CN101445234B - A preparation method of graphitized carbon nano material - Google Patents

Abstract

The invention discloses a preparation method of graphitized carbon nanometer material, which relates to a preparation method of carbon nanometer material. The invention solves the problems of high cost and environmental pollution in the prior preparation of graphitized carbon nanometer materials. The method of the present invention is as follows: 1. pretreatment of carbon source; 2. catalyst and pretreated carbon source in solvent; 3. pre-carbonization; 4. heat treatment; 5. acid treatment; 6. after physical activation or chemical activation That's it. The invention has the advantages of simple process, little environmental pollution, low cost, simple required equipment and easy commercialization.

Description

Preparation method of graphitized carbon nanomaterials

technical field

The invention relates to a preparation method of carbon nanometer material.

Background technique

In recent years, research on carbon nanomaterials has attracted great attention from academia and business circles due to their application value in separation, energy storage, electrocatalysis, drug delivery, etc. Because graphite has high thermal stability, chemical stability, electrical conductivity, high electronic conductivity, field emission performance, and metal and semiconductor properties, carbon nanomaterials with graphite structure have greatly improved performance and can be applied to the preparation of Industrial electrodes, anode materials for lithium-ion batteries and as supports for electrochemical catalysts. In addition, the microscopic morphology of carbon materials also has a great influence on its application. For example, graphite capsules can be used as catalyst supports, dye adsorption and drug storage, and flake graphite can be used as cold field transistor emitters. Therefore, exploiting new methods to prepare graphitized nanocarbon materials with various morphologies has attracted extensive attention of researchers.

At present, the methods for synthesizing graphitized carbon nanomaterials mainly include arc discharge method, chemical vapor deposition method, laser ablation method, electron beam irradiation method, and thermal decomposition of carbon-containing metal compounds. Depending on the method used and the carbon precursor used, graphitized carbon materials with various morphologies such as nanocapsules, nanotrees, nanoscrolls, nanofibers, nanoribbons, nanosheets, nanohorns, nanowalls, etc. have been successfully is synthesized. However, these methods have the following disadvantages: high reaction temperature, complex process, low yield and generation of by-products, and the prepared product needs further purification before use, thus greatly increasing the cost; in addition, the carbon source used is mostly benzene , toluene, acetylene, methane and other non-renewable resources extracted from coal and ore, from the perspective of preparation technology, the environmental pollution is relatively serious, so it is not conducive to commercial application. The solid-phase pyrolysis method is considered to be a more effective preparation method, and the product has uniform shape and size. By simply adjusting the type of carbon source and catalyst, graphitized nano-carbon materials with different shapes can be prepared. At present, phenolic resins are mostly used as carbon sources. These substances are all petroleum extracts. In today's resource-scarce situation, the cost will be high, which limits its commercial production.

Contents of the invention

The object of the present invention is to solve the problems of high cost and environmental pollution in the existing preparation of graphitized carbon nanomaterials; and to provide a preparation method of graphitized carbon nanomaterials.

The preparation method of graphitized carbon nanomaterials in the present invention is completed by following steps: one, carbon source is carried out pretreatment 1～10h; Two, add catalyst and pretreated carbon source in solvent, at 50 ℃, Stir at a stirring speed of 100-300r/min for 8h, wherein the mass ratio of carbon source to catalyst is 0.025-1:1; 3. Pre-carbonize the mixture in step 2 at a temperature of 80-450°C for 2-8h, and the pre-carbonization atmosphere is Air, oxygen, nitrogen, argon, helium, or a mixture of several gases; 4. Raise the temperature from room temperature to 400-1200°C at a rate of 1-15°C/min. Under the conditions of atmosphere flow rate of 30-2000mL/min and heat treatment temperature of 400-1200°C, the product of Step 3 is heat-treated for 10min-10h, wherein the heat-treatment atmosphere is nitrogen, argon, helium, carbon monoxide, carbon dioxide, hydrogen sulfide, hydrogen and One or a mixture of several gases in water vapor; 5. After grinding the product of step 4, add it to nitric acid or hydrochloric acid with a mass concentration of 15% to 20%, and reflux at 110 to 140°C for 6 to 14 hours , washed with distilled water until neutral, then dried at 110-120°C or vacuum-dried at 60-80°C for 6-8 hours; 6. Physically or chemically activate the product of step 5, and obtain graphite after drying carbon nanomaterials.

The carbon source in step 1 is agricultural and forestry crop extract or agricultural and forestry waste; the agricultural and forestry crop extract is glucose, sucrose, fructose or starch; the agricultural and forestry waste is corn stalk, sorghum stalk, sugar beet bagasse, bagasse or sawdust.

The carbon source pretreatment method described in step 1 is a microwave method, a hydrothermal method, an ultrasonic method, a spray method, an acid treatment method or an alkali treatment method.

The catalyst described in step 2 is ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, potassium ferricyanide, potassium ferrocyanide, potassium ferrite trioxalate, chlorine One or a mixture of cobalt oxide, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickel sulfate, nickel acetate.

The solvent described in step 2 is one of water, methanol, ethanol, isopropanol or a mixture of several of them.

The physical activation method described in step 6 is as follows: under the conditions of water vapor, carbon dioxide, hydrogen or carbon monoxide atmosphere, and the physical activation temperature is 200-500°C, and the physical gas flow rate is 100-4000mL/min, the product of step 5 is Physical activation 0.5 ~ 24h.

The chemical activation method described in step 6 is as follows: the product of step 5 is activated in an inorganic solution for 3 to 12 hours at an activation temperature of 80 to 180° C., wherein the mass concentration of the inorganic solution is 10% to 45%. It is one of potassium hydroxide, sodium hydroxide, phosphoric acid, hydrochloric acid, nitric acid, potassium permanganate or a mixture of two of them.

The drying described in step 6 is drying at 110-120° C. or vacuum drying at 60-80° C. for 6-8 hours.

The invention adopts agricultural and forestry crop extracts and agricultural and forestry wastes as carbon sources, and the sources are extensive and cheap. On the one hand, the problem of environmental protection is solved, and on the other hand, the cost of synthesizing graphitized carbon nanometer materials is greatly reduced. The invention is based on the coordination process of electrostatic interaction, complexation and other weak interactions, covers the low-temperature dissolution-coordination-high-temperature graphitization process, and has low energy consumption. The invention has simple preparation process, simple experimental equipment, low cost and easy commercialization. The method of the present invention can prepare graphitized carbon nanomaterials and graphitized carbon/magnetic particle composite materials with nano-sized capsules, sheets, fibers, spirals, rolls, tubes, horns, strips, etc. , used in the adsorption and separation of organic dyes, electrochemical aspects, and super capacitors.

Description of drawings

Fig. 1 is the X-ray diffraction spectrum of the graphitized carbon nanomaterial prepared in Embodiment 53. Fig. 2 is a Raman spectrum of graphitized carbon nanomaterials prepared in Embodiment 53. Fig. 3 is a transmission electron micrograph of graphitized carbon nanomaterials prepared in Embodiment 53. Fig. 4 is a high-resolution transmission electron fiber microscope photo of graphitized carbon nanomaterials prepared in Embodiment 53.

Detailed ways

The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.

Specific Embodiment 1: The preparation method of graphitized carbon nanomaterials in this embodiment is completed by the following steps: 1. Pretreat the carbon source for 1 to 10 hours; 2. Add catalyst and pretreated carbon source to the solvent , stirring at 50°C and 100-300r/min stirring speed for 8h, wherein the mass ratio of carbon source to catalyst is 0.025-1:1; 3. Pre-carbonize the mixture in step 2 at a temperature of 80-450°C for 2-8h , the pre-carbonization atmosphere is air, oxygen, nitrogen, argon, helium or a mixture of several gases; 4. The temperature rises from room temperature to 400-1200°C at a rate of 1-15°C/min. Under the condition of heat treatment atmosphere, the heat treatment atmosphere flow rate is 30-2000mL/min, and the heat treatment temperature is 400-1200°C, heat-treat the product of step 3 for 10min-10h, wherein the heat treatment atmosphere is nitrogen, argon, helium, carbon monoxide, carbon dioxide, Hydrogen sulfide, hydrogen gas and a mixed gas of one or more gases in water vapor; 5. After grinding the product of step 4, add it to nitric acid or hydrochloric acid with a mass concentration of 15% to 20%, at 110 to 140°C Reflux for 6-14 hours, wash with distilled water until neutral, then dry at 110-120°C or vacuum-dry at 60-80°C for 6-8 hours; 6. Physically activate or chemically activate the product of step 5 , to obtain graphitized carbon nanomaterials after drying.

When the pre-carbonization atmosphere in Step 3 of this embodiment is a mixture, various pre-carbonization atmospheres are mixed in any ratio. When the heat treatment atmosphere in step 4 is a mixture, various heat treatment atmospheres are mixed in any ratio. In step 5, the particle size is 20-40nm through grinding.

Embodiment 2: This embodiment differs from Embodiment 1 in that the carbon source in Step 1 is agricultural and forestry crop extracts or agricultural and forestry wastes. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 3: This embodiment is different from Embodiment 2 in that: the agricultural and forestry crop extract is glucose, sucrose, fructose or starch. Other steps and parameters are the same as in the second embodiment.

Embodiment 4: This embodiment is different from Embodiment 2 in that the agricultural and forestry wastes are corn stalks, sorghum stalks, sugar beet bagasse, bagasse or sawdust. Other steps and parameters are the same as in the second embodiment.

Embodiment 5: This embodiment differs from Embodiment 4 in that the agricultural and forestry wastes are corn stalks or sorghum stalks. In step 1, the agricultural and forestry wastes are crushed and pretreated for 1 to 10 hours before the operation of step 2. After centrifugation, wash with water until the pH of the washing solution is 6-8. Other steps and parameters are the same as those in Embodiment 4.

Embodiment 6: The difference between this embodiment and Embodiment 1, 2, 3 or 4 is that the carbon source pretreatment method described in step 1 is microwave method, hydrothermal method, ultrasonic method, spray method, acid treatment or alkaline treatment. Other steps and parameters are the same as those in Embodiment 1, 2, 3 or 4.

Specific embodiment seven: the difference between this embodiment and specific embodiment six is that the carbon source pretreatment by microwave method is carried out according to the following reaction: under the condition that the microwave intensity is 3.0～8.0kW, the carbon source is treated with microwave for 10 ~60min, the pretreatment of carbon source is completed. Other steps and parameters are the same as those in Embodiment 6.

Embodiment 8: The difference between this embodiment and Embodiment 6 is that the carbon source is pretreated by the hydrothermal method according to the following reaction: at a temperature of 120 to 180°C, the carbon source is hydrothermally treated for 4 to 10 °C. 8h, that is, the pretreatment of carbon source is completed. Other steps and parameters are the same as those in Embodiment 6.

Specific embodiment nine: the difference between this embodiment and specific embodiment six is that the pretreatment of the carbon source by the ultrasonic method is carried out according to the following reaction: the pretreatment of the carbon source by the ultrasonic method is carried out according to the following reaction: at a frequency of Under the condition of 2-6KHz, the carbon source is ultrasonically treated for 0.5-2h to complete the pretreatment of the carbon source. Other steps and parameters are the same as those in Embodiment 6.

Embodiment 10: The difference between this embodiment and Embodiment 6 is that the pretreatment of the carbon source by spraying is carried out according to the following reaction: the carbon source is mixed with the activator, and sprayed at 220V, 60-100Hz frequency Pretreatment, wherein the activator is hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide or potassium hydroxide with a mass concentration of 10-20%. Other steps and parameters are the same as those in Embodiment 6.

Embodiment 11: The difference between this embodiment and Embodiment 6 is that the pretreatment of the carbon source by acid treatment is carried out according to the following reaction: the carbon source is added to a hydrochloric acid solution with a mass concentration of 10-15%. Ultrasonic treatment for 3 to 6 hours is enough. Other steps and parameters are the same as those in Embodiment 6.

Embodiment 12: The difference between this embodiment and Embodiment 6 is that the pretreatment of the carbon source by alkali treatment is carried out according to the following reaction: the carbon source is added to a KOH solution with a mass concentration of 10% to 20%. Stir for 0.5-4 hours, then hydrothermally treat for 2-5 hours, wash with distilled water until the pH of the lotion is 6-8, and then dry at 80-100°C. Other steps and parameters are the same as those in Embodiment 6.

Specific embodiment thirteen: this embodiment is different from specific embodiment one or six: the catalyst described in step two is ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate , Potassium ferricyanide, Potassium ferrocyanide, Potassium ferrioxalate, Cobalt chloride, Cobalt nitrate, Cobalt sulfate, Cobalt acetate, Nickel chloride, Nickel nitrate, Nickel sulfate, Nickel acetate or one of them A mix of several. Other steps and parameters are the same as those in Embodiment 1 or Embodiment 6.

In this embodiment, when the catalyst is a mixture, various catalysts are mixed in any ratio.

Embodiment 14: The difference between this embodiment and Embodiment 1 or 13 is that the solvent described in step 2 is one of water, methanol, ethanol, and isopropanol or a mixture of several of them. Other steps and parameters are the same as those in Embodiment 1 or Embodiment 13.

In this embodiment, when the solvent is a mixture, various solvents are mixed in any ratio.

Embodiment 15: This embodiment is different from Embodiment 1 in that: the pre-carbonization temperature in step 3 is 100-400°C. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 16: This embodiment is different from Embodiment 1 in that: the pre-carbonization temperature in step 3 is 150-350°C. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 17: This embodiment is different from Embodiment 1 in that: the pre-carbonization temperature in step 3 is 200-300°C. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 18: The difference between this embodiment and Embodiment 1 is that the pre-carbonization temperature in Step 3 is 250°C. Other steps and parameters are the same as those in Embodiment 1.

Specific Embodiment Nineteen: This embodiment differs from Specific Embodiment 1 in that: the pre-carbonization time in step 3 is 3-7 hours. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 20: This embodiment is different from Embodiment 1 in that: the pre-carbonization time in step 3 is 4-6 hours. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 21: The difference between this embodiment and Embodiment 1 is that the pre-carbonization time in step 3 is 5 hours. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 22: This embodiment is different from Embodiment 1 in that: the flow rate of the heat treatment atmosphere in step 4 is 100-1000 mL/min. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 23: This embodiment is different from Embodiment 1 in that the flow rate of the heat treatment atmosphere in step 4 is 200-800 mL/min. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 24: This embodiment is different from Embodiment 1 in that the flow rate of the heat treatment atmosphere in step 4 is 500 mL/min. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 25: This embodiment is different from Embodiment 1 in that: the heat treatment temperature in step 4 is 500-1000°C. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 26: This embodiment is different from Embodiment 1 in that: the heat treatment temperature in step 4 is 600-800°C. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 27: The difference between this embodiment and Embodiment 1 is that the heat treatment temperature in step 4 is 700°C. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 28: This embodiment is different from Embodiment 1 in that: in step 4, the heat treatment is for 30 minutes to 8 hours. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 29: This embodiment is different from Embodiment 1 in that: in step 4, heat treatment for 1-5 hours. Other steps and parameters are the same as those in Embodiment 1.

Specific Embodiment Thirty: The difference between this embodiment and Specific Embodiment 1 is: heat treatment for 2 hours in Step 4. Other steps and parameters are the same as those in Embodiment 1.

Specific Embodiment Thirty-one: This embodiment differs from Specific Embodiment 1 in that: in step 5, dry at 100-120°C. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 32: This embodiment is different from Embodiment 1 in that it is dried at 110°C in Step 5. Other steps and parameters are the same as those in Embodiment 1.

Specific Embodiment Thirty-Three: The difference between this embodiment and specific embodiment 1 is that in step 5, vacuum drying is carried out at 65-75° C. for 6.5-7.5 hours. Other steps and parameters are the same as those in Embodiment 1.

Specific Embodiment Thirty-Four: The difference between this embodiment and specific embodiment 1 is that in step 5, vacuum drying is carried out at 70° C. for 7 hours. Other steps and parameters are the same as those in Embodiment 1.

Embodiment 35: The difference between this embodiment and Embodiments 1, 2, 13 or 14 is that the physical activation method described in step 6 is as follows: under the atmosphere of water vapor, carbon dioxide, hydrogen or carbon monoxide, And under the condition that the physical activation temperature is 200-500° C. and the physical gas flow rate is 100-4000 mL/min, the product in step 5 is physically activated for 0.5-24 hours. Other steps and parameters are the same as those in Embodiment 1, 2, 13 or 14.

In this embodiment, the heating rate from room temperature to 200-500° C. is 5-10° C./min.

Specific Embodiment Thirty-Six: The difference between this embodiment and Specific Embodiment Thirty-five is that the physical activation temperature is 250-450°C. Other steps and parameters are the same as those in Embodiment 35.

Specific embodiment thirty-seven: the difference between this embodiment and specific embodiment thirty-five is that the physical activation temperature is 300°C. Other steps and parameters are the same as those in Embodiment 35.

Specific Embodiment Thirty-Eight: This embodiment differs from Specific Embodiment Thirty-five in that: the physical gas flow rate is 200-3000 mL/min. Other steps and parameters are the same as those in Embodiment 35.

Specific Embodiment Thirty-Nine: This embodiment differs from Specific Embodiment Thirty-five in that: the physical gas flow rate is 500-2000 mL/min. Other steps and parameters are the same as those in Embodiment 35.

Specific Embodiment 40: This embodiment differs from Specific Embodiment 35 in that: the physical gas flow rate is 1000 mL/min. Other steps and parameters are the same as those in Embodiment 35.

Specific Embodiment 41: The difference between this embodiment and Specific Embodiment 35 is that the physical activation is 1-20 hours. Other steps and parameters are the same as those in Embodiment 35.

Embodiment 42: The difference between this embodiment and Embodiment 35 is that the physical activation is 5-15 hours. Other steps and parameters are the same as those in Embodiment 35.

Embodiment 43: The difference between this embodiment and Embodiment 35 is that the physical activation is 10 hours. Other steps and parameters are the same as those in Embodiment 35.

Embodiment 44: The difference between this embodiment and Embodiment 1, 2, 13 or 14 is that the chemical activation method described in step 6 is as follows: at an activation temperature of 80-180°C, the step The five products are activated in an inorganic solution for 3 to 12 hours, wherein the mass concentration of the inorganic solution is 10% to 45%, and the inorganic solution is one of potassium hydroxide, sodium hydroxide, phosphoric acid, hydrochloric acid, nitric acid, and potassium permanganate or a mixture of two of them. Other steps and parameters are the same as those in Embodiment 1, 2, 13 or 14.

In this embodiment, when the inorganic solution is a mixture, various inorganic solutions are mixed in any ratio. The method in this embodiment prepares graphitized carbon nanomaterials with a large specific surface area.

Embodiment 45: The difference between this embodiment and Embodiment 44 is that the activation temperature is 100-150°C. Other steps and parameters are the same as those in Embodiment 44.

Embodiment 46: The difference between this embodiment and Embodiment 44 is that the activation temperature is 120°C. Other steps and parameters are the same as those in Embodiment 44.

Embodiment 47: The difference between this embodiment and Embodiment 44 is that the activation time is 5-10 hours. Other steps and parameters are the same as those in Embodiment 44.

Embodiment 48: The difference between this embodiment and Embodiment 44 is that the activation time is 8 hours. Other steps and parameters are the same as those in Embodiment 44.

Embodiment 49: The difference between this embodiment and Embodiment 44 is that the mass concentration of the inorganic solution is 20%-35%. Other steps and parameters are the same as those in Embodiment 44.

Embodiment 50: This embodiment is different from Embodiment 44 in that the mass concentration of the inorganic solution is 30%. Other steps and parameters are the same as those in Embodiment 44.

Specific Embodiment 51: The difference between this embodiment and specific embodiments 1, 2, 13 or 14 is that the drying in step 6 is carried out at 110-120°C. Other steps and parameters are the same as those in Embodiment 1, 2, 13 or 14.

Embodiment 52: This embodiment is different from Embodiments 1, 2, 13 or 14 in that: the drying in step 6 is vacuum drying at 60-80°C for 6-8 hours. Other steps and parameters are the same as those in Embodiment 1, 2, 13 or 14.

Specific embodiment fifty-three: The preparation method of graphitized carbon nanomaterials in this embodiment is completed by the following steps: 1. Add 10 g of sorghum stalk scraps (40-60 mesh) to 150 mL of KOH solution with a mass concentration of 10% Stir for 0.5 to 4 hours, then hydrothermally treat for 2 to 5 hours, wash with distilled water until the pH of the lotion is 6 to 8, and then dry at 80 to 100°C; 2. Add the pretreated carbon source to a concentration of 100mL 1mol/L ferric chloride aqueous solution, stirred at 50°C, 120-180r/min stirring speed for 8h, centrifuged and washed with water until the pH of the washing liquid = 6-8; 3. In a nitrogen atmosphere, the pre-carbonization temperature is Under the condition of 100°C, pre-carbonize the product of step 2 for 2 hours; 4. Raise the temperature from room temperature to 1000°C at a rate of 10°C/min, in the heat treatment atmosphere, the flow rate of the heat treatment atmosphere is 60mL/min, and the heat treatment temperature is 1000°C Next, heat-treat the product of Step 3 for 2 hours; 5. Grind the product of Step 4 and add it to 150 mL of hydrochloric acid with a mass concentration of 20%, reflux at 110 for 14 hours, and wash with distilled water until the pH of the lotion is 6-8 , and then dried at 110°C; 6. In a carbon dioxide atmosphere, with a physical activation temperature of 300°C and a physical gas flow rate of 100mL/min, physically activate the product in step 5 for 4 hours, and dry it at 100°C After drying, graphitized carbon nanomaterials are obtained.

In this embodiment, the heating rate from room temperature to 300° C. is 5° C./min.

The X-ray diffraction spectrum of this graphitized carbon nanomaterial is shown in Figure 1, as can be seen from the figure, there are obvious crystal plane diffraction peaks on three crystal planes of (002), (100) and (004) , indicating that the material has a graphitized structure. The Raman spectrogram of this graphitized carbon nanomaterial is as shown in Figure 2, as can be clearly seen from the figure, two characteristic peaks G band and D band of graphite, the ratio IG/ID=3.1 of the intensity of two peaks , which further proves that the degree of graphitization of the product is relatively high. The transmission electron microscope photograph of this graphitized carbon nanomaterial is shown in Figure 3, and it can be seen from the figure that the microscopic appearance of the product is a hollow capsule with uniform size, and the size is about 40nm. The high-resolution transmission electron microscope photo of this graphitized carbon nanomaterial is shown in Figure 4. From the figure, it can be clearly seen that the capsule-like curved structure has a measured interplanar spacing of 0.34nm, which is the (002) interplanar spacing of graphite. .

Embodiment 54: The difference between this embodiment and Embodiment 53 is that the catalyst in step 2 is ferrous chloride, ferrous sulfate or ferric sulfate. Other steps and parameters are the same as those in Embodiment 53.

Embodiment 55: This embodiment is different from Embodiment 53 in that: the carbon source in step 1 is corn stalk, the catalyst in step 2 is 0.015mol nickel chloride, and the heat treatment temperature in step 4 is 800 ℃. Other steps and parameters are the same as those in Embodiment 53.

Tested by transmission electron microscope, the result shows that the product is nano-helical graphitic carbon with uniform size.

Embodiment 56: This embodiment is different from Embodiment 55 in that: the catalyst in step 2 is nickel sulfate, nickel acetate, and cobalt acetate. Other steps and parameters are the same as those in Embodiment 55.

Embodiment 57: The difference between this embodiment and Embodiment 56 is that the carbon source in step 1 is beet pulp, the catalyst in step 2 is 0.02mol cobalt chloride, and the heat treatment temperature in step 4 is 1100°C . Other steps and parameters are the same as those in Embodiment 55.

Tested by transmission electron microscope, the result shows that the product is nano flake graphitic carbon with uniform size.

Embodiment 58: This embodiment differs from Embodiment 53 in that the carbon source in step 1 is bagasse, the catalyst in step 2 is 0.015mol cobalt sulfate, and the heat treatment temperature in step 4 is 900°C . Other steps and parameters are the same as those in Embodiment 55.

Tested by transmission electron microscope, the result shows that the product is nanofibrous graphitic carbon with uniform size.

Embodiment 59: This embodiment differs from Embodiment 53 in that: in step 1, the carbon source is wood chips, the catalyst is 0.02 mol trioxalic acid and 0.02 mol potassium ferrite, and the heat treatment time is 4 hours. Other steps and parameters are the same as those in Embodiment 55.

Tested by transmission electron microscope, the results show that the product is nano-tubular graphitic carbon with uniform size.

Specific Embodiment Sixty: The preparation method of graphitized carbon nanomaterials in this embodiment is completed by the following steps: 1. Weigh 10 g of starch, add it to 200 mL of hydrochloric acid solution with a mass concentration of 10%, and use it at a frequency of 4KHz Ultrasonic treatment for 3-6 hours; 2. Add 0.015mol cobalt nitrate and pretreated carbon source to 300mL water, and stir for 8 hours at 50°C and 150-160r/min stirring speed; 3. Pre-carbonize in an air atmosphere at a temperature of 200 Under the condition of ℃, pre-carbonize the product of step 2 for 4 hours; 4. Raise the temperature from room temperature to 900 ℃ at a rate of 10 ℃/min, under the conditions of nitrogen atmosphere, heat treatment atmosphere flow rate of 60mL/min, and heat treatment temperature of 900 ℃ , heat-treat the product of step 3 for 3 hours; 5. Grind the product of step 4 and add it to 150 mL of nitric acid with a mass concentration of 15%, reflux at 110°C for 14 hours, and wash with distilled water until the pH of the lotion=6～8 , and then dried at 110°C or vacuum-dried at 80°C for 6 hours; 6. Under the conditions of water vapor atmosphere, physical activation temperature of 300°C, and physical gas flow rate of 100mL/min, the product of step 5 was After physical activation for 4 hours, graphitized carbon nanomaterials were obtained after vacuum drying at 60° C. for 7 hours.

Then the product was activated at 300° C. for 4 h to obtain the final product. Tested by transmission electron microscope, the results show that the product is nanoribbon graphitic carbon with uniform size.

Embodiment 61: This embodiment is different from Embodiment 60 in that: the catalyst in step 2 is nickel nitrate, iron nitrate or ferrous nitrate. Other steps and parameters are the same as those in Embodiment 60.

Embodiment 62: This embodiment differs from Embodiment 60 in that the carbon source in step 1 is glucose, the catalyst in step 2 is 0.025mol nickel nitrate, and the physical activation time in step 6 is 6 hours. Other steps and parameters are the same as those in Embodiment 60.

Tested by transmission electron microscope, the result shows that the product is nano-horn graphitic carbon with uniform size.

Embodiment 63: The difference between this embodiment and Embodiment 60 is that the carbon source in step 1 is fructose, the catalyst in step 2 is 0.015mol iron sulfate, the heat treatment time in step 4 is 4h, and in step 5, use 25% sulfuric acid solution for acid treatment. Other steps and parameters are the same as those in Embodiment 60.

Tested by transmission electron microscope, the results show that the product is nanoribbon graphitic carbon with uniform size.

Embodiment 64: This embodiment differs from Embodiment 60 in that the carbon source in step 1 is sucrose, the catalyst in step 2 is 0.03mol potassium ferricyanide, and the heat treatment time in step 4 is 4 hours. Other steps and parameters are the same as those in Embodiment 60.

Tested by transmission electron microscope, the results show that the product is nanocapsular graphitic carbon with uniform size.

Claims (5)

1. The preparation method of graphitized carbon nanomaterial is characterized in that the preparation method of graphitized carbon nanomaterial is completed by following steps: one, carbon source is carried out pretreatment 1～10h; Two, add catalyst and in solvent The pretreated carbon source is stirred for 8 hours at 50°C and a stirring speed of 100-300r/min, wherein the mass ratio of carbon source to catalyst is 0.025-1:1; 3. Pre-treated at a temperature of 80-450°C The mixture obtained in carbonization step 2 is 2-8h, and the pre-carbonization atmosphere is a mixed gas of one or more gases in air, oxygen, nitrogen, argon, helium; The room temperature is raised to 400-1200°C, and the product of step 3 is heat-treated for 10min-10h in a heat treatment atmosphere, the flow rate of the heat treatment atmosphere is 30-2000mL/min, and the heat treatment temperature is 400-1200°C, wherein the heat treatment atmosphere is nitrogen, Argon, helium, carbon monoxide, carbon dioxide, hydrogen sulfide, hydrogen and a mixed gas of one or more gases in water vapor; 5. After grinding the product of step 4, add nitric acid with a mass concentration of 15% to 20% Or in hydrochloric acid, reflux at 110-140°C for 6-14h, wash with distilled water until neutral, then dry at 110-120°C or vacuum-dry at 60-80°C for 6-8h; The product of step 5 is activated physically or chemically, and dried to obtain a graphitized carbon nanomaterial; wherein, the carbon source of step 1 is an agricultural and forestry crop extract or agricultural and forestry waste; the agricultural and forestry crop extract is glucose, sucrose, fructose or starch; The agricultural and forestry wastes are corn stalks, sorghum stalks, sugar beet bagasse, bagasse or wood chips; the pretreatment method described in step 1 is microwave method, hydrothermal method, ultrasonic method, spray method, acid treatment method or alkali treatment method; Pretreatment of carbon source by microwave method is carried out according to the following reaction: under the condition of microwave intensity of 3.0 ~ 8.0kW, microwave treatment of carbon source for 10 ~ 60min; pretreatment of carbon source by hydrothermal method is carried out according to the following reaction Method: Under the condition of temperature of 120-180°C, hydrothermally treat the carbon source for 4-8 hours; pretreat the carbon source by ultrasonic method according to the following reaction: under the condition of frequency of 2-6KHz, ultrasonically treat the 0.5～2h; Pretreatment of carbon source by spraying method is carried out according to the following reaction: mix carbon source and activator, spray pretreatment at 220V, 60～100Hz frequency, wherein the mass concentration of activator is 10%～ 20% hydrochloric acid, sulfuric acid, nitric acid, sodium hydroxide or potassium hydroxide; the pretreatment of carbon source by acid treatment is carried out according to the following reaction: the carbon source is added to a hydrochloric acid solution with a mass concentration of 10% to 15% Ultrasonic treatment for 3 to 6 hours; the pretreatment of carbon sources by alkali treatment is carried out according to the following reaction: add carbon sources to KOH solution with a mass concentration of 10% to 20% and stir for 0.5 to 4 hours, then hydrothermally treat for 2 to 5 hours, Wash with distilled water until the pH of the lotion is 6-8, and then dry at 80-100°C; The catalyst described is ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, potassium ferricyanide, potassium ferrocyanide, potassium ferrioxalate, cobalt chloride, nitric acid One or a mixture of cobalt, cobalt sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickel sulfate, nickel acetate. 2. The preparation method of graphitized carbon nanomaterial according to claim 1, characterized in that the solvent described in step 2 is one or a mixture of several of them in water, methanol, ethanol, isopropanol. 3. according to the preparation method of claim 1 and 2 described graphitized carbon nanomaterials, it is characterized in that the method for physical activation described in step 6 is as follows: under steam, carbon dioxide, hydrogen or carbon monoxide atmosphere, and physical activation Under the condition that the temperature is 200-500° C. and the gas flow rate in the physical activation is 100-4000 mL/min, the product in step 5 is physically activated for 0.5-24 hours. 4. according to the preparation method of claim 1 or 2 described graphitized carbon nanomaterials, it is characterized in that the method for the chemical activation described in step six is as follows: under the condition of 80～180 ℃ of activation temperature, the step five The product is activated in an inorganic solution for 3-12 hours, wherein the mass concentration of the inorganic solution is 10-45%, and the inorganic solution is a solution of potassium hydroxide, sodium hydroxide, phosphoric acid, hydrochloric acid, nitric acid or potassium permanganate. 5. The preparation method of graphitized carbon nanomaterial according to claim 1 or 2, characterized in that the drying described in step 6 is drying at 110 to 120°C or vacuum drying at 60 to 80°C 6～8h.

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