rises to 755 ℃ at the rate of 5 ℃/min, the roasting temperature is kept for roasting for 2.5h, and the iron source of the iron carbide can be obtained.
Wherein the preparation of the cobalt source comprises the steps of:
step L1: the preparation process of the spherical carbon comprises the following steps:
step P1: mixing glucose and distilled water at solid-to-liquid ratio of 0.3:1g/ml, ultrasonic frequency of 30kHz, and working density of 1.5Wcm-2Dissolving for 30min under the condition to obtain glucose solution N1；
Step P2: step P1The glucose solution N obtained in (1)1Transferring to a concentration reaction kettle, crystallizing at 190 deg.C for 12 hr to obtain colloidal concentrate N2；
Step P3: step P2To obtain a colloidal concentrate N2Cleaning and filtering the mixture by adopting 30 percent ethanol solution to obtain a filter cake N3；
Step P4: filtering the filter cake N3Transferring into a drying oven, drying at 115 deg.C for 12 hr, ball milling to 240 mesh to obtain powder N4；
Step P5: step P4Powder N obtained in (1)4Transferring to a tubular roasting furnace, heating and roasting under blowing high-purity nitrogen atmosphere at 820 ℃, keeping the roasting temperature for 2.5h to obtain the final productSpherical carbon N5。
Step L2: the preparation process of the spherical carbon-supported cobalt oxide comprises the following steps:
step Q1: cobalt acetylacetonate and spherical carbon N5Placing the mixture and the Carbamine in a flask according to the solid-to-liquid ratio of 0.015:0.02:1, and performing ultrasonic treatment at the working frequency of 30kHz and the working density of 1.5Wcm-2Dispersing for 30min under the condition to obtain clear mixed solution W1；
Step Q2: step Q1In which mixed solution W is contained1The flask is placed in an oil bath kettle, the temperature is raised to 195 ℃ under the conditions of reflux stirring and the heating rate of 10 ℃/min, and the reaction temperature is kept for 1.0 h; cooling to room temperature under the condition of reflux stirring to obtain solid powder W2；
Step Q3: step Q2The fixed powder W obtained in (1)2Washing with 30% ethanol solution for 8 times, and vacuum filtering to obtain filter cake W3；
Step Q4: step Q3The filter cake W obtained in (1)3And (4) transferring the mixture into an oven, and drying the mixture at the drying temperature of 75 ℃ for 12h to obtain the cobalt source of the spherical carbon-supported cobalt oxide.
Example 6:
a method for preparing an iron-cobalt catalyst for preparing carbon nanotubes, the catalyst being prepared by mechanically mixing iron sources and cobalt sources in a ratio of:
wherein the preparation of the iron source comprises the following steps:
step S1: firstly, glucose, urea and distilled water are mixed according to the solid-to-liquid ratio of 2.5:4:100g/ml under the conditions that the reaction temperature is 155 ℃ and the stirring speed is 800rpm to obtain a completely clear mixed solution M1；
Step S2: to step S1Medium mixed solution M1Adding 0.1mol/l ferric nitrate, stirring at 600rpm until no obvious bubbles emerge to obtain mixed solution M2；
Step S3: will step S2The mixed solution M obtained in (1)2Transferring the mixture into a drying oven, drying the mixture at the drying temperature of 160 ℃ for 18h to obtain black powder, and ball-milling the black powder to 260 meshes to obtain powder M3；
Step S4: will step S3The powder M obtained in (1)3Transferring to a tubular roasting furnace, and carrying out secondary heating roasting under the condition of blowing high-purity nitrogen atmosphere; wherein, first-stage temperature rising: heating from room temperature to 400 ℃ at the heating rate of 2 ℃/min, and keeping the roasting temperature for roasting for 45 min; and (3) second-stage heating: after the temperature is raised to 750 ℃ at the temperature raising rate of 4 ℃/min, the roasting temperature is kept for roasting for 2.0h, and the iron source of the iron carbide can be obtained.
Wherein the preparation of the cobalt source comprises the steps of:
step L1: the preparation process of the spherical carbon comprises the following steps:
step P1: mixing glucose and distilled water at solid-to-liquid ratio of 0.25:1g/ml, ultrasonic frequency of 20kHz, and working density of 1.0Wcm-2Dissolving for 20min under the condition to obtain glucose solution N1；
Step P2: step P1The glucose solution N obtained in (1)1Transferring to a concentration reaction kettle, crystallizing at 180 deg.C for 10 hr to obtain colloidal concentrate N2；
Step P3: step P2To obtain a colloidal concentrate N2Cleaning and filtering the mixture by adopting an ethanol solution with the concentration of 20 percent to obtain a filter cake N3；
Step P4: filtering the filter cake N3Transferring into a drying oven, drying at 110 deg.C for 10 hr, ball milling to 220 mesh to obtain powder N4；
Step P5: step P4Powder N obtained in (1)4Transferring to a tubular roasting furnace, heating and roasting under high-purity nitrogen atmosphere at 790 ℃, keeping the roasting temperature for 2.0h to obtain the spherical carbon N5。
Step L2: the preparation process of the spherical carbon-supported cobalt oxide comprises the following steps:
step Q1: cobalt acetylacetonate and spherical carbon N5Placing the mixture and Carbamine in a flask according to the solid-to-liquid ratio of 0.1:0.15:1, and performing ultrasonic treatment at the working frequency of 20kHz and the working density of 1.0Wcm-2Dispersing for 20min under the condition to obtain clear mixed solution W1；
Step Q2: step Q1In which mixed solution W is contained1The flask is placed in an oil bath kettle, the temperature is raised to 190 ℃ under the conditions of reflux stirring and the temperature raising rate of 6 ℃/min, and the reaction temperature is kept for 1.0 h; cooling to room temperature under the condition of reflux stirring to obtain solid powder W2；
Step Q3: step Q2The fixed powder W obtained in (1)2Washing with 20% ethanol solution for 6 times, and vacuum filtering to obtain filter cake W3；
Step Q4: step Q3The filter cake W obtained in (1)3And (4) transferring the mixture into an oven, and drying the mixture at the drying temperature of 65 ℃ for 9h to obtain the cobalt source of the spherical carbon-supported cobalt oxide.
The above description is only a detailed description of the preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention should be covered within the scope of the present invention.
Claims (10)
1. An iron-cobalt-based catalyst for preparing carbon nanotubes, the catalyst comprising: the iron source comprises the following components in parts by weight: 10 percent of cobalt source (2-8);
the iron source is iron carbide prepared by a melting method;
the cobalt source is spherical carbon-supported cobalt oxide.
2. The method of claim 1, wherein the catalyst is prepared by mechanically mixing an iron source and a cobalt source.
3. The method of claim 2, wherein the preparing the iron source comprises the following steps:
step S1: firstly, glucose, urea and distilled water are mixed according to a solid-to-liquid ratio of 1-4: 2-6: 100g/ml, and a completely clear mixed solution M is obtained under the conditions that the reaction temperature is 145-165 ℃ and the stirring speed is 500-1200 rpm1；
Step S2: to step S1Medium mixed solution M1Adding ferric nitrate with the concentration of 0.05-0.15 mol/l, stirring at the stirring speed of 400-800 rpm until no obvious bubbles emerge from the mixed solution, and obtaining a mixed solution M2；
Step S3: will step S2The mixed solution M obtained in (1)2Transferring the mixture into an oven, drying the mixture at the drying temperature of 135-185 ℃ for 12-24 h to obtain black powder, and ball-milling the black powder to 220-360 meshes to obtain powder M3；
Step S4: will step S3The powder M obtained in (1)3Transferring the mixture to a tubular roasting furnace, and carrying out secondary heating roasting under a high-purity nitrogen atmosphere to obtain the iron source of the iron carbide.
4. The method of claim 3, wherein the step S is a step of preparing an Fe-Co based catalyst for preparing carbon nanotubes4Heating in the middle stage: heating the temperature 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) second-stage heating: after raising the temperature to 745-755 ℃ at the rate of 2-5 ℃/min, keeping the roasting temperature for roasting for 1.5-2.5 h.
5. The method of claim 2, wherein the preparing the cobalt source comprises the following steps:
step L1: preparing spherical carbon;
step L2: in step L1And preparing a cobalt source by loading cobalt oxide on the spherical carbon obtained in the step (1).
6. The method of claim 5, wherein the step L is a step of preparing an Fe-Co based catalyst for preparing carbon nanotubes1The preparation process of the medium spherical carbon comprises the following steps:
step P1: dissolving glucose and distilled water according to a solid-to-liquid ratio of 0.2-0.3: 1g/ml for 10-30 min under the action of ultrasonic waves to obtain a glucose solution N1；
Step P2: step P1The glucose solution N obtained in (1)1Transferring the mixture into a concentration reaction kettle, and crystallizing and concentrating for 8-12 h at the temperature of 175-190 ℃ to obtain a colloidal concentrate N2；
Step P3: step P2To obtain a colloidal concentrate N2Cleaning and suction-filtering by adopting an ethanol solution with the concentration of 15-30% to obtain a filter cake N3；
Step P4: filtering the filter cake N3Transferring the mixture into an oven, drying the mixture at the drying temperature of 105-115 ℃ for 8-12 h, and ball-milling the obtained dried mixture to 200-240 meshes to obtain powder N4；
Step P5: step P4Powder N obtained in (1)4Transferring to a tubular roasting furnace, and heating and roasting under the condition of blowing high-purity nitrogen atmosphere to obtain spherical carbon N5。
7. The method of claim 6, wherein the step P comprises5Middle powder N4And roasting at 750-820 ℃ for 1.5-2.5 h while keeping the roasting temperature.
8. The method of claim 5, wherein the iron-cobalt catalyst is selected from the group consisting of iron, cobalt, ironCharacterized in that step L2The preparation process of the medium spherical carbon-supported cobalt oxide comprises the following steps:
step Q1: cobalt acetylacetonate and spherical carbon N5Placing the mixture and the Carbamine in a flask according to the solid-to-liquid ratio of (0.005-0.015): (0.01-0.02): 1, and dispersing for 10-30 min under the action of ultrasonic waves to obtain a clear mixed solution W1；
Step Q2: step Q1In which mixed solution W is contained1The flask is placed in an oil bath kettle, the temperature is raised to 185-195 ℃ under the conditions of reflux stirring and the temperature raising rate of 2-10 ℃/min, and the reaction temperature is kept for 0.5-1.0 h; cooling to room temperature under the condition of reflux stirring to obtain solid powder W2；
Step Q3: step Q2The fixed powder W obtained in (1)2Washing the filter cake for 5 to 8 times by adopting an ethanol solution with the concentration of 15 to 30 percent, and filtering the washed filter cake to obtain a filter cake W3；
Step Q4: step Q3The filter cake W obtained in (1)3And transferring the mixture into an oven, and drying the mixture at the drying temperature of 55-75 ℃ for 6-12 h to obtain the cobalt source of the spherical carbon-supported cobalt oxide.
9. The method of claim 6 or 8, wherein the step P comprises1Or step Q1The medium ultrasonic wave has the working frequency of 15-30 kHz and the working density of 0.2-1.5 Wcm-2。
10. The use of the ferrocobalt-based catalyst for the preparation of carbon nanotubes according to claim 1, wherein the ferrocobalt-based catalyst is used for the preparation of array-type thin-walled carbon nanotubes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110217663.9A CN112958126B (en) | 2021-02-26 | 2021-02-26 | Iron-cobalt catalyst for preparing carbon nano tube and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110217663.9A CN112958126B (en) | 2021-02-26 | 2021-02-26 | Iron-cobalt catalyst for preparing carbon nano tube and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112958126A true CN112958126A (en) | 2021-06-15 |
| CN112958126B CN112958126B (en) | 2023-10-20 |
Family
ID=76275735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110217663.9A Active CN112958126B (en) | 2021-02-26 | 2021-02-26 | Iron-cobalt catalyst for preparing carbon nano tube and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112958126B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110195013A1 (en) * | 2008-10-17 | 2011-08-11 | Cheil Industries Inc. | Supported Catalyst for Synthesizing Carbon Nanotubes, Method for Preparing the Same and Carbon Nanotubes Made Using the Same |
| US20140255698A1 (en) * | 2012-01-11 | 2014-09-11 | Lg Chem, Ltd. | Cnt and method for manufacturing thereof |
| US20150238937A1 (en) * | 2013-07-10 | 2015-08-27 | Lg Chem. Ltd. | Supported catalyst, carbon nanotube assembly, and preparation method therefor |
| CN109908916A (en) * | 2019-04-11 | 2019-06-21 | 上海兖矿能源科技研发有限公司 | Carbon nanotube loaded iron-base fischer-tropsch synthesis catalyst and its preparation method and application |
| CN209081433U (en) * | 2018-06-21 | 2019-07-09 | 河南国碳纳米科技有限公司 | A kind of carbon nanotube production production line |
-
2021
- 2021-02-26 CN CN202110217663.9A patent/CN112958126B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110195013A1 (en) * | 2008-10-17 | 2011-08-11 | Cheil Industries Inc. | Supported Catalyst for Synthesizing Carbon Nanotubes, Method for Preparing the Same and Carbon Nanotubes Made Using the Same |
| US20140255698A1 (en) * | 2012-01-11 | 2014-09-11 | Lg Chem, Ltd. | Cnt and method for manufacturing thereof |
| US20150238937A1 (en) * | 2013-07-10 | 2015-08-27 | Lg Chem. Ltd. | Supported catalyst, carbon nanotube assembly, and preparation method therefor |
| CN209081433U (en) * | 2018-06-21 | 2019-07-09 | 河南国碳纳米科技有限公司 | A kind of carbon nanotube production production line |
| CN109908916A (en) * | 2019-04-11 | 2019-06-21 | 上海兖矿能源科技研发有限公司 | Carbon nanotube loaded iron-base fischer-tropsch synthesis catalyst and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112958126B (en) | 2023-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shen | Carbothermal synthesis of metal-functionalized nanostructures for energy and environmental applications | |
| CN102892533B (en) | Process for production of nickel nanoparticles | |
| WO2019113993A1 (en) | Carbon nanotube and method for fabrication thereof | |
| KR101331112B1 (en) | Nanocomposites consisting of carbon nanotube and metal oxide and a process for preparing the same | |
| CN102002652B (en) | Carbon nano tube reinforced metal matrix composite material and in-situ preparation method thereof | |
| JP2009525841A (en) | Method for producing a composition of nanoparticles on a solid surface | |
| CN103754878B (en) | The method of the spontaneous carbon nanotube of a kind of silicon-carbide particle surface in situ | |
| CN1678416A (en) | Metallic nickel powder and method for production thereof | |
| JP2010137222A (en) | Metal nano catalyst, manufacturing method therefor, and adjusting method of growth mode of carbon nanotube using therewith | |
| CN113058605B (en) | Catalyst for carbon nanotube and preparation method and application thereof | |
| CN112094623B (en) | Preparation method and application of titanium dioxide coated nickel-carbon hollow core-shell nano microsphere wave-absorbing material | |
| CN109665512A (en) | A kind of preparation method of multi-walled carbon nanotube | |
| CN110577209A (en) | Preparation method for in-situ synthesis of carbon nano tube surface loaded copper oxide nano particles | |
| Zou et al. | Controllable self-catalytic fabrication of carbon nanomaterials mediated by a nickel metal organic framework | |
| WO2023109596A1 (en) | Copper phthalocyanine polymer@copper nanowire core-shell nanomaterial, preparation method, and application | |
| Tu et al. | Preparation of lignin-based carbon nanotubes using micelles as soft template | |
| JP5585275B2 (en) | Carbon nanotube manufacturing method | |
| CN112958126A (en) | Iron-cobalt catalyst for preparing carbon nano tube and preparation method and application thereof | |
| KR20100134479A (en) | Cnt powder coated metal nano particles and manufacturing method of thereof | |
| CN112978716B (en) | Preparation method of array type thin-wall small-caliber carbon nano tube | |
| CN109226740B (en) | Iridium nano particle and application thereof in catalytic growth of carbon nano tube | |
| CN110482529B (en) | Black phosphorus carbon nanotube composite material and preparation method thereof | |
| KR101141716B1 (en) | Large-scale manufacturing method of high-surface area iron oxide nanoparticles | |
| KR102254960B1 (en) | Synthetic method of multi-walled carbon nanotubes conductive dispersion liquid using milling process | |
| Afolabi et al. | Continuous production of carbon nanotubes and diamond films by swirled floating catalyst chemical vapour deposition method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |