CN107814374B - Method for regulating morphology of carbon material - Google Patents
Method for regulating morphology of carbon material Download PDFInfo
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- CN107814374B CN107814374B CN201711087218.5A CN201711087218A CN107814374B CN 107814374 B CN107814374 B CN 107814374B CN 201711087218 A CN201711087218 A CN 201711087218A CN 107814374 B CN107814374 B CN 107814374B
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- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
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- C01B2203/1205—Composition of the feed
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- C01B2203/1223—Methanol
Abstract
A method for regulating and controlling the morphology of a carbon material belongs to the technical field of carbon material preparation. According to the invention, a carbon source, a catalyst, a template agent and a solvent are used as raw materials, the mixing effect of the raw material premixing process is enhanced by means of chemical process enhancement through the premixing of a super-gravity machine, and carbon materials with different morphologies are prepared by a solvothermal method under the experimental conditions that the reaction temperature is 80-170 ℃ and the reaction time is 15-48 h. The morphology of the carbon material is regulated and controlled by changing the preparation process conditions such as the hypergravity level, the raw material proportion, the reaction temperature, the dosage of the template agent and the like, so that the carbon materials with various morphologies such as monodisperse solid carbon spheres, necklace-shaped solid carbon spheres, hollow carbon spheres, bowl-shaped hollow carbon spheres, ribbon-shaped carbon fibers, carbon nanorods and the like can be obtained. The preparation method has the advantages of short flow, simple operation and the like, and the prepared carbon material can be used as a catalyst carrier to prepare high-performance catalysts, hydrogen storage materials, impurity adsorbents and the like.
Description
Technical Field
The invention relates to a method for regulating and controlling the morphology of a carbon material, in particular to a method for regulating and controlling the morphology of the carbon material by using a chemical process strengthening means, namely a high gravity machine to pre-mix and strengthen the mixing effect of a raw material pre-mixing process, adopting a solvothermal method and changing process conditions, and belongs to the technical field of carbon material preparation.
Background
Chinese patent No. CN107039191-A discloses a method for preparing nitrogen functionalized hollow mesoporous carbon nanospheres, which uses resorcinol and formaldehyde solution as carbon sources, mechanically stirs and mixes the carbon sources in advance, and obtains the nitrogen functionalized hollow mesoporous carbon nanospheres through solvothermal reaction, wherein the operation process is complex. Chinese patent No. CN105217601-A discloses a preparation method of a multi-hollow carbon sphere with high specific surface area, which uses SiO2The ball is taken as a template, silane is taken as a pore-forming agent, formaldehyde and resorcinol are taken as carbon sources, ultrasonic premixing is carried out, and the coating technology is adopted,and carrying out the operation processes of carbonization, silicon removal and the like to obtain the hollow carbon spheres. Chinese patent No. CN201010225264.9 discloses a method for simultaneously synthesizing carbon nanoribbon and helical carbon nanotube, which comprises using acetylene gas as carbon source, and adopting vapor deposition method to catalytically crack acetylene in situ on the surface of Fe-Cu nanoparticle, wherein the reaction temperature is 400-. Chinese patent No. CN104843665-a discloses a preparation method of single-layer and multi-layer hollow carbon nanospheres, which comprises placing phenols and aldehydes in a solvent, mechanically stirring, reacting to obtain hollow spheres of phenolic resin polymers, and calcining in a reducing atmosphere to obtain the hollow carbon spheres.
Carbon materials are generally prepared by arc discharge, laser evaporation, vapor deposition and solvothermal methods. The arc discharge method is the earliest and most typical carbon material synthesis method, the carbon material can be graphitized to the greatest extent under the high-temperature condition, the defects are few, and the real performance of the carbon material can be reflected, but the arc discharge is violent, the process and the product are difficult to control, impurities in the composition are difficult to separate, and the reaction condition is harsh. The laser evaporation method can prepare the high-purity carbon nano material, basically does not need to purify, but has complex equipment, high energy consumption and high investment cost. The reaction process of the vapor deposition method is easy to control, the equipment is simple, but the growth process needs high temperature, the graphitization degree is poor, more crystallization defects exist, and the mechanical property and the physical and chemical properties of the carbon material are adversely affected. The method of directly obtaining nano powder material by carrying out related chemical reactions in solvent fluid at high temperature and high pressure is called solvothermal method. Solvent conditions can accelerate ionic reactions and promote hydrolysis reactions, and reactions that are difficult or worthless under conventional conditions can be achieved under solvothermal conditions. Under the solvothermal condition, the solvent can act as a chemical component and participate in the reaction, is a solvent, is a pressure and temperature transfer medium, realizes the formation and modification of an inorganic compound by controlling the physical and chemical factors of the process, and can overcome certain crystal form transformation, decomposition, volatilization and the like which cannot be overcome in the high-temperature preparation process. The solvothermal method can prepare the carbon material under mild experimental conditions, has controllable appearance and good crystal form, can effectively inhibit the oxidation of raw materials and products and the oxygen pollution in an organic solvent, but cannot observe the specific process of crystal growth in the synthesis process, is not beneficial to the research of the growth mechanism, and has higher requirements on a reaction vessel. The nucleation in the solvothermal reaction is a rapid instant reaction, and the reaction must be instantly mixed uniformly at a molecular level in a reactor, namely micro-mixing, so that the nonuniformity of supersaturation in the reactor can be avoided, and the product form is consistent as much as possible. Through literature research, the current researchers mostly adopt modes such as mechanical stirring premixing, ultrasonic premixing and the like in the solvent thermal premixing stage, and special feeding and mixing modes are required to achieve micro mixing, so that premixing in a supergravity environment is proposed. And the product appearance can be influenced to a certain extent by premixing in a hypergravity environment.
The carbon material comprises graphene, fullerene, carbon quantum dots, carbon nanotubes and a large amount of carbon materials with other morphologies, wherein the graphene can be regarded as a basic structure forming other heteromorphic bodies, and other important morphologies comprise: bamboo-like carbon nanotubes, herringbone carbon nanotubes, spiral carbon nanotubes, necklace-shaped solid carbon spheres, hollow carbon spheres, carbon fibers and the like. At present, carbon materials with different morphologies are widely applied to various high-tech fields such as biology, environment, energy, aerospace, catalysis, composite materials and the like. For example, the carbon nano tube can be used as a reinforcing agent and a conductive agent to manufacture an automobile protection part with excellent performance, can be used as a catalyst carrier to obviously improve the activity and selectivity of the catalyst, and has stronger microwave absorption performance, so that the carbon nano tube can be used as an absorbent to prepare a stealth material, an electromagnetic shielding material or a darkroom wave-absorbing material and the like; the carbon microspheres can be used in the aspects of nano-reactors, batteries, novel super-capacitor electrodes, drug delivery and imaging systems, adsorption, catalysis and the like, and the PtRu alloy with the particle size of 2-3nm is loaded on hollow mesoporous carbon spheres with the diameter of 300nm by Chai and the like, and the result shows that the carbon microspheres have higher methanol oxidation activity; liyadona and the like adopt colloidal carbon spheres as templates to synthesize GaN hollow spheres.
Researches show that the factors such as the structure, the dimension, the morphology and the size of the carbon material directly influence the physical and chemical properties of the carbon material, and the development of a controllable synthesis technology to obtain an ordered structure system of the carbon material is necessary for researching the properties of the carbon material, developing application and exploration of the carbon material and realizing the industrialization and the practicability of the carbon nano material. Therefore, the preparation method which can regulate the morphology of the carbon material, has proper process conditions and simple operation process needs to be invented.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for regulating and controlling the morphology of a carbon material by changing process conditions, so that carbon materials with various morphologies such as monodisperse solid carbon spheres, necklace-shaped solid carbon spheres, hollow carbon spheres, bowl-shaped hollow carbon spheres, ribbon-shaped carbon fibers, carbon nanorods and the like can be obtained, and the method is simple to operate, mild in process conditions and capable of controllably regulating the morphology of the carbon material.
The method for regulating and controlling the morphology of the carbon material mainly regulates and controls the morphology of the carbon material by changing process conditions such as the supergravity level, the raw material ratio, the reaction temperature, the reaction time, the template agent dosage and the like, the preparation process comprises a premixing stage, a solvothermal reaction stage and a post-treatment stage, and the method comprises the following steps:
(1) a premixing stage: weighing raw materials, namely taking a carbon source, a catalyst precursor, a template agent and a solvent as raw materials, putting the raw materials into a clean and dry reaction container, and premixing the raw materials by a chemical process strengthening means super-gravity machine;
(2) solvothermal reaction stage: putting the premixed raw materials in the step (1) into a reaction kettle, putting the reaction kettle into a heating box, reacting for a period of time, and taking the reaction kettle out;
(3) and (3) post-treatment stage: and naturally cooling the reaction kettle to normal temperature, taking out liquid in the kettle, and filtering, washing and drying to obtain the carbon material with controllable morphology.
One of ferrocene, nickelocene, cobaltocene, glucose and sucrose is used as a precursor of a carbon source and a catalyst, one of sodium oleate, oleic acid, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and hexadecyl trimethyl ammonium bromide is used as a template, one of benzene, o-dichlorobenzene, hexachlorocyclopentadiene, hexachlorobenzene and deionized water is used as a solvent, and the dosage relationship of the carbon source, the catalyst, the template and the solvent is 0.2-10 g: 0-0.3 g: 20-60 ml;
the mixing effect of the premixing process of the raw materials is enhanced by a supergravity machine through a chemical process enhancing means, the supergravity level is 0-250g (0-1g is the conventional mechanical stirring and mixing evenly, and more than 1g is the mixing adopting the supergravity level), the premixed raw materials are put into a reaction kettle, then the reaction kettle is put into a heating box to keep the reaction temperature at 80-170 ℃, after the reaction is carried out for 15-48h, the reaction kettle is taken out of the heating box and naturally cooled to the room temperature, the liquid in the reaction kettle is taken out to be filtered by one or more of centrifugal separation and vacuum filtration, one or more of hydrochloric acid, ethanol and deionized water are used for washing, and the product is dried in vacuum at 50-60 ℃ for 4-6 h. The morphology of the carbon material can be regulated and controlled by changing one or more process conditions, such as the supergravity level, the raw material ratio, the reaction temperature, the reaction time and the dosage of the template agent.
Further, the precursor of the carbon source and the catalyst is one of ferrocene, nickelocene and cobaltocene, benzene, o-dichlorobenzene, hexachlorocyclopentadiene and hexachlorobenzene are used as solvents, and the dosage relationship of the carbon source, the catalyst, the template agent and the solvent is 0.2-0.04 g: 0.01-0.02 g: 20-60 ml; obtaining the branch strip fiber product under the condition that the supergravity level is 100-200g, wherein the branch strip is the condition that the main trunk is provided with branches and the branches are provided with branches.
The carbon source and the catalyst precursor are one of ferrocene, nickelocene and cobaltocene, benzene, o-dichlorobenzene, hexachlorocyclopentadiene and hexachlorobenzene are used as solvents, and the dosage relationship of the carbon source, the catalyst, the template agent and the solvent is 0.2-0.04 g: 0.01-0.02 g: 20-60ml, and obtaining an independently dispersed hollow carbon sphere structure under the condition that the supergravity level is 0-1 g; the dosage relationship of the carbon source, the catalyst, the template agent and the solvent is 0.2-0.04 g: 0.04-0.06 g: 30ml, the reaction temperature is 140-160 ℃, and a small amount of hollow carbon spheres which are adhered into a chain shape are obtained.
The carbon source and the catalyst precursor are one of ferrocene, nickelocene and cobaltocene, benzene, o-dichlorobenzene, hexachlorocyclopentadiene and hexachlorobenzene are used as solvents, and the dosage relationship of the carbon source, the catalyst, the template agent and the solvent is 0.2-0.08 g: 0: 20-60ml, and the solid carbon ball is adhered to form a necklace-shaped structure, namely a necklace-shaped solid carbon ball, under the condition that the super-gravity level is 0-250 g.
Glucose or sucrose is used as a precursor of a carbon source and a catalyst, water is used as a solvent, and the dosage relation of the carbon source, the catalyst, a template agent and the solvent is 2-10 g: 0: 20-60ml, and 0-1g of super-gravity level to obtain the carbon nano rod with the rod-shaped structure.
Glucose or sucrose is used as a precursor of a carbon source and a catalyst, water is used as a solvent, and the dosage relation of the carbon source, the catalyst, a template agent and the solvent is 2-10 g: 0: 20-60ml, and 50-100g of hypergravity level, and obtaining the monodisperse solid nano carbon spheres.
Glucose or sucrose is used as a precursor of a carbon source and a catalyst, water is used as a solvent, one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and hexadecyl trimethyl ammonium bromide is used as a template agent, and the dosage relationship of the carbon source, the catalyst, the template agent and the solvent is 1-3 g: 0.1-0.3: 20-60ml, and 0-1g of super-gravity level to obtain the monodisperse hollow nano carbon spheres.
Glucose or sucrose is used as a precursor of a carbon source and a catalyst, water is used as a solvent, oleic acid or sodium oleate is used as a template agent, and the dosage relationship of the carbon source, the catalyst, the template agent and the solvent is 4-6 g: 0.1-0.3: 20-60ml, and 0-1g of super-gravity level to obtain the hemispherical hollow nano carbon structure, namely the bowl-shaped hollow carbon sphere.
The carbon material as catalyst carrier may be used in selective hydrogenation, selective oxidation, olefin hydroformylation, ammonia synthesis, Fischer-Tropsch synthesis, methanol steam reforming to produce hydrogen and other chemical reactions.
Drawings
FIG. 1 is a schematic diagram of the experimental procedure of the present invention.
FIG. 2 is a transmission electron microscope image of the ribbon-shaped carbon fiber prepared in example 1 of the present invention.
FIG. 3 is a transmission electron microscope image of the ribbon-shaped carbon fiber prepared in example 2 of the present invention.
FIG. 4 is a transmission electron micrograph of a hollow carbon sphere prepared in example 3 of the present invention.
Fig. 5 and 6 are transmission electron micrographs of hollow carbon spheres prepared in example 4 of the present invention.
FIG. 7 is a transmission electron micrograph of necklace-shaped solid carbon spheres prepared in example 5 of the present invention.
FIG. 8 is a transmission electron micrograph of necklace-shaped solid carbon spheres prepared in example 6 of the present invention.
FIG. 9 is a transmission electron micrograph of necklace-shaped solid carbon spheres prepared in example 7 of the present invention.
Fig. 10 and 11 are transmission and scanning electron micrographs of the carbon nanorods prepared in example 8 of the present invention.
FIG. 12 is a transmission electron micrograph of monodisperse solid carbon spheres prepared in example 9 of the present invention.
FIG. 13 is a transmission electron micrograph of hollow carbon spheres prepared in example 10 of the present invention.
FIG. 14 is a scanning electron micrograph of a bowl-shaped hollow carbon sphere prepared in example 11 of the present invention.
Detailed Description
The invention will be further illustrated by the following examples. The scope of the invention as claimed is not limited to the following examples.
Example 1
Taking 0.02g of ferrocene, 0.01g of sodium oleate and 20-40ml of o-dichlorobenzene in a clean dry beaker. And feeding by a peristaltic pump, premixing under the condition that the supergravity level is 100-200g, and filling the premixed raw materials into a reaction kettle. And (3) putting the reaction kettle into a heating box, reacting at the temperature of 80-160 ℃ for 18-24h, and taking the reaction kettle out of the heating box to cool to room temperature. Taking out the product in the reaction kettle, putting the product into a centrifugal tube, centrifuging for 6-10min at the speed of 5000 plus 7500rpm by a centrifuge, and pouring out the upper liquid. Then washed with hydrochloric acid, ethanol, deionized water, respectively, leaving a black powdered product. And (3) drying the product at 50-60 ℃ for 4-6h in vacuum to obtain a ribbon carbon fiber product.
Example 2
Taking 0.04g of ferrocene, 0.01g of sodium oleate and 20-40ml of o-dichlorobenzene in a clean dry beaker. And feeding by a peristaltic pump, premixing under the condition that the supergravity level is 100-200g, and filling the premixed raw materials into a reaction kettle. And (3) putting the reaction kettle into a heating box, reacting at the temperature of 80-160 ℃ for 18-24h, and taking the reaction kettle out of the heating box to cool to room temperature. Taking out the product in the reaction kettle, putting the product into a centrifugal tube, centrifuging for 6-10min at the speed of 5000 plus 7500rpm by a centrifuge, and pouring out the upper liquid. Then washed with hydrochloric acid, ethanol, deionized water, respectively, leaving a black powdered product. And (3) drying the product at 50-60 ℃ for 4-6h in vacuum to obtain a ribbon carbon fiber product.
Example 3
Taking 0.02-0.04g of ferrocene, 0.01-0.02g of sodium oleate and 20-40ml of o-dichlorobenzene in a clean dry beaker. Feeding by a peristaltic pump, premixing under the condition that the supergravity level is 0-1g, and filling the premixed raw materials into a reaction kettle. And (3) putting the reaction kettle into a heating box, reacting at the temperature of 80-160 ℃ for 18-24h, and taking the reaction kettle out of the heating box to cool to room temperature. Taking out the product in the reaction kettle, putting the product into a centrifugal tube, centrifuging for 6-10min at the speed of 5000 plus 7500rpm by a centrifuge, and pouring out the upper liquid. Then washed with hydrochloric acid, ethanol, deionized water, respectively, leaving a black powdered product. And (3) drying the product at 50-60 ℃ for 4-6h in vacuum to obtain a hollow carbon sphere product.
Example 4
Taking 0.02-0.04g of ferrocene, 0.04-0.06g of sodium oleate and 30ml of o-dichlorobenzene in a clean dry beaker. Feeding by a peristaltic pump, premixing under the condition that the supergravity level is 0-1g, and filling the premixed raw materials into a reaction kettle. And (3) placing the reaction kettle into a heating box, reacting at the temperature of 140 ℃ and 160 ℃ for 18-24h, and taking out the reaction kettle from the heating box to cool to room temperature. Taking out the product in the reaction kettle, putting the product into a centrifugal tube, centrifuging for 6-10min at the speed of 5000 plus 7500rpm by a centrifuge, and pouring out the upper liquid. Then washed with hydrochloric acid, ethanol, deionized water, respectively, leaving a black powdered product. And (3) drying the product at 50-60 ℃ for 4-6h in vacuum to obtain a hollow carbon sphere product.
Example 5
Taking 0.02-0.04g of ferrocene and 20-40ml of o-dichlorobenzene in a clean dry beaker. And feeding by a peristaltic pump, premixing under the condition that the supergravity level is 100-200g, and filling the premixed raw materials into a reaction kettle. And (3) putting the reaction kettle into a heating box, reacting at the temperature of 80-160 ℃ for 18-24h, and taking the reaction kettle out of the heating box to cool to room temperature. Taking out the product in the reaction kettle, putting the product into a centrifugal tube, centrifuging for 6-10min at the speed of 5000 plus 7500rpm by a centrifuge, and pouring out the upper liquid. Then washed with hydrochloric acid, ethanol, deionized water, respectively, leaving a black powdered product. And (3) drying the product at 50-60 ℃ for 4-6h in vacuum to obtain the necklace-shaped solid carbon sphere product.
Example 6
Ferrocene, 0.08g, o-dichlorobenzene, 40ml was taken in a clean dry beaker. And feeding by a peristaltic pump, premixing under the condition that the supergravity level is 100-250g, and filling the premixed raw materials into a reaction kettle. . And (3) placing the reaction kettle into a heating box, reacting at the temperature of 150 ℃ for 36h, taking the reaction kettle out of the heating box, cooling to room temperature, carrying out reduced pressure suction filtration on the product in the reaction kettle, and washing with deionized water to obtain a black powdery product. And (3) drying the product at 50-60 ℃ for 4-6h in vacuum to obtain the necklace-shaped solid carbon sphere product.
Example 7
Taking 0.04g of nickelocene and 20ml of hexachlorobenzene in a clean dry beaker. Feeding by a peristaltic pump, wherein the super-gravity level is 0-1g, and filling into a reaction kettle. And (3) placing the reaction kettle into a heating box, reacting at the temperature of 130 ℃ for 36h, taking the reaction kettle out of the heating box, cooling to room temperature, carrying out reduced pressure suction filtration on the product in the reaction kettle, and washing with deionized water to obtain a black powdery product. And (3) drying the product at 50-60 ℃ for 4-6h in vacuum to obtain the necklace-shaped solid carbon sphere product.
Example 8
10g of glucose and 40ml of deionized water were taken in a clean dry beaker. Feeding by a peristaltic pump, wherein the super-gravity level is 0-1g, and filling into a reaction kettle. And (3) putting the reaction kettle into a heating box, reacting at 160 ℃, taking the reaction kettle out of the heating box after reacting for 36 hours, and cooling to room temperature. And (3) centrifugally separating the product in the reaction kettle, and washing the product for multiple times by using ethanol and deionized water to obtain a black powdery product. And (3) drying the product at 50-60 ℃ for 4-6h in vacuum to obtain the carbon nano rod.
Example 9
2-6g of glucose and 20-60ml of deionized water are taken and put in a clean dry beaker. The peristaltic pump feeds the materials, the super-gravity level is 50-100g, and the materials are put into a reaction kettle. And (3) putting the reaction kettle into a heating box, reacting at the temperature of 100 ℃, taking the reaction kettle out of the heating box after reacting for 12 hours, and cooling to room temperature. And (3) centrifugally separating the product in the reaction kettle, and washing the product for multiple times by using ethanol and deionized water to obtain a black powdery product. And (3) drying the product at 50-60 ℃ for 4-6h in vacuum to obtain the monodisperse solid nano carbon spheres.
Example 10
1-3g of glucose, 0.1-0.3g of sodium dodecyl sulfate and 20-60ml of deionized water are put into a clean dry beaker. Feeding by a peristaltic pump, wherein the super-gravity level is 0-1g, and filling into a reaction kettle. And (3) placing the reaction kettle into a heating box, reacting at the temperature of 120-170 ℃, taking out the reaction kettle from the heating box after reacting for 24-36h, and cooling to room temperature. And (3) centrifugally separating the product in the reaction kettle, and washing the product with ethanol and deionized water in sequence to obtain a black powdery product. And (3) drying the product at 50-60 ℃ for 4-6h in vacuum to obtain the monodisperse hollow nano carbon spheres.
Example 11
Taking 4-6g of glucose, 0.1-0.3g of sodium oleate and 20-60ml of deionized water in a clean dry beaker. Feeding by a peristaltic pump, wherein the super-gravity level is 0-1g, and filling into a reaction kettle. And (3) placing the reaction kettle into a heating box, reacting at the temperature of 140 ℃ and 170 ℃, taking out the reaction kettle from the heating box after reacting for 8-16h, and cooling to room temperature. And (3) centrifugally separating the product in the reaction kettle, and washing the product with ethanol and deionized water in sequence to obtain a black powdery product. And (3) drying the product at 50-60 ℃ for 4-6h in vacuum to obtain the bowl-shaped hollow carbon spheres.
The prepared carbon material is used for methanol oxygen-steam reforming hydrogen production reaction for performance test.
1. And (3) copper deposition: a solution impregnation method is adopted to introduce metal phase Cu from a copper nitrate aqueous solution onto the surface of a carbon material, and then a carrier catalyst is dried at 120 ℃ for 2 hours and calcined at 350 ℃ for 4 hours, wherein the loading amount of copper is 20 wt.%.
2. Catalyst performance testing experiment: the copper-loaded carbon material catalyst was maintained at 5% H before the measurement of catalytic activity2Pre-reducing for 1h in a mixed gas of-95% Ar. Under normal pressure, methanol is reformed by oxygen-steam in a flow quartz reactor, the reaction temperature is 300 ℃, the dosage of the catalyst is 0.1g, and the mobile phase groupIs converted into H2O/CH3OH/O 21/1/0.4 (molar ratio) and 26700h of volume space velocity-1A total flow rate of 31.5ml/min was maintained, and Ar was used as an equilibrium gas (methanol content in the reaction mixture: 6%). The experimental result shows that under the condition of the catalyst, the conversion rate of the methanol can reach 60-80%.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications belonging to the technical solutions of the present invention may still fall within the protection scope of the present invention.
Claims (8)
1. The method for regulating and controlling the morphology of the carbon material is characterized in that the preparation process comprises a premixing stage, a solvothermal reaction stage and a post-treatment stage, and the method comprises the following steps:
(1) a premixing stage: weighing raw materials, namely taking a carbon source, a catalyst precursor, a template agent and a solvent as raw materials, putting the raw materials into a clean and dry reaction container, and premixing the raw materials by a chemical process strengthening means super-gravity machine;
(2) solvothermal reaction stage: putting the premixed raw materials in the step (1) into a reaction kettle, putting the reaction kettle into a heating box, reacting for a period of time, and taking the reaction kettle out;
(3) and (3) post-treatment stage: naturally cooling the reaction kettle to normal temperature, taking out liquid in the kettle, and filtering, washing and drying to obtain a carbon material with controllable morphology;
the morphology of the carbon material is regulated and controlled by changing one or more of the process conditions, the hypergravity level, the raw material ratio, the reaction temperature and the dosage of the template agent, so that the carbon materials with various morphologies, such as monodisperse solid carbon spheres, necklace-shaped solid carbon spheres, hollow carbon spheres, ribbon-shaped carbon fibers and carbon nanorods, are respectively obtained;
taking one of ferrocene, nickelocene and cobaltocene as a precursor of a carbon source and a catalyst, taking one of sodium oleate, oleic acid, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and hexadecyl trimethyl ammonium bromide as a template, taking one of benzene, o-dichlorobenzene, hexachlorocyclopentadiene, hexachlorobenzene and deionized water as a solvent, wherein the dosage relationship of the carbon source, the precursor of the catalyst, the template and the solvent is 0.2-10 g: 0-0.3 g: 20-60 ml;
the method comprises the steps of premixing and enhancing the mixing effect of the raw materials in the premixing process by a supergravity machine through a chemical process enhancing means, wherein the supergravity level is 0-250g, loading the premixed raw materials into a reaction kettle, then putting the reaction kettle into a heating box, keeping the reaction temperature at 80-170 ℃, taking the reaction kettle out of the heating box after reacting for 15-48h, naturally cooling to room temperature, taking out liquid in the reaction kettle, filtering by one of centrifugal separation and vacuum filtration, washing by one or more of hydrochloric acid, ethanol and deionized water, and vacuum-drying the product for 4-6h at 50-60 ℃.
2. The method for regulating morphology of carbon material according to claim 1, wherein dosage relationship of carbon source, catalyst precursor, template agent and solvent is 0.2-0.04 g: 0.01-0.02 g: 20-60 ml; obtaining the branch strip fiber product under the condition that the supergravity level is 100-200g, wherein the branch strip is the condition that the main trunk is provided with branches and the branches are provided with branches.
3. The method for regulating and controlling morphology of carbon material according to claim 1, wherein the carbon source and the catalyst precursor are one of ferrocene, nickelocene and cobaltocene, benzene, o-dichlorobenzene, hexachlorocyclopentadiene and hexachlorobenzene are used as solvents, and the dosage relationship of the carbon source and the catalyst precursor, the template and the solvent is 0.2-0.04 g: 0.01-0.02 g: 20-60ml, and obtaining an independently dispersed hollow carbon sphere structure under the condition that the supergravity level is 0-1 g; the dosage relationship of the carbon source, the catalyst precursor, the template agent and the solvent is 0.2-0.04 g: 0.04-0.06 g: 30ml, the reaction temperature is 140-160 ℃, and a small amount of hollow carbon spheres which are adhered into a chain shape are obtained.
4. The method for regulating and controlling the morphology of a carbon material according to claim 1, wherein the carbon source and the catalyst precursor are one of ferrocene, nickelocene and cobaltocene, benzene, o-dichlorobenzene, hexachlorocyclopentadiene and hexachlorobenzene are used as solvents, and the dosage relationship of the carbon source and the catalyst precursor, the template and the solvent is 0.2-0.08 g: 0: 20-60ml, and the solid carbon ball is adhered to form a necklace-shaped structure, namely a necklace-shaped solid carbon ball, under the condition that the super-gravity level is 0-250 g.
5. The method for regulating morphology of carbon material according to claim 1, wherein glucose or sucrose is used as precursor of carbon source and catalyst, water is used as solvent, and dosage relationship of carbon source and catalyst precursor, template agent and solvent is 2-10 g: 0: 20-60ml, and 0-1g of super-gravity level to obtain the carbon nano rod with the rod-shaped structure.
6. The method for regulating morphology of carbon material according to claim 1, wherein glucose or sucrose is used as precursor of carbon source and catalyst, water is used as solvent, and dosage relationship of carbon source and catalyst precursor, template agent and solvent is 2-10 g: 0: 20-60ml, and 50-100g of hypergravity level, and obtaining the monodisperse solid nano carbon spheres.
7. The method for regulating morphology of a carbon material, according to claim 1, wherein glucose or sucrose is used as a precursor of a carbon source and a catalyst, water is used as a solvent, one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate and cetyl trimethyl ammonium bromide is used as a template, and the dosage relationship among the carbon source, the precursor of the catalyst, the template and the solvent is 1-3 g: 0.1-0.3: 20-60ml, and 0-1g of super-gravity level to obtain the monodisperse hollow nano carbon spheres.
8. The method for regulating morphology of carbon material according to claim 1, wherein glucose or sucrose is used as a carbon source and a precursor of a catalyst, water is used as a solvent, oleic acid or sodium oleate is used as a template agent, and the dosage relationship of the carbon source, the precursor of the catalyst, the template agent and the solvent is 4-6 g: 0.1-0.3: 20-60ml, and 0-1g of super-gravity level to obtain the hemispherical hollow nano carbon structure, namely the bowl-shaped hollow carbon sphere.
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