CN111501133B - Carbon nanofiber based on inorganic structure template and preparation method thereof - Google Patents
Carbon nanofiber based on inorganic structure template and preparation method thereof Download PDFInfo
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Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention relates to a carbon nanofiber based on an inorganic structure template and a preparation method thereof, belongs to the technical field of carbon nanofibers, and solves the technical problems that the existing carbon nanofiber is high in preparation cost, the arrangement and orientation of the nanofibers are disordered, and the diameter and the length of the fibers cannot be controlled in the preparation process of the carbon nanofiber. The preparation method comprises the following steps: step 1, pretreating an inorganic structure template material; step 2, dipping and structural intercalation treatment are carried out on the pretreated inorganic structure template by utilizing tetrahydrofuran solution containing a mixture of a cross-linking agent and polycyclic aromatic hydrocarbon; step 3, carrying out high-temperature carbonization treatment on the obtained inorganic structure template-condensed ring aromatic hydrocarbon mixture to obtain a carbonized product; and 4, removing the inorganic structure template to prepare the carbon nanofiber. The invention adopts an inorganic structure template, and forms a continuous carbon nanofiber structure through the controllable carbonization of a condensed ring aromatic hydrocarbon structure, thereby realizing the preparation of the carbon nanofiber with low cost and controllable process.
Description
Technical Field
The invention relates to the technical field of carbon nanofibers, in particular to a carbon nanofiber based on an inorganic structure template and a preparation method thereof.
Background
With the rapid development of nano science and technology in recent years, nano materials with excellent performance and various forms are continuously emerged, including: nanoparticles, nanofibers, nanorods, nanowires, nanosheets, and the like. Among them, the discovery of fullerene and carbon nanotube opened the era of nanotechnology, and the significant discovery of graphene pushed the research of nanocarbon materials to a new climax. The types of nanocarbon materials are expanding and include graphene, fullerene, carbon nanotubes, nanodiamonds, nanoparticles, nanofibers, nanoporous materials and nanocomposites.
Carbon nanofibers are a new material between carbon nanotubes and carbon fibers. The size of the carbon fiber is about tens of microns, and the size of the carbon nanofiber is between tens of nanometers and hundreds of nanometers; carbon nanofibers are internally structurally distinct from carbon nanotubes. The carbon nanofiber can be used as a key substance form for transition from a molecular material to a macroscopic material, has excellent physical and chemical properties, and is widely applied to the fields of multifunctional composite materials, super-capacitor electrode materials, lithium battery cathode materials, metal nanoparticle carriers, bone tissue support structures and the like.
There are two approaches to the preparation of carbon nanofibers in the prior art: 1) catalytic vapor deposition; 2) electrostatic spinning and heat treatment. The catalytic vapor deposition mainly adopts the carbon hydrogen molecules to deposit on the catalyst at high temperature to generate the carbon nanofibers, the length of the carbon nanofibers generated in the process is too short, the carbon nanofibers are difficult to disperse and treat, and the economical and efficient large-scale preparation cannot be realized.
Electrostatic spinning-heat treatment adopts electrostatic spinning to prepare a polymer nanofiber precursor, and then the polymer nanofiber precursor is converted into carbon nanofibers through a heat treatment process, the technical route of electrostatic spinning is relatively mature, and the preparation of large-scale polymer nanofibers can be realized, but a plurality of unsolved problems exist in the aspects of stabilization and controllable carbonization of the polymer nanofibers. In general, carbon nanofiber materials still exist some distance from large-scale industrial applications, and two key technical challenges need to be addressed:
firstly, a method and equipment for preparing defect-free carbon nanofibers on a large scale at low cost are needed to be solved; the second need is to solve the problem of controlling the diameter and length of the fiber in the preparation process of the carbon nanofiber and the post-treatment and dispersion technology of the material.
Disclosure of Invention
In view of the foregoing analysis, embodiments of the present invention are directed to provide a carbon nanofiber based on an inorganic structure template and a method for preparing the same, so as to solve the technical problems of the existing carbon nanofiber that the preparation cost is high, the arrangement and orientation of the nanofiber are disordered, and the diameter and length of the fiber cannot be controlled in the carbon nanofiber preparation process.
The purpose of the invention is mainly realized by the following technical scheme:
in one aspect, the invention provides carbon nanofibers based on an inorganic structure template, and the raw materials for preparing the carbon nanofibers comprise an inorganic structure template material and a tetrahydrofuran solution containing a mixture of a cross-linking agent and polycyclic aromatic hydrocarbon;
the inorganic structure template material is one of halloysite, sepiolite or serpentine.
Further, fused ring aromatic hydrocarbon mixtures include naphthalene, phenanthrene, and pyrene; 20-60% of phenanthrene, 10-30% of pyrene and the balance of naphthalene;
the cross-linking agent is one of benzaldehyde, terephthalyl alcohol, terephthaloyl chloride, divinylbenzene, terephthaloyl chloride and trioxymethylene, and the usage amount of the cross-linking agent is 0.45-1.3 times of the mass of the polycyclic aromatic hydrocarbon mixture.
In another aspect, the present invention further provides a method for preparing carbon nanofibers based on an inorganic structure template, for preparing the carbon nanofibers based on an inorganic structure template, including the following steps:
step 1, pretreating an inorganic structure template material to obtain a pretreated inorganic structure template material;
step 2, dipping and structural intercalation treatment are carried out on the pretreated inorganic structure template by utilizing tetrahydrofuran solution containing a mixture of a cross-linking agent and polycyclic aromatic hydrocarbon;
step 3, carrying out high-temperature carbonization treatment on the obtained inorganic structure template-condensed ring aromatic hydrocarbon mixture to obtain a carbonized product;
and 4, removing the inorganic structure template to prepare the carbon nanofiber.
Further, in the step 1, a sulfuric acid solution with a mass concentration of 1.0-10% is used for pretreating the inorganic structure template material, the dosage ratio of the sulfuric acid solution to the inorganic structure template material is 10-100 ml/g, the pretreatment temperature is 40-90 ℃, and the pretreatment time is 10-90 min.
Further, in the step 2, the loading amount of the mixture of the cross-linking agent and the polycyclic aromatic hydrocarbon is 5-25% of the mass of the inorganic structure template material, the temperature for carrying out the dipping and structure intercalation treatment is 60-150 ℃, and the time for carrying out the dipping and structure intercalation treatment is 30-120 min.
Further, in the step 3, the inorganic structure template-polycyclic aromatic hydrocarbon mixture is heated to 850-1200 ℃ at a heating rate of 3-15 ℃/min for high-temperature carbonization treatment.
Further, the high-temperature carbonization treatment time is 45-120 min, and the flow of nitrogen in the treatment process is 60-700 ml/min.
Further, in step 4, acid washing and alkali washing are sequentially carried out by adopting a sulfuric acid solution and a sodium hydroxide solution, and the inorganic structure template material is removed by elution;
the mass concentration of the sulfuric acid solution is 5.0-15%, and the ratio of the sulfuric acid solution to the carbonized product is 20-150 ml/g; the pickling treatment temperature is 50-90 ℃, and the treatment time is 30-120 min.
Further, in the step 4, the mass concentration of the sodium hydroxide solution is 8.0-16%, and the ratio of the sodium hydroxide solution to the carbonized product is 30-170 ml/g.
Further, the temperature of the alkali washing treatment is 60-95 ℃, and the treatment time is 30-120 min
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
(1) according to the method, the natural inorganic mineral is used as a structural template, the structure of the continuous carbon nanofiber is formed through controllable carbonization of the condensed ring aromatic hydrocarbon structure, the carbon nanofiber can be obtained after the inorganic template structure is removed, and the preparation of the carbon nanofiber with low cost and controllable process is realized.
(2) The method adopts natural cheap inorganic mineral as a structural template, simultaneously takes a condensed ring aromatic hydrocarbon mixture separated from coal tar as a precursor substance of a carbon structure, directly forms a continuous carbon nanofiber structure by controllable carbonization in the structure of the inorganic template, has simple and efficient process and strong equipment universality, is easy to realize scale preparation, prepares raw materials and method for economy and practicability, and provides a solution for large-scale production and application of carbon nanofibers.
(3) In the prior art, the defects of the carbon nano fiber exist in the following two aspects: one is that the size and length of the carbon nano-fiber can not be controlled and adjusted, and the other is that the arrangement orientation of the nano-fiber is disordered, which is not beneficial to post-treatment and dispersion. The method adopts Halloysite (Halloyite), Sepiolite (Sepiolite) and serpentine (Chrysotile) as the structural templates, the fiber size of the inorganic structural template is uniform, the fiber orientation is regular, and the method also utilizes tetrahydrofuran solution containing a mixture of a cross-linking agent and polycyclic aromatic hydrocarbon to carry out impregnation and structural intercalation treatment on the pretreated inorganic structural template material, so that the method is more favorable for realizing uniform fiber size and regular fiber orientation through the inorganic structural template, and further achieves the aim of adjusting and controlling the diameter and the length of the carbon nanofiber.
(4) The carbon nanofiber prepared by the prior art mainly comprises two methods: the gas phase catalytic deposition method and the high molecular precursor electrostatic spinning have no relatively uniform range of relevant size distribution due to the fact that specific experimental conditions are different from those of adopted raw materials. The length L of the carbon nanofiber prepared by the method is 100-1200 nm, the diameter D of the nanofiber is 10-100 nm, and the L/D ratio is 10-60.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
FIG. 1 shows a polycyclic aromatic hydrocarbon mixture and a crosslinking agent in an inorganic structure template
A reaction process schematic diagram of polycyclic polynuclear aromatic hydrocarbon substances condensed at lower temperature under catalysis of acid sites;
FIG. 2 is a schematic diagram of the high-temperature carbonization process of the composite formed by the inorganic structure template-condensed ring aromatic hydrocarbon condensate.
Detailed Description
The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which form a part hereof, and which together with the embodiments of the invention serve to explain the principles of the invention and not to limit its scope.
The invention provides a carbon nanofiber based on an inorganic structure template, and a preparation material of the carbon nanofiber comprises the following components: inorganic structure template material, tetrahydrofuran solution containing cross-linking agent and fused ring arene mixture.
The inorganic structure template material is one of Halloysite (Halloyite), Sepiolite (Sepiolite) and serpentine (Chrysotile), and the three are natural inorganic minerals.
Halloysite is a hydrous layered structure silicate mineral of a monoclinic system in a crystal, belongs to a dioctahedral structure of a 1:1 structural unit layer, but interlayer water exists among structural units, and most of interlayer water is lost at 50-90 ℃ to form halloysite.
Halloysite is usually in a dense block or soil form; the microstructure is that the crystal is in a straight or bent tubular shape, the crystal form is 100 percent of all natural nano tubular structure, the diameter is 0.1-0.4 mu m, and the length is<0.5 μm. The halloysite mineral composition is 95% kaolinite, trace quartz and sodium alunite, and the molecular formula of the pure halloysite is Al2O3·2SiO2·4H2O。
Sepiolite is a fibrous hydrous magnesium silicate with a microstructure consisting of numerous filaments arranged together in a sheet form. The content range of MgO is 21-25%, and the octahedral position of 90-100% is filled with Mg. Most of the chemical compositions and structures of sepiolite show that the mineral has enough cations and can basically fill 8 (7.74-8.14) octahedral positions. The sepiolite has a special structure which makes it have a tubular through channel with a cross-section of 0.36nm x 1.06nm and a diameter of up to 900m2Theoretical surface area in g. Serpentine (Mg)6Si4O10(OH)8) Is prepared from silicon oxide (SiO)2) Tetrahedra and magnesium hydroxide Mg (OH)2The octahedron silicate mineral is a double-layer structure composed of octahedrons.
Due to the incompatibility between the tetrahedral and octahedral layers, three basic structural minerals are formed: flat structure of plate-shaped serpentine, alternate wave structure of leaf serpentine, and curly cylindrical structure of chrysotile. The chrysotile mineral in nature has wide output, high crystallization degree and good separability. The serpentine splitting performance is excellent, the serpentine splitting performance can be furthest split into filaments, the splitting diameter is 1-2 mu m, the microstructure is mostly in a hollow tubular shape, the inner diameter of the serpentine splitting performance is generally 6-8 nm, and the outer diameter of the serpentine splitting performance is 20-50 nm.
The invention also provides a preparation method of the carbon nanofiber based on the inorganic structure template, which comprises the following steps:
step 1, pretreating an inorganic structure template material;
the inorganic structure template material is one of Halloysite (Halloysite), Sepiolite (Sepiolite) and serpentine (Chrysotile). The inorganic structure template material is pretreated by using a sulfuric acid solution with the mass concentration of 1.0-10%, the using ratio of the sulfuric acid solution to the inorganic template is 10-100 ml/g, the treatment temperature is 40-90 ℃, and the treatment time is 10-90 min.
The method mainly aims at adopting a sulfuric acid solution with the mass concentration of 1.0-10% to pretreat the inorganic structure template material and control the pretreatment conditions to three points: 1) the oxide in the inorganic structural template material is etched to expand the size of the tubular fiber structure and remove structural defects or blocked areas. Part of alumina in halloysite is dissolved out in the form of aluminum sulfate, and part of magnesia in sepiolite and serpentine is dissolved out in the form of magnesium sulfate; 2) acidifying active ion sites on the surface of an inorganic structural template material to form
The acidic sites are beneficial to catalyzing polymerization of polycyclic aromatic hydrocarbon molecules to form a carbonized structure; 3) removing impurity metals such as iron, manganese, calcium, chromium and the like so as to avoid metal ion pollution brought into the carbon nano-fiber. If the concentration of the sulfuric acid solution is too high, the etching process is uncontrollable, and the tubular fiber structure of the inorganic template material is easy to collapse or the fault layer defect is easy to occur.
The solid treated by the sulfuric acid solution is further cleaned by deionized water with the mass being 3-10 times that of the solid for 3-6 times, and dried in the air at the temperature of 100-150 ℃ for 1-3 hours, so that the sulfuric acid solution on the pretreated inorganic structure template is fully removed.
Step 2, dipping and structural intercalation treatment are carried out on the pretreated inorganic structure template material by utilizing tetrahydrofuran solution containing a mixture of a cross-linking agent and polycyclic aromatic hydrocarbon;
according to the invention, a carbonaceous precursor substance is introduced into the inorganic tubular fiber structure in a solution impregnation mode, wherein the carbonaceous precursor is a polycyclic aromatic hydrocarbon mixture, a crosslinking agent and a polycyclic aromatic hydrocarbon mixture, and the composition of the polycyclic aromatic hydrocarbon mixture is designed according to the polymerization reaction characteristics, specific reaction environment and conditions. The material consists of 20-60% of phenanthrene, 10-30% of pyrene and the balance of naphthalene; the cross-linking agent is one of benzaldehyde, terephthalyl alcohol, terephthaloyl chloride, divinylbenzene, terephthaloyl chloride and trioxymethylene, and the using amount of the cross-linking agent is 0.45-1.3 times of the mass of the polycyclic aromatic hydrocarbon mixture. The three polycyclic aromatic hydrocarbon molecules of naphthalene, phenanthrene and pyrene have different reactivity with the cross-linking agent, and uniform polymerization with the cross-linking agent is facilitated by controlling the mass ratio of the naphthalene, the phenanthrene and the pyrene to obtain the carbonized precursor substance meeting the requirements.
The method comprises the steps of carrying out impregnation and structural intercalation treatment on a pretreated inorganic structure template material by utilizing a tetrahydrofuran solution containing a mixture of a crosslinking agent and fused ring aromatic hydrocarbon (the mass concentration of the crosslinking agent and the fused ring aromatic hydrocarbon is 20%), wherein the impregnation load of the mixture of the crosslinking agent and the fused ring aromatic hydrocarbon is 5-25% of the mass of the inorganic structure template material, and controlling the load within the range is favorable for realizing uniform fiber size and regular fiber orientation through the inorganic structure template, so that the purpose of adjusting and controlling the diameter and the length of the carbon nanofiber is achieved. Too low a loading can result in poor fiber continuity and failure to maintain uniform size; too high a loading can cause aggregation and disorientation of the fibers, and can also cause embedding of the inorganic template structure, which makes removal of the template difficult.
The temperature of the intercalation treatment of the structure is 60-150 ℃, and the treatment time is 30-120 min. The strict control of the intercalation processing conditions is favorable for the primary polymerization of aromatic hydrocarbon molecules through a cross-linking agent to form precursor substances of the carbon nanofibers.
Method for preparing condensed ring aromatic hydrocarbon mixture and cross-linking agent in inorganic structure template
Acid sitesThe polycyclic polynuclear aromatic hydrocarbon is condensed into a polycyclic polynuclear aromatic hydrocarbon substance under the catalysis of (90-150 ℃) at a lower temperature, and the substance is a precursor for forming the carbon nanofiber. The reaction of the polycyclic aromatic hydrocarbon mixture with the crosslinking agent is a cationic polycondensation reaction in view of the process mechanism. The cross-linking agent is in
Under the action of an acid catalyst, carbocations are formed, electrophilic substitution reaction is carried out on aromatic rings, one cross-linking agent molecule can connect two aromatic rings, and polycyclic and polynuclear aromatic hydrocarbon macromolecules with long chains or network structures are formed through condensation polymerization. The specific reaction process is shown in figure 1.
And step 3: carrying out high-temperature carbonization treatment on the inorganic structure template-condensed ring aromatic hydrocarbon mixture to obtain a carbonized product;
specifically, when the inorganic structure template-fused ring aromatic hydrocarbon mixture is subjected to high-temperature carbonization treatment, the structure of the polycyclic and polynuclear aromatic hydrocarbon condensate gradually condenses with the increase of the treatment temperature to form a graphite sheet structure, and finally, continuous carbon nanofibers are formed in the inorganic structure template, and a specific heat treatment carbonization process is shown in fig. 2.
And heating the high-temperature carbonization treatment by adopting a tubular furnace, taking nitrogen as a carrier gas, wherein the heating rate in the carbonization process is 3-15 ℃/min, the temperature range of the heat treatment of the high-temperature carbonization treatment is 850-1200 ℃, the treatment time is 45-120 min, the flow of the nitrogen in the treatment process is 60-700 ml/min, and the carbonized solid is cooled to the room temperature in the corresponding nitrogen.
The strict control of the carbonization treatment conditions is favorable for gradually converting the polycyclic aromatic hydrocarbon molecular polymer into a carbon structure, so that a continuous fibrous material is generated, and meanwhile, the defects of nonuniform micro-area structure and fibers caused by the carbonization process can be avoided.
Step 4, removing the inorganic structure template material to prepare and obtain the carbon nanofiber;
in the step 4, the inorganic structure template needs to be removed after the complete high-temperature carbonization, and the inorganic structure template material is removed by adopting a method of sequentially dissolving and eluting a sulfuric acid solution and a sodium hydroxide solution. The method of dissolving by hydrofluoric acid is avoided, the use of hydrofluoric acid is easy to cause a large amount of fluorine-containing wastewater, and meanwhile, hydrogen fluoride has strong toxicity and corrosivity and has special requirements on equipment and operation, so that the difficulty and the cost of treatment operation are increased. It is mainly common in the prior art to prepare relatively small quantities for laboratory studies, and to remove the template quickly using hydrofluoric acid. However, the use of hydrofluoric acid in large amounts causes many problems when large-scale production is required. Because the invention mostly adopts composite natural minerals as the structural template, the template can be removed by adopting a mild and environment-friendly method of sequentially dissolving and eluting sulfuric acid solution and sodium hydroxide solution.
According to the method, the carbon nanofiber is prepared by removing the inorganic structure template by sequentially adopting the sulfuric acid solution with the mass concentration of 5.0-15% and the sodium hydroxide solution with the mass concentration of 8.0-16%, and the mass concentration of the sulfuric acid and the sodium hydroxide solution is controlled, so that the inorganic template structure can be effectively removed, and a large amount of pollution solution or inorganic salt waste can be avoided. Part of alumina in halloysite dissolved by sulfuric acid solution is dissolved out in the form of aluminum sulfate, part of magnesia in sepiolite and serpentine is dissolved out in the form of magnesium sulfate, and metal salt can be recovered while removing the template structure. The sodium hydroxide solution is utilized to dissolve the silicon dioxide component in the inorganic structure, and the silicon dioxide is recovered in the form of sodium silicate of water glass, so that new pollution is avoided.
It is noted that, when the acid washing is carried out, the ratio of the sulfuric acid solution to the carbonized product is 20-150 ml/g, the treatment temperature is 50-90 ℃, and the treatment time is 30-120 min. The strict control of the acid washing condition is favorable for dissolving part of alumina in halloysite in a sulfuric acid solution to be dissolved out in the form of aluminum sulfate, and dissolving part of magnesia in sepiolite and serpentine in the form of magnesium sulfate, so that the metal salt can be recovered while the template structure is removed.
And (3) carrying out alkali washing treatment after acid washing treatment, wherein the ratio of the sodium hydroxide solution to the carbonized product is 30-170 ml/g, the treatment temperature is 60-95 ℃, and the treatment time is 30-120 min. And further cleaning the treated solid for 3-6 times by using deionized water with the mass 5-15 times, and drying for 1-3 h at 100-120 ℃ in the air. And preparing the carbon nanofiber. Strict control of the alkali washing condition is favorable for dissolving the silicon dioxide component in the inorganic structure, and the silicon dioxide is recovered in the form of sodium silicate of water glass, so that new pollution is avoided.
Compared with the prior art, the method adopts natural cheap inorganic mineral as the structural template, simultaneously takes the polycyclic aromatic hydrocarbon mixture separated from the coal tar as the precursor substance of the carbon structure, and directly forms the continuous carbon nanofiber structure by controllable carbonization in the structure of the inorganic template.
Example 1
The embodiment provides a preparation method of carbon nanofibers based on an inorganic structure template, which comprises the following steps:
step 1, pre-treating 100g of inorganic structure template material (shown in table 1) by using 7kg of sulfuric acid solution with the mass concentration of 6%, wherein the treatment temperature is 60 ℃ and the treatment time is 30 min. The solid treated by the sulfuric acid solution is further washed for 5 times by using deionized water with the mass being 4 times that of the solid, and is dried for 1.5 hours at the temperature of 120 ℃ in the air.
And 2, carrying out impregnation and structure intercalation treatment on the pretreated inorganic structure template material by utilizing a tetrahydrofuran solution of a mixture of a crosslinking agent and fused ring aromatic hydrocarbon (the mass concentration of the crosslinking agent and the fused ring aromatic hydrocarbon is 10%), wherein the impregnation load is 20% of the mass of the inorganic structure template material, the temperature of the structure intercalation treatment is 120 ℃, and the treatment time is 60 min. The polycyclic aromatic hydrocarbon mixture consists of 40% of naphthalene, 20% of pyrene and the balance of naphthalene; the cross-linking agent is terephthalyl alcohol, and the using amount of the cross-linking agent is 0.8 time of the mass of the polycyclic aromatic hydrocarbon mixture.
And 3, carrying out high-temperature carbonization treatment on the mixture of the inorganic structure template and the polycyclic aromatic hydrocarbon, and removing the inorganic structure template to prepare the carbon nanofiber. The high-temperature carbonization treatment adopts a tubular furnace for heating, nitrogen is used as carrier gas, the temperature rise rate in the carbonization process is 6 ℃/min, the temperature interval of the heat treatment of the high-temperature carbonization treatment is 950 ℃, the treatment time is 90min, and the flow rate of the nitrogen in the treatment process is 220 ml/min. The carbonized solid (carbonized product) was cooled to room temperature under a corresponding nitrogen atmosphere.
And 4, removing the inorganic structure template material to prepare the carbon nanofiber.
Firstly, carrying out acid washing treatment by adopting a sulfuric acid solution with the mass concentration of 10%, wherein the ratio of the sulfuric acid solution to a carbonized product is 100ml/g, the treatment temperature is 70 ℃, and the treatment time is 50 min. And sequentially adopting a sodium hydroxide solution with the mass concentration of 12% to carry out alkali washing treatment, wherein the ratio of the sodium hydroxide solution to the carbonized product is 100ml/g, the treatment temperature is 80 ℃, and the treatment time is 90 min. The treated solid was further washed 5 times with deionized water 10 times the mass and dried in air at 110 ℃ for 1.5 h. Thus obtaining the carbon nano fiber without the inorganic structure template.
TABLE 1 Properties of carbon nanofibers made from different inorganic structure template materials
The diameter and the length of the existing carbon nano fiber are difficult to realize effective control, the fiber orientation is disordered, and the carbon nano fiber is difficult to disperse, so that the specific application of the material has some problems. The invention adopts Halloysite (Halloysite), Sepiolite (Sepiolite) and serpentine (Chrysotile) as inorganic structure templates, and the inorganic structure templates have uniform fiber size and regular fiber orientation, thereby achieving the purpose of adjusting and controlling the diameter and the length of the carbon nano-fiber. The length L of the carbon nanofiber prepared by the method is 100-1200 nm, the diameter D of the nanofiber is 10-100 nm, and the L/D ratio is 10-60.
Example 2
The embodiment provides a preparation method of carbon nanofibers based on an inorganic structure template, which comprises the following steps:
step 1, pretreating 100g of halloysite by adopting 7kg of sulfuric acid solution with the mass concentration of 6%, wherein the treatment temperature is 60 ℃, and the treatment time is 30 min. The solid treated by the sulfuric acid solution is further washed for 5 times by using deionized water with the mass being 4 times that of the solid, and is dried for 1.5 hours at the temperature of 120 ℃ in the air.
And 2, carrying out impregnation and structure intercalation treatment on the pretreated inorganic structure template material by using a tetrahydrofuran solution containing a mixture of a crosslinking agent and fused ring aromatic hydrocarbon (the mass concentration of the crosslinking agent and the fused ring aromatic hydrocarbon is 10%), wherein the impregnation load amount, the dosage of the fused ring aromatic hydrocarbon mixture and the crosslinking agent are shown in the table 2, the temperature of the structure intercalation treatment is 120 ℃, and the treatment time is 60 min.
And 3, carrying out high-temperature carbonization treatment on the inorganic structure template-condensed ring aromatic hydrocarbon mixture to obtain a carbonized product. The high-temperature carbonization treatment adopts a tubular furnace for heating, nitrogen is used as carrier gas, the temperature rise rate in the carbonization process is 6 ℃/min, the temperature interval of the heat treatment of the high-temperature carbonization treatment is 950 ℃, the treatment time is 90min, and the flow rate of the nitrogen in the treatment process is 220 ml/min. The carbonized solid (carbonized product) was cooled to room temperature under a corresponding nitrogen atmosphere.
And 4, removing the inorganic structure template material to prepare the carbon nanofiber.
Firstly, carrying out acid washing treatment by adopting a sulfuric acid solution with the mass concentration of 10%, wherein the ratio of the sulfuric acid solution to a carbonized product is 100ml/g, the treatment temperature is 70 ℃, and the treatment time is 50 min. And sequentially adopting a sodium hydroxide solution with the mass concentration of 12% to carry out alkali washing treatment, wherein the ratio of the sodium hydroxide solution to the carbonized product is 100ml/g, the treatment temperature is 80 ℃, and the treatment time is 90 min. The treated solid was further washed 5 times with deionized water 10 times the mass and dried in air at 110 ℃ for 1.5 h. Thus obtaining the carbon nano fiber without the inorganic structure template.
TABLE 2 composition of impregnated polycyclic polynuclear aromatic hydrocarbon mixtures
Example 3
The embodiment provides a preparation method of carbon nanofibers based on an inorganic structure template, which comprises the following steps:
step 1, pretreating 100g of halloysite by adopting 7kg of sulfuric acid solution with the mass concentration of 6%, wherein the treatment temperature is 60 ℃, and the treatment time is 30 min. The solid treated by the sulfuric acid solution is further washed for 5 times by using deionized water with the mass being 4 times that of the solid, and is dried for 1.5 hours at the temperature of 120 ℃ in the air.
And 2, carrying out impregnation and structure intercalation treatment on the pretreated inorganic structure template material by using a tetrahydrofuran solution containing a mixture of a crosslinking agent and fused ring aromatic hydrocarbon (the mass concentration of the crosslinking agent and the fused ring aromatic hydrocarbon is 10%), wherein the impregnation load is 20% of the mass of the inorganic structure template material, the temperature of the structure intercalation treatment is 120 ℃, and the treatment time is 60 min. The polycyclic aromatic hydrocarbon mixture consists of 40% of naphthalene, 20% of pyrene and the balance of naphthalene; the cross-linking agent is terephthalyl alcohol, and the using amount of the cross-linking agent is 0.8 time of the mass of the polycyclic aromatic hydrocarbon mixture.
And 3, carrying out high-temperature carbonization treatment on the inorganic structure template-condensed ring aromatic hydrocarbon mixture to obtain a carbonized product. The high temperature carbonization treatment was carried out in a tube furnace with nitrogen as carrier gas and the carbonization process parameters are listed in Table 3. The carbonized solid (carbonized product) was cooled to room temperature under a corresponding nitrogen atmosphere.
And 4, removing the inorganic structure template material to prepare the carbon nanofiber.
Firstly, carrying out acid washing treatment by adopting a sulfuric acid solution with the mass concentration of 10%, wherein the ratio of the sulfuric acid solution to a carbonized product is 100ml/g, the treatment temperature is 70 ℃, and the treatment time is 50 min. And sequentially adopting a sodium hydroxide solution with the mass concentration of 12% to carry out alkali washing treatment, wherein the ratio of the sodium hydroxide solution to the carbonized product is 100ml/g, the treatment temperature is 80 ℃, and the treatment time is 90 min. The treated solid was further washed 5 times with deionized water 10 times the mass and dried in air at 110 ℃ for 1.5 h. Thus obtaining the carbon nano fiber without the inorganic structure template.
TABLE 3 parameters of carbonization treatment conditions
Example 4
The embodiment provides a preparation method of carbon nanofibers based on an inorganic structure template, which comprises the following steps:
step 1, pretreating 100g of halloysite by adopting 7kg of sulfuric acid solution with the mass concentration of 6%, wherein the treatment temperature is 60 ℃, and the treatment time is 30 min. The solid treated by the sulfuric acid solution is further washed for 5 times by using deionized water with the mass being 4 times that of the solid, and is dried for 1.5 hours at the temperature of 120 ℃ in the air.
And 2, carrying out impregnation and structure intercalation treatment on the pretreated inorganic structure template material by using a tetrahydrofuran solution containing a mixture of a crosslinking agent and fused ring aromatic hydrocarbon (the mass concentration of the crosslinking agent and the fused ring aromatic hydrocarbon is 10%), wherein the impregnation load is 20% of the mass of the inorganic structure template material, the temperature of the structure intercalation treatment is 120 ℃, and the treatment time is 60 min. The polycyclic aromatic hydrocarbon mixture consists of 40% of naphthalene, 20% of pyrene and the balance of naphthalene; the cross-linking agent is terephthalyl alcohol, and the using amount of the cross-linking agent is 0.8 time of the mass of the polycyclic aromatic hydrocarbon mixture.
And 3, carrying out high-temperature carbonization treatment on the inorganic structure template-condensed ring aromatic hydrocarbon mixture to obtain a carbonized product. The high-temperature carbonization treatment adopts a tubular furnace for heating, nitrogen is used as carrier gas, the temperature rise rate in the carbonization process is 6 ℃/min, the temperature interval of the heat treatment is 950 ℃, the treatment time is 90min, and the flow rate of the nitrogen in the treatment process is 220 ml/min. The carbonized solid (carbonized product) was cooled to room temperature under a corresponding nitrogen atmosphere.
And 4, removing the inorganic structure template material to prepare the carbon nanofiber.
Firstly, acid cleaning treatment is carried out by adopting sulfuric acid solution, the treatment temperature is 70 ℃, and the treatment time is 50 min. And sequentially performing alkali washing treatment by using a sodium hydroxide solution, wherein the treatment temperature is 80 ℃, the treatment time is 90min, and the parameters of the sulfuric acid solution and the sodium hydroxide solution are shown in Table 4. The treated solid was further washed 5 times with deionized water 10 times the mass and dried in air at 110 ℃ for 1.5 h. Thus obtaining the carbon nano fiber without the inorganic structure template.
TABLE 4 Condition parameters for removing inorganic structural template materials
Example 5
The embodiment provides a preparation method of carbon nanofibers based on an inorganic structure template, which comprises the following steps:
step 1, pretreating 100g of halloysite by adopting 7kg of sulfuric acid solution with the mass concentration of 6%, wherein the treatment temperature is 60 ℃, and the treatment time is 30 min. The solid treated by the sulfuric acid solution is further washed for 5 times by using deionized water with the mass being 4 times that of the solid, and is dried for 1.5 hours at the temperature of 120 ℃ in the air.
And 2, carrying out impregnation and structural intercalation treatment on the pretreated inorganic structure template material by using a tetrahydrofuran solution containing a mixture of a crosslinking agent and fused ring aromatic hydrocarbon (the mass concentration of the mixture of the crosslinking agent and the fused ring aromatic hydrocarbon is 10%), wherein the treatment condition parameters are listed in Table 5. The polycyclic aromatic hydrocarbon mixture consists of 40% of naphthalene, 20% of pyrene and the balance of naphthalene; the cross-linking agent is terephthalyl alcohol, and the using amount of the cross-linking agent is 0.8 time of the mass of the polycyclic aromatic hydrocarbon mixture.
And 3, carrying out high-temperature carbonization treatment on the inorganic structure template-condensed ring aromatic hydrocarbon mixture to obtain a carbonized product. The high-temperature carbonization treatment adopts a tubular furnace for heating, nitrogen is used as carrier gas, the temperature rise rate in the carbonization process is 6 ℃/min, the temperature interval of the heat treatment of the high-temperature carbonization treatment is 950 ℃, the treatment time is 90min, and the flow rate of the nitrogen in the treatment process is 220 ml/min. The carbonized solid (carbonized product) was cooled to room temperature under a corresponding nitrogen atmosphere.
And 4, removing the inorganic structure template material to prepare the carbon nanofiber.
Firstly, carrying out acid washing treatment by adopting a sulfuric acid solution with the mass concentration of 10%, wherein the ratio of the sulfuric acid solution to a carbonized product is 100ml/g, the treatment temperature is 70 ℃, and the treatment time is 50 min. And sequentially adopting a sodium hydroxide solution with the mass concentration of 12% to carry out alkali washing treatment, wherein the ratio of the sodium hydroxide solution to the carbonized product is 100ml/g, the treatment temperature is 80 ℃, and the treatment time is 90 min. The treated solid was further washed 5 times with deionized water 10 times the mass and dried in air at 110 ℃ for 1.5 h. Thus obtaining the carbon nano fiber without the inorganic structure template.
TABLE 5 Effect of intercalation processing Condition parameters on the Properties of the materials obtained
The above description is only for the preferred embodiment 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 are included in the scope of the present invention.
Claims (10)
1. A method for preparing carbon nano-fiber based on inorganic structure template is characterized in that,
the raw materials for preparing the carbon nano fiber comprise an inorganic structure template material and a tetrahydrofuran solution containing a mixture of a cross-linking agent and polycyclic aromatic hydrocarbon;
the inorganic structure template material is one of halloysite, sepiolite or serpentine;
the polycyclic aromatic hydrocarbon mixture comprises naphthalene, phenanthrene and pyrene; 20-60% of phenanthrene, 10-30% of pyrene and the balance of naphthalene;
the usage amount of the cross-linking agent is 0.45-1.3 times of the mass of the polycyclic aromatic hydrocarbon mixture;
the preparation method of the carbon nanofiber based on the inorganic structure template comprises the following steps:
step 1, pretreating an inorganic structure template material to obtain a pretreated inorganic structure template material;
in the step 1, a sulfuric acid solution with the mass concentration of 1.0-10% is used for pretreating the inorganic structure template material, the dosage ratio of the sulfuric acid solution to the inorganic structure template material is 10-100 ml/g, the pretreatment temperature is 40-90 ℃, and the pretreatment time is 10-90 min;
step 2, dipping and structural intercalation treatment are carried out on the pretreated inorganic structure template by utilizing tetrahydrofuran solution containing a mixture of a cross-linking agent and polycyclic aromatic hydrocarbon;
in the step 2, the loading amount of the mixture of the cross-linking agent and the polycyclic aromatic hydrocarbon is 5-25% of the mass of the inorganic structure template material, the temperature for carrying out the dipping and the structure intercalation treatment is 60-150 ℃, and the time for carrying out the dipping and the structure intercalation treatment is 30-120 min;
step 3, carrying out high-temperature carbonization treatment on the obtained inorganic structure template-condensed ring aromatic hydrocarbon mixture to obtain a carbonized product;
step 4, removing the inorganic structure template to prepare and obtain the carbon nanofiber;
in the step 4, acid washing and alkali washing are sequentially carried out by adopting a sulfuric acid solution and a sodium hydroxide solution, and the inorganic structure template material is removed by elution;
the mass concentration of the sulfuric acid solution is 5.0-15%, and the ratio of the sulfuric acid solution to the carbonized product is 20-150 ml/g; the pickling treatment temperature is 50-90 ℃, and the treatment time is 30-120 min.
2. The method of claim 1, wherein the crosslinking agent is one of benzaldehyde, terephthalyl alcohol, terephthaloyl chloride, divinylbenzene, terephthalaldehyde, and trioxymethylene.
3. The method for preparing carbon nanofibers based on inorganic structure templates as claimed in claim 1, wherein the length L of the carbon nanofibers is in the range of 100 to 1200nm, the diameter D of the carbon nanofibers is in the range of 10 to 100nm, and the L/D ratio is in the range of 10 to 60.
4. The method for preparing carbon nanofibers based on inorganic structure templates as claimed in claim 1, wherein in the step 1, the inorganic structure template material is pretreated by using a sulfuric acid solution with a mass concentration of 6.0-10%, the dosage ratio of the sulfuric acid solution to the inorganic structure template material is 10-100 ml/g, the pretreatment temperature is 60-90 ℃, and the pretreatment time is 30-90 min.
5. The method for preparing carbon nanofibers based on inorganic structure templates according to claim 1, wherein in the step 2, the loading amount of the mixture of the crosslinking agent and the polycyclic aromatic hydrocarbon is 10-25% of the mass of the inorganic structure template material, the temperature for carrying out the impregnation and structure intercalation treatment is 120-150 ℃, and the time for carrying out the impregnation and structure intercalation treatment is 60-120 min.
6. The method for preparing carbon nanofibers based on inorganic structure templates according to claim 1, wherein in the step 3, the inorganic structure template-condensed ring aromatic hydrocarbon mixture is heated to 850-1200 ℃ at a heating rate of 3-15 ℃/min for high temperature carbonization.
7. The method for preparing carbon nanofibers based on inorganic structure templates as claimed in claim 6, wherein the high temperature carbonization treatment time is 45-120 min, and the flow rate of nitrogen gas during the treatment process is 60-700 ml/min.
8. The method for preparing carbon nanofibers based on inorganic structure templates according to claim 7, wherein in the step 4, the inorganic structure template material is removed by using sulfuric acid solution and sodium hydroxide solution to carry out acid washing and alkali washing in sequence and eluting;
the mass concentration of the sulfuric acid solution is 10.0-15%, and the ratio of the sulfuric acid solution to the carbonized product is 100-150 ml/g; the pickling treatment temperature is 70-90 ℃, and the treatment time is 50-120 min.
9. The method for preparing carbon nanofibers based on inorganic structure templates according to claim 8, wherein in the step 4, the mass concentration of the sodium hydroxide solution is 8.0-16%, and the ratio of the sodium hydroxide solution to the carbonized product is 30-170 ml/g.
10. The method for preparing the carbon nanofiber based on the inorganic structure template according to claim 8, wherein the temperature of the alkali washing treatment is 60-95 ℃, and the treatment time is 30-120 min.
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| CN108190865A (en) * | 2018-02-08 | 2018-06-22 | 东华大学 | A kind of method that graphene is prepared based on template-solid-phase carbon source thermal cracking |
| CN110055625A (en) * | 2019-03-28 | 2019-07-26 | 西南科技大学 | A method of using galapectite as catalyst preparation carbon nano-fiber |
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| CN101723352A (en) * | 2009-11-20 | 2010-06-09 | 上海奥威科技开发有限公司 | Height ratio capacity organic mixed type super capacitor anode material and preparation method thereof |
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| CN105836727A (en) * | 2016-03-21 | 2016-08-10 | 陕西师范大学 | Method for low-cost preparation of multi-walled carbon nanotubes |
| CN107128903A (en) * | 2017-06-02 | 2017-09-05 | 扬州大学 | To crimp the method that the halloysite nanotubes of layer structure prepare graphene |
| CN108190865A (en) * | 2018-02-08 | 2018-06-22 | 东华大学 | A kind of method that graphene is prepared based on template-solid-phase carbon source thermal cracking |
| CN110055625A (en) * | 2019-03-28 | 2019-07-26 | 西南科技大学 | A method of using galapectite as catalyst preparation carbon nano-fiber |
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