CN112978716B - Preparation method of array type thin-wall small-caliber carbon nano tube - Google Patents

Preparation method of array type thin-wall small-caliber carbon nano tube Download PDF

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CN112978716B
CN112978716B CN202110217664.3A CN202110217664A CN112978716B CN 112978716 B CN112978716 B CN 112978716B CN 202110217664 A CN202110217664 A CN 202110217664A CN 112978716 B CN112978716 B CN 112978716B
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temperature
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roasting
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CN112978716A (en
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刘保生
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Henan Guotan Nanotechnology Co ltd
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
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Abstract

The invention discloses a preparation method of array type small-caliber carbon nano tubes, which comprises the following steps: step X1: to be cleanedPutting quartz and a silicon wafer carrier into a porcelain boat, and uniformly mixing an iron-cobalt catalyst and PET material powder in a weight ratio of 0.05-0.15: 1 to obtain a raw material; step X2: starting the tubular roasting furnace in advance to a preset temperature; step X3: introducing nitrogen and hydrogen into the tubular roasting furnace at a certain speed; step X4: moving the raw materials to a reaction zone of a tubular roasting furnace for maintaining a certain reaction time; step X5: after the preset reaction time is reached, the power supply and the hydrogen source of the tube-type roasting furnace are closed, and the temperature is reduced to 200 ℃; step X6: and (5) closing the nitrogen source to obtain the carbon nanotube material. The PET material is used as a carbon source, the iron-cobalt catalyst is used as a catalyst, a chemical vapor deposition method is adopted, the process is simple, industrial large-scale production is easy to realize, and the carbon nanotube material with excellent performance is obtained.

Description

Preparation method of array type thin-wall small-caliber carbon nano tube
Technical Field
The invention relates to the technical field of carbon nanotube synthesis, in particular to a preparation method of array type thin-wall small-caliber carbon nanotubes.
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 of the preparation of the synthesized carbon nano tube by adopting the chemical vapor deposition method is the preparation and selection of the catalyst, the components, the morphology, 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 morphology 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 about 600 ℃ at lower temperature at present, the improvement of the growth temperature has strong effect on the growth speed of the carbon nano tube, but when the growth temperature is improved, 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.
With the improvement of national standard of living, soft drinks have been developed vigorously, wherein the proportion of the drinks bottles mainly made of plastic is high, however, the quantity of PET wastes is increased sharply due to the mass production, consumption and short service cycle of the plastic bottles (PET material). The waste of plastics not only causes huge waste of resources, but also brings great harm to the environment. Under the new situation that the energy problem is increasingly prominent and the environmental problem is increasingly severe, how to realize the recycling of the waste PET material in an environment-friendly and efficient manner is urgent to be solved.
Therefore, it is desirable to provide a method for preparing an array-type thin-walled small-diameter carbon nanotube, which uses a waste PET material as a raw material, and an iron-cobalt catalyst with high stability and dispersion degree as a catalyst under a higher temperature condition to obtain a carbon nanotube material with good electrical and physical and chemical properties, so as to overcome the above problems.
Disclosure of Invention
In order to solve the above problems, embodiments of the present invention provide a method for preparing an array-type thin-walled small-diameter carbon nanotube, and the purpose of the present invention is achieved by the following technical scheme:
a method for preparing array type thin-wall small-caliber carbon nano-tubes, wherein the carbon nano-tubes are prepared by adopting a normal-pressure chemical vapor deposition method, and the method comprises the following steps:
step X1: putting the cleaned quartz and the silicon wafer carrier into a porcelain boat, wherein the weight ratio of the quartz to the silicon wafer carrier is 0.05-0.15: 1, uniformly mixing the iron-cobalt catalyst and PET material powder to obtain a raw material Y1Mixing raw material Y1Placing in a porcelain boat;
step X2: opening a tubular roasting furnace in advance, and heating to a preset reaction temperature of 750-850 ℃ at a heating rate of 5-10 ℃/min;
step X3: in step X2Introducing nitrogen and hydrogen into the tubular roasting furnace at a certain speed 30min before the medium-tube roasting furnace reaches the preset temperature;
step X4: step X1In which the raw material Y is contained1The ceramic boat is moved to a reaction zone from a preheating zone of the tube type roasting furnace, and the reaction time is maintained to be 20-40 min;
step X5: step X4After the preset reaction time is reached, closing the power supply of the tubular roasting furnace, closing the hydrogen source, and keeping the nitrogen introduced into the tubular roasting furnace until the temperature is reduced to 200 ℃;
step X6: step X5After the nitrogen source is closed, the temperature of the tubular roasting furnace is reduced to room temperature, and the porcelain boat is taken out, thus obtaining the array type thin-walled carbon nanotube material Y2。
Further, the iron-cobalt-based catalyst includes: 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; the catalyst is prepared by mechanically mixing an iron source and a cobalt source.
Further, the preparation of the iron source comprises the steps of:
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 0.05-0.15 mol/l ferric nitrate into the mixture, and stirring the mixtureStirring at the stirring speed of 400-800 rpm until no obvious bubbles emerge from the mixed solution to obtain 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 roasting at a second stage under the condition of blowing high-purity nitrogen atmosphere, wherein the first stage is heating: 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.
Further, preparing the cobalt source comprises the steps of:
step L1: the process for preparing the 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)4Transferred to a tubular roasting furnaceIn the method, the mixture is heated and roasted under the condition of blowing high-purity nitrogen atmosphere, the roasting temperature is kept at 750-820 ℃ for 1.5-2.5 h, and the spherical carbon N is obtained5；
Step L2: in step L1The preparation process of the spherical carbon supported cobalt oxide obtained in the step (A) 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 pot, the temperature is raised to 185-plus-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.
Further, step P1Or step Q1The medium-ultrasonic working frequency is 15-30 kHz, and the working density is 0.2-1.5 Wcm-2。
Further, step X3The flow rates of the nitrogen and the hydrogen are 350 sccm.
Further, the PET material is a waste PET packaging material subjected to alcoholization treatment, and comprises the following steps:
step R1: crushing the waste PET packaging material in a crusher to obtain waste PET particles;
step R2: step R1Washing the obtained waste PET particles with water, and filtering to obtain purified PET particles;
step R3: step R2Cleaning the PET material in 10-30% ethanol solution for 5-8 times, controlling the cleaning temperature at 45-65 ℃, filtering to obtain clean PET particles, and drying the clean PET particles under the conditions that the vacuum degree is 0.02-0.08MPa and the temperature is 55-75 ℃;
step R4: r is to be3And crushing the clean and dry PET particles obtained in the step (1) to 200-240 meshes to obtain PET material raw material powder.
Compared with the prior art, the embodiment of the invention at least has the following beneficial effects:
1. the invention provides a preparation method of an array type thin-wall carbon nano tube, which takes a clean waste PET packaging material as a raw material, takes an iron-cobalt catalyst with good stability and dispersion degree under a high-temperature reaction condition as a catalyst, adopts a conventional chemical vapor deposition method to prepare the carbon nano tube, and has the advantages of simple process, easy industrial large-scale production, low material production cost, safety, environmental protection and the like;
2. 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 at a higher temperature, the catalytic performance of the catalyst is improved, and the production efficiency of the carbon nano tubes is improved;
3. the method adopts spherical carbon-supported cobalt oxide to realize high dispersion on a spherical carbon substrate, the particles are controllable, the particle size of the cobalt oxide particles in growth is controlled by increasing the heating rate, and the problem of agglomeration 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 method is suitable for preparing the thin-walled carbon nano tube with small particle size;
4. when the iron-cobalt catalyst is used for preparing the array thin-wall carbon nano tube, part of catalyst particles can realize that iron-cobalt metal particles are filled in the carbon nano tube by controlling the growth condition of the carbon nano tube, thereby being beneficial to increasing the conductivity and the mechanical property of the carbon nano tube.
5. The high-value recovery of the waste PET can be realized, the waste is changed into valuable, and the existing environmental protection problem is favorably solved;
6. the carbon nanotube material has the characteristics of array, thin wall, small pipe diameter, low length-diameter ratio, uniform structure, narrow chirality, metal particle filling and the like, thereby obtaining good electrical property and physical and chemical properties and having wide application.
Drawings
FIG. 1 is an XRD (X-ray diffraction) pattern of iron carbide catalyst (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) of samples with different iron contents loaded in the example of the present 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 spectra of samples of spherical carbon-supported cobalt oxide at different heating rates in the embodiment of the invention (a:2 ℃/min, b:5 ℃/min, c:8 ℃/min, d:10 ℃/min);
FIG. 5 is an SEM (plan view of carbon nanotube material, b and c are enlarged views of the 1-point position in the plan view of a, d, e and f are enlarged views of the 2-point position side wall in the a) of the array thin-walled carbon nanotube in the embodiment of the invention;
FIG. 6 is an SEM image of metal particle-filled carbon nanotubes (a is carbon nanotubes filled with no metal particles; b, c, and d are carbon nanotubes filled with metal particles) in an 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:
a method for preparing array type thin-wall small-caliber carbon nano-tubes, wherein the carbon nano-tubes are prepared by adopting a normal-pressure chemical vapor deposition method, and the method comprises the following steps:
step X1: putting the clean quartz and silicon chip carrier in a porcelain boat, and uniformly mixing an iron-cobalt catalyst with the weight ratio of 0.05:1 with PET material powder to obtain a raw material Y1Mixing raw material Y1Placing in a porcelain boat;
wherein step X1The PET material is a waste PET packaging material subjected to alcoholization treatment, and comprises the following steps:
step R1: crushing the waste PET packaging material in a crusher to obtain waste PET particles;
step R2: step R1Washing the obtained waste PET particles with water, and filtering to obtain purified PET particles;
step R3: step R2Washing the purified PET material in 20% ethanol solution for 5 times, controlling the washing temperature at 45 ℃, filtering to obtain clean PET particles, and drying the clean PET particles under the conditions that the vacuum degree is 0.05MPa and the temperature is 55 ℃;
step R4: r is to be3Crushing the clean and dry PET particles obtained in the step (1) to 200 meshes to obtain PET material raw material powder;
step X2: opening a tubular roasting furnace in advance, and heating to a preset reaction temperature of 750 ℃ at a heating rate of 5 ℃/min;
step X3: in step X2Introducing nitrogen and hydrogen into the tubular roasting furnace at a certain speed 30min before the medium-tube roasting furnace reaches the preset temperature, wherein the introduction flow of the nitrogen and the hydrogen is 350 sccm;
step X4: step X1In which the raw material Y is contained1The ceramic boat is moved to a reaction zone from a preheating zone of the tubular roasting furnace, and the reaction time is maintained to be 20 min;
step X5: step X4After the preset reaction time is reached, closing the power supply of the tube type roasting furnace, closing the hydrogen source, and keeping the nitrogen introduced into the tube type roasting furnace until the temperature is reduced to 200 ℃;
step X6: step X5After the nitrogen source is closed, the temperature of the tubular roasting furnace is reduced to room temperature, and the ceramic boat is taken out to obtain the array type thin-walled carbon nanotube material Y2。
Example 2:
a method for preparing array thin-wall small-caliber carbon nano-tubes, wherein the carbon nano-tubes are prepared by adopting a normal-pressure chemical vapor deposition method, and the method comprises the following steps:
step X1: putting the clean quartz and silicon chip carrier in a porcelain boat, and uniformly mixing an iron-cobalt catalyst with the weight ratio of 0.15:1 with PET material powder to obtain a raw material Y1Mixing raw material Y1Placing in a porcelain boat;
wherein step X1The PET material is a waste PET packaging material subjected to alcoholization treatment, and comprises the following steps:
step R1: crushing the waste PET packaging material in a crusher to obtain waste PET particles;
step R2: step R1Washing the obtained waste PET particles with water, and filtering to obtain purified PET particles;
step R3: step R2Washing the obtained purified PET material in 30% ethanol solution for 8 times, controlling the washing temperature at 65 ℃, filtering to obtain clean PET particles, and drying the clean PET particles under the conditions that the vacuum degree is 0.05MPa and the temperature is 75 ℃;
step R4: r is to be3The clean and dry PET particles obtained in (a) were pulverized to 240 mesh to obtain PET material raw material powder.
Step X2: opening the tubular roasting furnace in advance, and heating up at a heating rate of 10 ℃/min to a preset reaction temperature of 850 ℃;
step X3: in step X2Introducing nitrogen and hydrogen into the tubular roasting furnace at a certain speed 30min before the medium-tube roasting furnace reaches the preset temperature, wherein the introduction flow of the nitrogen and the hydrogen is 350 sccm;
step X4: step X1In which raw material Y is contained1The ceramic boat moves from the preheating zone of the tube type roasting furnace to the reactionKeeping the reaction time at 40 min;
step X5: step X4After the preset reaction time is reached, closing the power supply of the tube type roasting furnace, closing the hydrogen source, and keeping the nitrogen introduced into the tube type roasting furnace until the temperature is reduced to 200 ℃;
step X6: step X5After the nitrogen source is closed, the temperature of the tubular roasting furnace is reduced to room temperature, and the porcelain boat is taken out, thus obtaining the array type thin-walled carbon nanotube material Y2。
Example 3:
a method for preparing array type thin-wall small-caliber carbon nano-tubes, wherein the carbon nano-tubes are prepared by adopting a normal-pressure chemical vapor deposition method, and the method comprises the following steps:
step X1: putting clean quartz and a silicon wafer carrier in a porcelain boat, and uniformly mixing an iron-cobalt catalyst and PET material powder in a weight ratio of 0.1:1 to obtain a raw material Y1Mixing raw material Y1Placing in a porcelain boat;
wherein step X1The PET material is a waste PET packaging material subjected to alcoholization treatment, and comprises the following steps:
step R1: crushing the waste PET packaging material in a crusher to obtain waste PET particles;
step R2: step R1Washing the obtained waste PET particles with water, and filtering to obtain purified PET particles;
step R3: step R2Washing the obtained purified PET material in 20% ethanol solution for 6 times, controlling the washing temperature at 55 ℃, filtering to obtain clean PET particles, and drying the clean PET particles under the conditions that the vacuum degree is 0.05MPa and the temperature is 65 ℃;
step R4: r is to be3Pulverizing the clean and dry PET particles obtained in the step (2) to 220 meshes to obtain PET material raw material powder.
Step X2: opening the tubular roasting furnace in advance, and heating up to a preset reaction temperature of 800 ℃ at a heating rate of 8 ℃/min;
step X3: in step X2Medium tube type roasting30min before the furnace reaches the preset temperature, introducing nitrogen and hydrogen into the tubular roasting furnace at a certain speed, wherein the introduction flow of the nitrogen and the hydrogen is 350 sccm;
step X4: step X1In which raw material Y is contained1The ceramic boat is moved to a reaction zone from a preheating zone of the tube type roasting furnace, and the reaction time is maintained for 30 min;
step X5: step X4After the preset reaction time is reached, closing the power supply of the tubular roasting furnace, closing the hydrogen source, and keeping the nitrogen introduced into the tubular roasting furnace until the temperature is reduced to 200 ℃;
step X6: step X5After the nitrogen source is closed, the temperature of the tubular roasting furnace is reduced to room temperature, and the porcelain boat is taken out, thus obtaining the array type thin-walled carbon nanotube material Y2。
Example 4:
an iron-cobalt based 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 catalyst is prepared by mechanically mixing an iron source and a cobalt source:
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, 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 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 toIn the tubular roasting furnace, the two-stage heating roasting is carried out under the condition of blowing high-purity nitrogen atmosphere; wherein, first-stage temperature rise: 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, heating and roasting under high-purity nitrogen atmosphere at 750 deg.C for 1.5h 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 solutionLiquid 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:
an iron-cobalt based 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 catalyst is prepared by mechanically mixing an iron source and a cobalt source:
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 S3ZhongdeTo powder M3Transferring 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 the condition of blowing high-purity nitrogen atmosphere, wherein the roasting temperature is 820 ℃, and keeping the roasting temperature for roasting for 2.5 hours 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 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-2Under the condition ofDispersing for 30min 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:
an iron-cobalt based 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 catalyst is prepared by mechanically mixing an iron source and a cobalt source:
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 ferric nitrate with the concentration of 0.1mol/l, stirring the mixture under the condition that the stirring speed is 600rpm until no obvious bubbles emerge from the mixed solution to obtain a 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: glucose and distilled water are mixed according to the solid-to-liquid ratio of 0.25:1g/ml, the ultrasonic working frequency is 20kHz, and the working density is 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 by using 20% ethanol solution to obtain 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 the Carbamine in a flask according to the solid-to-liquid ratio of 0.1:0.15:1, and working at the ultrasonic working frequency of 20kHzThe density was 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 (4)

1. A preparation method of array type thin-wall small-caliber carbon nano-tubes is characterized in that the carbon nano-tubes are prepared by a normal-pressure chemical vapor deposition method and comprises the following steps:
step X1: putting the cleaned quartz and the silicon wafer carrier into a porcelain boat, wherein the weight ratio of the quartz to the silicon wafer carrier is 0.05-0.15: 1, uniformly mixing the iron-cobalt catalyst and PET material powder to obtain a raw material Y1Mixing raw material Y1Placing in a porcelain boat;
step X2: opening the tubular roasting furnace in advance, and heating up to a preset reaction temperature of 750-850 ℃ at a heating rate of 5-10 ℃/min;
step X3: in step X2Introducing nitrogen and hydrogen into the tubular roasting furnace at a certain speed 30min before the medium-tube roasting furnace reaches the preset temperature;
step X4: step X1In which raw material Y is contained1The ceramic boat is moved to a reaction zone from a preheating zone of the tube type roasting furnace, and the reaction time is maintained to be 20-40 min;
step X5: step X4After the preset reaction time is reached, closing the power supply of the tubular roasting furnace, closing the hydrogen source, and keeping the nitrogen introduced into the tubular roasting furnace until the temperature is reduced to 200 ℃;
step X6: step X5After the nitrogen source is closed, the temperature of the tubular roasting furnace is reduced to room temperature, and the porcelain boat is taken out, thus obtaining the array type thin-walled carbon nanotube material Y2；
Wherein the iron-cobalt catalyst comprises: the iron source comprises the following components in parts by weight: a 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 catalyst is prepared by mechanically mixing an iron source and a cobalt source;
the preparation of 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: adding ferric nitrate with the concentration of 0.05-0.15 mol/l into the mixed solution M1 obtained in the step S1, and stirring the mixed solution at the stirring speed of 400-800 rpm until no obvious bubbles emerge from the mixed solution to obtain the 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 roasting at a second temperature rise under the condition of blowing high-purity nitrogen atmosphere, wherein the first temperature rise is as follows: heating the mixture 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: at a rate of 2 to 5 ℃/mAfter the in heating rate is raised to 745-755 ℃, keeping the roasting temperature for roasting for 1.5-2.5 h;
the preparation of the cobalt source comprises the following steps:
step L1: the process for preparing the 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 the mixture to a tubular roasting furnace, heating and roasting the mixture in a high-purity nitrogen gas blowing atmosphere at the temperature of 750-820 ℃ for 1.5-2.5 h while keeping the roasting temperature to obtain the spherical carbon N5；
Step L2: in step L1The preparation process of the spherical carbon supported cobalt oxide obtained in the step (2) comprises the following steps:
step Q1: cobalt acetylacetonate and spherical carbon N5Putting the mixture and the Carbamine into a flask according to the solid-to-liquid ratio of (0.005-0.015) to (0.01-0.02) to 1g/ml, 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 solid 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.
2. The method for preparing array type thin-wall small-caliber carbon nano-tubes according to claim 1, characterized in that 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。
3. The method for preparing array type thin-wall small-caliber carbon nano-tubes according to claim 1, characterized in that the step X3The flow rates of the nitrogen and the hydrogen are 350 sccm.
4. The preparation method of the array-type thin-wall small-caliber carbon nano tube as claimed in claim 1, wherein the PET material is a waste PET packaging material subjected to alcoholization treatment, comprising the following steps:
step R1: crushing the waste PET packaging material in a crusher to obtain waste PET particles;
step R2: step R1Washing the obtained waste PET particles with water, and filtering to obtain purified PET particles;
step R3: step R2Cleaning the PET material in 10-30% ethanol solution for 5-8 times, controlling the cleaning temperature at 45-65 ℃, filtering to obtain clean PET particles, and drying the clean PET particles under the conditions that the vacuum degree is 0.02-0.08MPa and the temperature is 55-75 ℃;
step R4: and (3) crushing the clean and dry PET particles obtained in the R3 to 200-240 meshes to obtain PET material raw material powder.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106981670A (en) * 2017-04-13 2017-07-25 湖南工业大学 A kind of hydrogen reduction composite catalyst and its preparation method and application
CN107442147A (en) * 2017-08-10 2017-12-08 中南民族大学 A kind of iron-carbonide catalyst of high Fe content graphite linings parcel and its synthetic method and application
CN108262013A (en) * 2018-01-24 2018-07-10 清华大学 Carbon nanotube adsorption component, preparation method and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106981670A (en) * 2017-04-13 2017-07-25 湖南工业大学 A kind of hydrogen reduction composite catalyst and its preparation method and application
CN107442147A (en) * 2017-08-10 2017-12-08 中南民族大学 A kind of iron-carbonide catalyst of high Fe content graphite linings parcel and its synthetic method and application
CN108262013A (en) * 2018-01-24 2018-07-10 清华大学 Carbon nanotube adsorption component, preparation method and application

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