CN111533121B - Preparation method of porous graphite hollow hemisphere with high specific surface area - Google Patents
Preparation method of porous graphite hollow hemisphere with high specific surface area Download PDFInfo
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- CN111533121B CN111533121B CN202010511928.1A CN202010511928A CN111533121B CN 111533121 B CN111533121 B CN 111533121B CN 202010511928 A CN202010511928 A CN 202010511928A CN 111533121 B CN111533121 B CN 111533121B
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Abstract
The invention discloses a preparation method of a porous hollow graphite hemisphere with high specific surface area, which uses polystyrene spheres as templates, glucose (or sucrose) as a carbon precursor, mixes a graphite catalyst, and combines a hydrothermal method, a microwave method and a high-temperature calcination method to obtain the porous hollow graphite hemisphere. The invention can control the graphitization degree, the pore diameter and the specific surface area of the material by adjusting the amount of the graphite catalyst, the diameter of the polystyrene spheres, the ratio of glucose (or sucrose) to the polystyrene spheres, the microwave time, the calcination temperature and the like. The porous hollow graphite hemisphere prepared by the invention is used as a catalytic material and has excellent material transmission performance and electrochemical stability.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a preparation method of a porous graphite hollow hemisphere with a high specific surface area.
Background
The ideal catalytic and energy storage material has the characteristics of large specific surface area, high porosity, chemical stability and the like; the electric, heat-conducting, electrochemical and electrode catalytic materials are also required to have good electric conductivity. The porous carbon material has developed pore structure, large specific surface area, good electric conductivity, low price and suitability for large-scale production, is often used for catalysis and energy storage material matrixes, and is widely researched in the fields of wear-resistant, heat-conducting, electric-conducting and electromagnetic shielding coatings. Generally, the conventional carbon material exists in an amorphous form, and has poor conductivity and stability, so that the application is limited; therefore, graphitized carbon materials have received great attention. The graphitized carbon material has excellent chemical stability, strong electron conductivity and very broad application prospect.
As is well known, porous carbon can be produced by various methods such as direct carbonization, template method, activation method, self-assembly method, etc. Wang et al synthesized a large area, self-supporting porous carbon film with single crystal graphite order and hierarchical pore structure by a simple top-down method [ Nat. Commun., 8 (2017) 13592 ]]. Wiesner et al uses a phenol-formaldehyde resin as a carbon source and polyisoprene-polystyreneThe alkene-polyethylene oxide triblock copolymer is used as a template to prepare a porous carbon material [ ACS Nano, 8 (2014) 731-743 with the pore diameter of up to 39 nanometers ]]. Li et al prepared porous carbon materials from nano-magnesia as a template and bio-oil as a raw material, tested the performance of their supercapacitors, and found that their cycling stability was excellent [ Fuel Pr < deg. > C ess technology, 192 (2019) 239-249 ]]. Lua et al use oil palm stone as a carbon source, CO 2 Preparing the activator with specific surface area as high as 1410 and 1410 m 2 Porous Carbon material/g [ Carbon, 38 (2000) 1089-1097]. Wang et al uses biomass as a carbon source and potassium bicarbonate as a pore-forming agent, and performs high-temperature calcination to obtain a carbon material with a multi-stage pore structure [ ACS Sustin. Chem. Eng., 4 (2016) 3750-3756 ]]. However, to date, no method for preparing porous carbon by microwave oxidation pore-forming has been reported.
Disclosure of Invention
The invention aims to provide a method for preparing a porous graphite hollow hemisphere with controllable specific surface area and pore diameter by a microwave oxidation method.
In order to achieve the above object, the present invention adopts the following technical scheme:
the preparation method of the porous graphite hollow hemisphere with the high specific surface area comprises the following steps:
step 1, uniformly mixing polystyrene balls, a carbon precursor, a graphitization catalyst and deionized water in a high-pressure reaction kettle lined with polytetrafluoroethylene liner according to a certain mass ratio, and carrying out a hydrothermal reaction in an oven;
step 2, collecting a solid product after cooling, and carrying out heating decomposition and oxidation in the air atmosphere of a microwave oven after drying;
step 3, placing the obtained product in a tube furnace, and carbonizing at high temperature under the condition of isolating oxygen;
step 4, soaking the obtained product with an acid solution to remove unstable substances.
In the preparation method of the porous graphite hollow hemispheres, the diameter of the polystyrene spheres in the step 1 is 100 micrometers to 1 millimeter.
In the preparation method of the porous graphite hollow hemispheres, the carbon precursor in the step 1 is glucose or sucrose, preferably glucose.
In the preparation method of the porous graphite hollow hemispheres, the graphitizing catalyst in the step 1 is a water-soluble salt of Fe, co or Ni, wherein the Fe salt is one or a mixture of more than two of potassium ferricyanide, potassium ferrocyanide, ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate and ferrous sulfate; wherein the Co salt is one or more of cobalt chloride, cobalt nitrate and cobalt sulfate; wherein the Ni salt is one or more of nickel chloride, nickel nitrate and nickel sulfate.
In the preparation method of the porous graphite hollow hemispheres, the mass ratio of the polystyrene spheres to the carbon precursor in the step 1 is 1:0.1-4, preferably 1:0.2-2.
In the preparation method of the porous graphite hollow hemispheres, the mass ratio of the carbon precursor to the graphitization catalyst in the step 1 is 1:0.002-0.2, preferably 1:0.02-0.1.
In the preparation method of the porous graphite hollow hemispheres, the mass ratio of the carbon precursor to the deionized water in the step 1 is 1:5-100, preferably 1:10-50.
In the preparation method of the porous graphite hollow hemispheres, the temperature of the hydrothermal reaction in the step 1 is 160-240 ℃, preferably 180-200 ℃; the incubation time is 3 to 24 hours, preferably 6 to 18 hours.
In the preparation method of the porous graphite hollow hemispheres, the heating temperature of the microwave oven in the step 2 is 300-900 ℃, preferably 400-700 ℃; the heating time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes.
In the preparation method of the porous graphite hollow hemispheres, the carbonization temperature in the step 3 is 600-1400 ℃, preferably 800-1000 ℃; the incubation time is 20 minutes to 10 hours, preferably 1 to 3 hours.
In the preparation method of the porous graphite hollow hemispheres, the acid solution in the step 4 is hydrochloric acid, nitric acid or sulfuric acid.
Firstly, uniformly mixing polystyrene spheres, a carbon precursor, a graphitization catalyst and water, and forming a polystyrene sphere compound wrapped by the carbon precursor and the graphitization catalyst through hydrothermal reaction; then the polystyrene spheres are decomposed by microwave oxidation, the semi-carbonized carbon precursor layer is collapsed into a hollow hemispherical shape, and then partial carbon is oxidized by microwaves to form a large number of holes, wherein the aggregation effect of the graphitization catalyst on heat further promotes the partial oxidation of carbon atoms to form larger holes; after that, high temperature carbonization and graphitization reactions are performed; finally removing graphitization catalyst and impurities to obtain porous graphite hollow hemispheres, wherein the removal of graphitization catalyst also generates larger pores. The pore diameter and specific surface area of the porous graphite hollow hemispheres mainly depend on the microwave oxidation temperature and time and the amount of graphitization catalyst; in addition, the diameter of the polystyrene spheres and the ratio of the polystyrene spheres to the carbon precursor also have an influence on the pore size and specific surface area of the product.
Compared with the prior art, the invention has the following characteristics:
1. the porous graphite hollow hemispheres prepared by the method have smaller volume than the graphite hollow hemispheres under the condition of similar specific surface areas.
2. The average pore diameter and specific surface area of the porous graphite hollow hemispheres prepared by the invention can be regulated by the microwave heating temperature and time and the dosage of graphitization catalyst, and the specific surface area can reach 3000 m 2 g -1 The above.
Drawings
FIG. 1 is a scanning electron microscope and a high resolution transmission electron microscope of a porous graphite hollow hemisphere obtained in example 1.
Detailed Description
The invention is further illustrated by way of example with reference to the accompanying drawings.
Example 1
Into a autoclave with a capacity of 50 mL lined polytetrafluoroethylene liner, 1 g of polystyrene balls with an average diameter of 1.6 μm, 0.1 g of glucose, 0.02 g of ferric chloride and 10 mL of deionized water were added and stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 180 ℃, and preserving heat for 18 hours. After cooling, the resulting solid was dried at 120 ℃ for 2 hours, then placed in a microwave oven, heated to 600-700 ℃ under an air atmosphere and held for 20 seconds. The product obtainedAfter cooling, it was placed in a tube furnace, heated to 800℃at a heating rate of 10℃per minute under a nitrogen stream, and kept for 3 hours. After cooling to room temperature, the product was triturated and taken up with 1 mol L -1 Soaking in sulfuric acid solution, stirring for 2 h, washing with deionized water, and drying to obtain a solution with average mesoporous diameter of 14 nm and specific surface area of 2113 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 2
1 g of polystyrene balls with average diameter of 1 mm, 1 g of sucrose, 0.02 g of ferrous nitrate and 10 mL of deionized water are added into a high-pressure reaction kettle with a volume of 50 mL and a lining of polytetrafluoroethylene liner, and the mixture is stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 240 ℃, and preserving heat for 3 hours. After cooling, the resulting solid was dried at 120 ℃ for 2 hours, then placed in a microwave oven, heated to 400-500 ℃ under an air atmosphere and held for 1 minute. After cooling the product obtained, it was placed in a tube furnace, heated to 1400 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and incubated for 20 minutes. After cooling to room temperature, the product was triturated and taken up with 1 mol L -1 Soaking in nitric acid solution, stirring for 2 h, washing with deionized water, and drying to obtain mesoporous powder with average diameter of 6 nm and specific surface area of 1003-1003 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 3
Into a high-pressure reaction kettle with 50-mL lining polytetrafluoroethylene liner, 1 g of polystyrene balls with average diameter of 100 nanometers, 4 g of glucose, 0.008 g of ferric nitrate and 20 mL of deionized water are added and stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 160 ℃, and preserving heat for 24 hours. After cooling, the resulting solid was dried at 120 ℃ for 2 hours, then placed in a microwave oven, heated to 300-400 ℃ under an air atmosphere and held for 3 minutes. After cooling the obtained product, it was placed in a tube furnace, heated to 600 ℃ at a heating rate of 10 ℃/min under a nitrogen stream, and kept for 10 hours. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution, stirring for 2 h, washing with deionized water, drying to obtain mesoporous powder with average diameter of 4 nm,specific surface area 872 and 872 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 4
Into a autoclave with a capacity of 50 mL lined polytetrafluoroethylene liner, 1 g of polystyrene balls with an average diameter of 1.6 μm, 0.1 g of glucose, 0.1 g of sucrose, 0.02 g of ferrous chloride and 10 mL of deionized water were added and stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 200 ℃, and preserving heat for 6 hours. After cooling, the resulting solid was dried at 120 ℃ for 2 hours, then placed in a microwave oven, heated to 600-700 ℃ under an air atmosphere and held for 30 seconds. After cooling the product obtained, it was placed in a tube furnace, heated to 1000 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and kept for 1 hour. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution, stirring for 2 h, washing with deionized water, and drying to obtain mesoporous powder with average diameter of 10 nm and specific surface area of 1878 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 5
2 g of polystyrene balls with average diameter of 1.6 microns, 4 g of glucose, 0.2 g of potassium ferricyanide and 10 mL of deionized water are added into a high-pressure reaction kettle with a volume of 50 mL and a lining of polytetrafluoroethylene liner, and the mixture is stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 200 ℃, and preserving heat for 6 hours. After cooling, the resulting solid was dried at 120 ℃ for 2 hours, then placed in a microwave oven, heated to 300-400 ℃ under an air atmosphere and held for 5 minutes. After cooling the product obtained, it was placed in a tube furnace, heated to 1000 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and kept for 1 hour. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution, stirring for 2 h, washing with deionized water, and drying to obtain a product with average mesoporous diameter of 8 nm and specific surface area of 1634 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 6
Into a high-pressure reaction kettle with 50-mL lining polytetrafluoroethylene liner, 2 g of polyphenyl with average diameter of 1.6 microns is addedEthylene balls, 4 g of glucose, 0.1 g of potassium ferricyanide and 10 mL of deionized water are stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 200 ℃, and preserving heat for 6 hours. After cooling, the resulting solid was dried at 120℃for 2 hours, then placed in a microwave oven, heated to 800-900℃under an air atmosphere and held for 20 seconds. After cooling the product obtained, it was placed in a tube furnace, heated to 1000 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and kept for 1 hour. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution, stirring for 2 h, washing with deionized water, and drying to obtain a product with average mesoporous diameter of 7 nm and specific surface area of 1562 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 7
Into a autoclave with a capacity of 50 mL lined polytetrafluoroethylene liner, 1 g of polystyrene balls with an average diameter of 1.6 μm, 1 g of glucose, 0.1 g of potassium ferrocyanide and 40 mL of deionized water were added and stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 180 ℃, and preserving heat for 12 hours. After cooling, the resulting solid was dried at 120 ℃ for 2 hours, then placed in a microwave oven, heated to 400-500 ℃ under an air atmosphere and held for 1 minute. After cooling the product obtained, it was placed in a tube furnace, heated to 1000 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and kept for 1 hour. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution and stirring for 2 h, washing with deionized water, and drying to obtain a solution with average mesoporous diameter of 9 nm and specific surface area of 1975 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 8
Into a autoclave with a capacity of 50 mL lined polytetrafluoroethylene liner, 1 g of polystyrene balls with an average diameter of 1.6 μm, 1 g of glucose, 0.1 g of ferric sulfate and 40 mL of deionized water were added and stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 180 ℃, and preserving heat for 12 hours. Cooling, drying the obtained solid at 120deg.C for 2 hr, placing in a microwave oven, and heating to 400-500deg.C under air atmosphereAnd held for 1 minute. After cooling the product obtained, it was placed in a tube furnace, heated to 1000 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and kept for 1 hour. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution and stirring for 2 h, washing with deionized water, and drying to obtain mesoporous powder with average diameter of 9 nm and specific surface area of 2003 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 9
Into a autoclave with a capacity of 50 mL lined polytetrafluoroethylene liner, 1 g of polystyrene balls with an average diameter of 1.6 μm, 0.5 g of glucose, 0.1 g of ferrous sulfate and 40 mL of deionized water were added and stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 180 ℃, and preserving heat for 12 hours. After cooling, the resulting solid was dried at 120 ℃ for 2 hours, then placed in a microwave oven, heated to 400-500 ℃ under an air atmosphere and held for 1 minute. After cooling the product obtained, it was placed in a tube furnace, heated to 1000 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and kept for 1 hour. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution, stirring for 2 h, washing with deionized water, and drying to obtain mesoporous powder with average diameter of 10 nm and specific surface area of 2318-2318 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 10
Into a high-pressure reaction kettle with a volume of 50 mL and a lining of polytetrafluoroethylene liner, 1 gram of polystyrene balls with an average diameter of 1.6 micrometers, 0.5 gram of glucose, 0.05 gram of ferric chloride, 0.02 gram of ferric nitrate, 0.03 gram of ferric sulfate and 40 mL of deionized water are added and stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 180 ℃, and preserving heat for 12 hours. After cooling, the resulting solid was dried at 120 ℃ for 2 hours, then placed in a microwave oven, heated to 400-500 ℃ under an air atmosphere and held for 1 minute. After cooling the product obtained, it was placed in a tube furnace, heated to 1000 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and kept for 1 hour. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution and stirring 2 hThen washing with deionized water and drying to obtain the product with average mesoporous diameter of 10 nm and specific surface area of 2322 and 2322 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 11
Into a high-pressure reaction kettle with 50-mL lining polytetrafluoroethylene liner, 1 g of polystyrene balls with the average diameter of 830 nanometers, 0.5 g of glucose, 0.07 g of cobalt chloride and 40 mL of deionized water are added and stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 180 ℃, and preserving heat for 12 hours. After cooling, the resulting solid was dried at 120 ℃ for 2 hours, then placed in a microwave oven, heated to 400-500 ℃ under an air atmosphere and held for 1 minute. After cooling the product obtained, it was placed in a tube furnace, heated to 1000 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and kept for 1 hour. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution, stirring for 2 h, washing with deionized water, and drying to obtain the final product with average mesoporous diameter of 8 nm and specific surface area of 3018 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 12
Into a autoclave with a capacity of 50 mL lined polytetrafluoroethylene liner, 1 g of polystyrene balls with an average diameter of 830 nm, 0.5 g of glucose, 0.1 g of cobalt nitrate and 40 mL of deionized water were added and stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 180 ℃, and preserving heat for 12 hours. After cooling, the resulting solid was dried at 120 ℃ for 2 hours, then placed in a microwave oven, heated to 400-500 ℃ under an air atmosphere and held for 1 minute. After cooling the product obtained, it was placed in a tube furnace, heated to 1000 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and kept for 1 hour. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution, stirring for 2 h, washing with deionized water, and drying to obtain a solution with average mesoporous diameter of 9 nm and specific surface area of 3218 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 13
A 50 mL volume liner of polytetrafluoroethylene1 g of polystyrene balls with the average diameter of 830 nanometers, 0.5 g of glucose, 0.1 g of cobalt nitrate and 40 mL of deionized water are added into a high-pressure reaction kettle of an ethylene container and stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 180 ℃, and preserving heat for 12 hours. After cooling, the resulting solid was dried at 120 ℃ for 2 hours, then placed in a microwave oven, heated to 400-500 ℃ under an air atmosphere and held for 1 minute. After cooling the product obtained, it was placed in a tube furnace, heated to 1000 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and kept for 1 hour. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution, stirring for 2 h, washing with deionized water, and drying to obtain mesoporous powder with average diameter of 9 nm and specific surface area of 3266 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 14
1 g of polystyrene balls with average diameter of 1.4 nanometers, 0.5 g of glucose, 0.1 g of cobaltous chloride and 40 mL of deionized water are added into a high-pressure reaction kettle with a volume of 50 mL and a lining of polytetrafluoroethylene liner, and the mixture is stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 180 ℃, and preserving heat for 12 hours. After cooling, the resulting solid was dried at 120 ℃ for 2 hours, then placed in a microwave oven, heated to 400-500 ℃ under an air atmosphere and held for 1 minute. After cooling the product obtained, it was placed in a tube furnace, heated to 1000 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and kept for 1 hour. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution, stirring for 2 h, washing with deionized water, and drying to obtain a product with average pore diameter of 6 nm and specific surface area of 2832 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 15
1 g of polystyrene balls with average diameter of 1.4 nanometers, 0.5 g of glucose, 0.1 g of cobalt sulfate and 40 mL of deionized water are added into a high-pressure reaction kettle with a volume of 50 mL and a lining of polytetrafluoroethylene liner, and the mixture is stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 180 ℃, and preserving heat for 12 hours. After cooling, the resulting solid was dried at 120℃for 2 hoursWhen it is, it is then placed in a microwave oven and heated to 400-500 c under an air atmosphere and maintained for 1 minute. After cooling the product obtained, it was placed in a tube furnace, heated to 1000 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and kept for 1 hour. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution, stirring for 2 h, washing with deionized water, and drying to obtain a powder with average pore diameter of 6 nm and specific surface area of 2798-2798 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 16
1 g of polystyrene balls with average diameter of 1.4 nanometers, 0.5 g of glucose, 0.05 g of cobalt sulfate, 0.05 g of cobalt nitrate and 40 mL of deionized water are added into a high-pressure reaction kettle with a volume of 50 mL and a lining of polytetrafluoroethylene liner, and the mixture is stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 180 ℃, and preserving heat for 12 hours. After cooling, the resulting solid was dried at 120 ℃ for 2 hours, then placed in a microwave oven, heated to 400-500 ℃ under an air atmosphere and held for 1 minute. After cooling the product obtained, it was placed in a tube furnace, heated to 1000 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and kept for 1 hour. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution, stirring for 2 h, washing with deionized water, and drying to obtain a product with average pore diameter of 6 nm and specific surface area of 2844 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 17
1 g of polystyrene balls with average diameter of 1.4 nanometers, 0.5 g of glucose, 0.1 g of nickel chloride and 40 mL of deionized water are added into a high-pressure reaction kettle with a volume of 50 mL and a lining of polytetrafluoroethylene liner, and the mixture is stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 180 ℃, and preserving heat for 12 hours. After cooling, the resulting solid was dried at 120 ℃ for 2 hours, then placed in a microwave oven, heated to 400-500 ℃ under an air atmosphere and held for 1 minute. After cooling the product obtained, it was placed in a tube furnace, heated to 1000 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and kept for 1 hour. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution, stirring for 2 h, washing with deionized water, and drying to obtain powder with average pore diameter of 6 nm and specific surface area of 2580-2580 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 18
1 g of polystyrene balls with average diameter of 1.4 nanometers, 0.5 g of glucose, 0.1 g of nickel nitrate and 40 mL of deionized water are added into a high-pressure reaction kettle with a volume of 50 mL and a lining of polytetrafluoroethylene liner, and the mixture is stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 180 ℃, and preserving heat for 12 hours. After cooling, the resulting solid was dried at 120 ℃ for 2 hours, then placed in a microwave oven, heated to 400-500 ℃ under an air atmosphere and held for 1 minute. After cooling the product obtained, it was placed in a tube furnace, heated to 1000 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and kept for 1 hour. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution and stirring for 2 h, washing with deionized water, and drying to obtain a powder with average pore diameter of 5 nm and specific surface area of 2712 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 19
Into a high-pressure reaction kettle with 50-mL lining polytetrafluoroethylene liner, 1 g of polystyrene balls with average diameter of 1.4 nanometers, 0.5 g of glucose, 0.1 g of nickel sulfate and 40 mL of deionized water are added and stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 180 ℃, and preserving heat for 12 hours. After cooling, the resulting solid was dried at 120 ℃ for 2 hours, then placed in a microwave oven, heated to 400-500 ℃ under an air atmosphere and held for 1 minute. After cooling the product obtained, it was placed in a tube furnace, heated to 1000 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and kept for 1 hour. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution, stirring for 2 h, washing with deionized water, and drying to obtain powder with average pore diameter of 6 nm and specific surface area of 2437 m 2 g -1 Porous graphite hollow hemispheres of (c).
Example 20
In a container1 g of polystyrene balls with average diameter of 1.4 nanometers, 0.5 g of glucose, 0.08 g of nickel nitrate, 0.02 g of nickel sulfate and 40 mL of deionized water are added into a high-pressure reaction kettle with a product of 50 and mL lining of polytetrafluoroethylene liner, and the mixture is stirred uniformly. Sealing the high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven, heating to 180 ℃, and preserving heat for 12 hours. After cooling, the resulting solid was dried at 120 ℃ for 2 hours, then placed in a microwave oven, heated to 400-500 ℃ under an air atmosphere and held for 1 minute. After cooling the product obtained, it was placed in a tube furnace, heated to 1000 ℃ at a heating rate of 10 ℃/min under a nitrogen flow, and kept for 1 hour. After cooling to room temperature, the product was triturated and taken up with 2 mol L -1 Soaking in hydrochloric acid solution, stirring for 2 h, washing with deionized water, and drying to obtain powder with average pore diameter of 5 nm and specific surface area of 2655 m 2 g -1 Porous graphite hollow hemispheres of (c).
Claims (1)
1. A preparation method of a porous graphite hollow hemisphere with high specific surface area is characterized by comprising the following steps: mixing a carbon precursor and a graphite catalyst by taking polystyrene spheres as templates, and preparing a porous graphite hollow hemisphere by combining a hydrothermal method, a microwave method and a high-temperature calcination method; the method comprises the following specific steps:
step 1, uniformly mixing polystyrene balls, a carbon precursor, a graphitization catalyst and deionized water in a high-pressure reaction kettle lined with polytetrafluoroethylene liner according to a certain mass ratio, and carrying out a hydrothermal reaction in an oven;
step 2, collecting a solid product after cooling, and carrying out heating decomposition and oxidation in the air atmosphere of a microwave oven after drying;
step 3, placing the obtained product in a tube furnace, and carbonizing at high temperature under the condition of isolating oxygen;
step 4, soaking the obtained product with an acid solution to remove residues of the graphitization catalyst;
the diameter of the polystyrene sphere is 100 micrometers to 1 millimeter;
the carbon precursor is glucose or sucrose;
the graphitizing catalyst in the step 1 is a water-soluble salt of Fe, co or Ni, wherein the Fe salt is one or a mixture of more than two of potassium ferricyanide, potassium ferrocyanide, ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate and ferrous sulfate; wherein the Co salt is one or more of cobalt chloride, cobalt nitrate and cobalt sulfate; wherein the Ni salt is one or more of nickel chloride, nickel nitrate and nickel sulfate;
in the step 1, the mass ratio of the polystyrene spheres to the carbon precursor is 1:0.1-4, the mass ratio of the carbon precursor to the graphitization catalyst is 1:0.002-0.2, and the mass ratio of the carbon precursor to the deionized water is 1:5-100;
the temperature of the hydrothermal reaction in the step 1 is 160-240 ℃, and the heat preservation time is 3-24 hours;
the heating temperature of the microwave oven in the step 2 is 300-900 ℃, and the heating time is 20 seconds-5 minutes;
in the step 3, the carbonization temperature is 600-1400 ℃, and the heat preservation time is 20 minutes-10 hours.
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