CN110697683A - Preparation method of porous spherical multilayer carbon material - Google Patents
Preparation method of porous spherical multilayer carbon material Download PDFInfo
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- CN110697683A CN110697683A CN201911049463.6A CN201911049463A CN110697683A CN 110697683 A CN110697683 A CN 110697683A CN 201911049463 A CN201911049463 A CN 201911049463A CN 110697683 A CN110697683 A CN 110697683A
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Abstract
The invention discloses a preparation method of a porous spherical multilayer carbon material, which comprises the following two steps: firstly, preparing a silicon dioxide template with a specific morphology by using an aerosol method, wherein the silicon dioxide template has stable physical and chemical properties, then introducing an organic carbon source into pores of the silicon dioxide template to obtain an organic-inorganic compound, polymerizing and carbonizing the compound to obtain a compound of the carbon template, then removing the template by using a proper chemical method to collect carbide, and obtaining the carbon material with a regular and ordered structure which cannot be obtained by using a conventional method. The method can prepare porous carbon materials with various shapes, ordered structures and uniform pore sizes according to different templates, has low cost and simple operation, and can be widely applied to the fields of energy, nano materials and the like.
Description
Technical Field
The invention relates to the technical field of carbon materials, in particular to a preparation method of a porous spherical multilayer carbon material.
Background
With the rapid development of modern science and technology, the application field of porous carbon materials is continuously expanded, the requirements of people on porous carbon materials are higher and higher, and the porous carbon materials with ordered structures and uniform pore sizes gradually become the targets pursued by people, so that researchers are promoted to continuously seek and explore new methods for controlling the pore structures. As a method capable of effectively controlling the pore structure, the template method opens up a brand new field of preparation research of novel porous carbon materials.
The most prominent feature of the templating method is the good structural controllability, which provides an effective means for controlling and improving the alignment of the nanoparticles in the structural material. The material prepared by the method has the structural characteristics similar to the pore cavity of the template, and if the adopted template has uniform pore diameter, the synthesized nano material also has a uniform structure.
The preparation method of the porous carbon material is complex, the cost is high, the porous carbon material is not easy to form, the inorganic template material has stable physical and chemical properties, then an organic carbon source is introduced into the pores of the inorganic template material to obtain an organic-inorganic compound, the compound is polymerized and carbonized to obtain a compound of the carbon template, then the template is removed by a proper chemical method to collect the carbide, and the carbon material with regular and ordered structure which can not be obtained by a conventional method is obtained. Porous carbon materials with various shapes, ordered structures and uniform pore sizes are prepared according to different templates, the cost is low, the operation is simple, and the porous carbon materials can be widely applied to the fields of energy sources, nano materials and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a porous spherical multilayer carbon material, which can be used for preparing a porous carbon material with an ordered structure and uniform pore size by using low-price raw materials and a simpler preparation method with high success rate, is low in cost and simple to operate, and can be widely applied to the fields of energy, nano materials and the like.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a porous spherical multilayer carbon material comprises the following steps:
(1) preparing a template:
a. weighing deionized water and absolute ethyl alcohol by using an analytical balance, mixing in a 500ml beaker, dissolving a P-123 template agent in the solution, and dissolving for 5-10min by ultrasonic to obtain a mixed solution;
b. quickly mixing tetraethoxysilane and 12mol/L concentrated hydrochloric acid with the mixed solution, stirring and ultrasonically dissolving for 5-15min to obtain a solution A;
c. gradually putting the solution A into an atomizer, and pressurizing by using nitrogen to ensure that the solution A passes through the tube pass of an aerosol generation system heated to 400-500 ℃ to obtain white P-123-silicon dioxide solid;
d. putting the P-123-silicon dioxide solid into a box-type furnace, and burning for 2-4h at 425 ℃ in an air atmosphere to obtain a white mesoporous spherical silicon dioxide solid template with the template agent removed;
(2) preparation of carbon material:
a. using a 50ml beaker, taking a proper amount of mesoporous spherical silicon dioxide solid template, and ultrasonically dispersing in 5.00g of deionized water to obtain template dispersion liquid;
b. taking proper amount of sugar or taking the mass of the sugar as 1: 1, placing the mixture of sugar and urea in a template dispersion liquid, ultrasonically dissolving for 5-10min, and then continuously dripping a proper amount of concentrated sulfuric acid for ultrasonically dissolving reaction for 5-10min to obtain a white suspension;
c. drying the white suspension in a constant-temperature drying oven at the temperature of 100-;
d. taking proper amount of sugar or taking the mass of the sugar as 1: 1, dissolving the mixture of sugar and urea in 5.00g of deionized water, dripping a proper amount of concentrated sulfuric acid, pouring into the solid A, and carrying out ultrasonic treatment for 5-10min to disperse the solid A to obtain a suspension B;
e. drying the suspension B in a constant-temperature drying oven at 100 ℃ for 6h, and then immediately heating to 160 ℃ for drying for 6h to obtain solid C;
f. grinding the solid C, placing the ground solid C in a high-purity argon atmosphere, and burning the ground solid C in a tubular furnace for 5 hours at 900 ℃ (the heating rate is 3 ℃/min) to obtain a solid D;
g. grinding the solid D to be extremely fine, pouring the ground solid D into a plastic bottle, adding a proper amount of deionized water and a proper amount of hydrofluoric acid, putting in a magnet, and stirring for 5-6 hours to obtain a suspension E;
h. filtering the suspension E by suction, and washing the suspension with ionized water until the pH value is 7 to obtain black solid powder F;
i. and (3) drying the black solid powder F in a constant-temperature drying oven or a vacuum drying oven at 60 ℃ for more than 4 hours to obtain the mesoporous spherical nitrogen-containing or nitrogen-free carbon material.
In a specific embodiment of the invention, in the template preparation step a, the mass ratio of the deionized water to the absolute ethyl alcohol is as follows: anhydrous ethanol ═ 1: 9.2.
in one embodiment of the present invention, in the template preparation step a, the mass of the P-123 template agent is 4.17-8.35 g.
In a specific embodiment of the present invention, in the step b of preparing the template, the amount of the concentrated hydrochloric acid is 0.2-0.4 mL.
In a specific embodiment of the invention, in the preparation steps a, b and d of the carbon material, the mass ratio of the mesoporous spherical silica solid template to the sugar in the step b and the sugar in the step d is 1: 1.25: 0.8.
in one embodiment of the present invention, in the steps b and d for preparing the carbon material, the sugar includes but is not limited to one or more of glucose, fructose, sucrose, maltose, starch, cellulose, ribose, and lactose.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts cheap anhydrous high-purity saccharide which is easy to obtain as the carbon source and the P-123 organic material as the template agent, and has the advantages that the prepared template is stable and uniform in size, and the minimum material can reach 20 nm. The instrument required by the operation is more common, the operation risk coefficient is small, the operation is simple, and the template agent have high stability and can be removed by common reagents or operation methods of transactions which do not influence the activity of the carbon material. The silica is used as the template, so that the method has the advantages of high temperature resistance, no reaction with filling materials, environmental friendliness and the like. When the carbon material is modified by carbonization and the like, the pore-forming or carbonization temperature can be reduced by using a urea adding method, and the energy is environment-friendly. The method can derive carbon material pore-forming techniques with different purposes, and can open up a brand new field of preparation research of novel porous carbon materials. The prepared carbon material can be widely applied to the fields of energy sources, nano materials and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings of the embodiments will be briefly described below.
FIG. 1 is a TEM image of a silica template prepared in example 1 of the present invention;
FIG. 2 is a TEM image of a mesoporous spherical nitrogen-free carbon material prepared in example 1 of the present invention;
FIG. 3 is a TEM image of the mesoporous spherical nitrogen-containing carbon material prepared in example 2 of the present invention.
Detailed Description
Other aspects, features and advantages of the present invention will become apparent from the following detailed description, taken in conjunction with the accompanying drawings, which form a part of this specification, and which illustrate, by way of example, the principles of the invention. In the referenced drawings, the same or similar components in different drawings are denoted by the same reference numerals.
Example 1: preparation of mesoporous spherical carbon material
A. The preparation method of the template comprises the following steps:
1. weighing 13.5g of deionized water and 151.80g of absolute ethyl alcohol by using an analytical balance, mixing and dissolving in a 500ml beaker, dissolving 8.35g of P-123 template agent in the solution, and dissolving for 10min by ultrasonic to obtain a mixed solution;
2. rapidly mixing 31.25g of tetraethoxysilane and 0.20g of concentrated hydrochloric acid with the mixed solution, stirring and ultrasonically dissolving for 10min to obtain a solution A;
3. gradually putting the solution A into an atomizer, and pressurizing by using nitrogen to ensure that the solution A passes through a tube pass of an aerosol generation system heated to 400 ℃ to obtain a white P-123-silicon dioxide solid;
4. putting the P-123-silicon dioxide solid into a box furnace, and burning for 4h at 425 ℃ (3 ℃/min heating rate) in the air atmosphere to obtain a white mesoporous spherical silicon dioxide solid template without a template agent.
B. The preparation steps of the carbon material are as follows:
1. using a 50ml beaker, taking 1.00g of mesoporous spherical silica template, and ultrasonically dispersing in 5.00g of deionized water to obtain template dispersion liquid;
2. placing 1.25g of anhydrous glucose into the template dispersion liquid, ultrasonically dissolving for 8min, and then continuously dripping 0.14g of concentrated sulfuric acid for ultrasonically dissolving reaction for 10min to obtain a white suspension;
3. drying the white suspension in a constant-temperature drying oven at 100 ℃ for 6h, and then immediately heating to 160 ℃ for drying for 6h to obtain a black solid A;
4. dissolving 0.80g of anhydrous glucose in 5.00g of deionized water, dropwise adding 0.09g of concentrated sulfuric acid, pouring into the solid A, and ultrasonically treating for 10min to disperse the solid A to obtain a suspension B;
5. drying the suspension B in a constant-temperature drying oven at 100 ℃ for 6h, and then immediately heating to 160 ℃ for drying for 6h to obtain a brownish black solid C;
6. grinding the solid C, placing the ground solid C in a high-purity argon atmosphere, and burning the ground solid C in a tubular furnace for 5 hours at 900 ℃ (the heating rate is 3 ℃/min) to obtain a black solid D;
7. grinding the black solid D to be extremely fine, pouring the superfine black solid D into a plastic bottle, adding a proper amount of deionized water and 2.4g of hydrofluoric acid, putting a magnet and stirring for 6 hours to obtain a suspension E;
8. filtering and washing the suspension E with ionized water until the pH value is 7 to obtain black solid powder F;
9. and (3) drying the black solid powder F in a constant-temperature drying oven or a vacuum drying oven at 60 ℃ for 4h to obtain the mesoporous spherical nitrogen-free carbon material.
Example 2: preparation of nitrogen-doped mesoporous spherical carbon material
A. The preparation method of the template comprises the following steps:
1. weighing 13.5g of deionized water and 151.80g of absolute ethyl alcohol by using an analytical balance, mixing and dissolving in a 500ml beaker, dissolving 8.35g of P-123 template agent in the solution, and dissolving for 8min by ultrasonic waves to obtain a mixed solution;
2. rapidly mixing 31.25g of tetraethoxysilane and 0.20g of concentrated hydrochloric acid with the mixed solution, stirring and ultrasonically dissolving for 15min to obtain a solution A;
3. gradually putting the solution A into an atomizer, and pressurizing by using nitrogen to ensure that the solution A passes through a tube pass of an aerosol generation system heated to 400 ℃ to obtain a white P-123-silicon dioxide solid;
4. putting the P-123-silicon dioxide solid into a box furnace, and burning for 4h at 425 ℃ (3 ℃/min heating rate) in the air atmosphere to obtain a white mesoporous spherical silicon dioxide solid template without a template agent.
B. Preparing a nitrogen-doped mesoporous spherical carbon material:
1. using a 50ml beaker, taking 1.00g of mesoporous spherical silica template, and ultrasonically dispersing in 5.00g of deionized water to obtain template dispersion liquid;
2. 1.25g of anhydrous glucose and 1.25g of urea are taken and placed in the template dispersion liquid, after ultrasonic dissolution is carried out for 10min, 0.14g of concentrated sulfuric acid is continuously dropped in for ultrasonic dissolution reaction for 10min, and white suspension is obtained;
3. drying the white suspension in a constant-temperature drying oven at 100 ℃ for 6h, and then immediately heating to 160 ℃ for drying for 6h to obtain a brown yellow solid A;
4. dissolving 0.80g of anhydrous glucose and 0.80g of urea in 5.00g of deionized water, dropwise adding 0.09g of concentrated sulfuric acid, pouring into the solid A, and ultrasonically treating for 5min to disperse the solid A to obtain a suspension B;
5. drying the suspension B in a constant-temperature drying oven at 100 ℃ for 6h, and then immediately heating to 160 ℃ for drying for 6h to obtain a brown yellow solid C;
6. grinding the solid C, placing the ground solid C in a high-purity argon atmosphere, and burning the ground solid C in a tubular furnace for 5 hours at 900 ℃ (the heating rate is 3 ℃/min) to obtain a black solid D;
7. grinding the black solid D to be extremely fine, pouring the superfine black solid D into a plastic bottle, adding a proper amount of deionized water and 2.4g of hydrofluoric acid, putting a magnet and stirring for 5 hours to obtain a suspension E;
8. filtering and washing the suspension E with ionized water until the pH value is 7 to obtain black solid powder F;
9. and (3) drying the black solid powder F in a constant-temperature drying oven or a vacuum drying oven at 60 ℃ for 8 hours to obtain the mesoporous spherical nitrogen-containing carbon material.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (6)
1. A preparation method of a porous spherical multilayer carbon material is characterized by comprising the following steps:
(1) preparing a template:
a. weighing deionized water and absolute ethyl alcohol by using an analytical balance, mixing in a 500ml beaker, dissolving a P-123 template agent in the solution, and dissolving for 5-10min by ultrasonic to obtain a mixed solution;
b. quickly mixing tetraethoxysilane and 12mol/L concentrated hydrochloric acid with the mixed solution, stirring and ultrasonically dissolving for 5-15min to obtain a solution A;
c. gradually putting the solution A into an atomizer, and pressurizing by using nitrogen to ensure that the solution A passes through the tube pass of an aerosol generation system heated to 400-500 ℃ to obtain white P-123-silicon dioxide solid;
d. putting the P-123-silicon dioxide solid into a box-type furnace, and burning for 2-4h at 425 ℃ in an air atmosphere to obtain a white mesoporous spherical silicon dioxide solid template with the template agent removed;
(2) preparation of carbon material:
a. using a 50ml beaker, taking a proper amount of mesoporous spherical silicon dioxide solid template, and ultrasonically dispersing in 5.00g of deionized water to obtain template dispersion liquid;
b. taking proper amount of sugar or taking the mass of the sugar as 1: 1, placing the mixture of sugar and urea in a template dispersion liquid, ultrasonically dissolving for 5-10min, and then continuously dripping a proper amount of concentrated sulfuric acid for ultrasonically dissolving reaction for 5-10min to obtain a white suspension;
c. drying the white suspension in a constant-temperature drying oven at the temperature of 100-;
d. taking proper amount of sugar or taking the mass of the sugar as 1: 1, dissolving the mixture of sugar and urea in 5.00g of deionized water, dripping a proper amount of concentrated sulfuric acid, pouring into the solid A, and carrying out ultrasonic treatment for 5-10min to disperse the solid A to obtain a suspension B;
e. drying the suspension B in a constant-temperature drying oven at 100 ℃ for 6h, and then immediately heating to 160 ℃ for drying for 6h to obtain solid C;
f. grinding the solid C, placing the ground solid C in a high-purity argon atmosphere, and burning the ground solid C in a tubular furnace at 900 ℃ for 5 hours to obtain a solid D;
g. grinding the solid D to be extremely fine, pouring the ground solid D into a plastic bottle, adding a proper amount of deionized water and a proper amount of hydrofluoric acid, putting in a magnet, and stirring for 5-6 hours to obtain a suspension E;
h. filtering the suspension E by suction, and washing the suspension with ionized water until the pH value is 7 to obtain black solid powder F;
i. and (3) drying the black solid powder F in a constant-temperature drying oven or a vacuum drying oven at 60 ℃ for more than 4 hours to obtain the mesoporous spherical nitrogen-containing or nitrogen-free carbon material.
2. The method for preparing the porous spherical multilayer carbon material according to claim 1, wherein in the step a of preparing the template, the mass ratio of the deionized water to the absolute ethyl alcohol is as follows: anhydrous ethanol ═ 1: 9.2.
3. the method for preparing a porous spherical multilayer carbon material according to claim 1, wherein in the template preparation step a, the mass of the P-123 template is 4.17 to 8.35 g.
4. The method for preparing a porous spherical multilayer carbon material according to claim 1, wherein the amount of concentrated hydrochloric acid used in the template preparation step b is 0.2 to 0.4 mL.
5. The method for preparing a porous spherical multilayer carbon material according to claim 1, wherein the mass ratio of the mesoporous spherical silica solid template to the saccharides in step b and the saccharides in step d in the steps a, b and d for preparing the carbon material is 1: 1.25: 0.8.
6. the method for preparing a porous spherical multilayer carbon material according to claim 1, wherein in the steps b and d for preparing the carbon material, the sugar comprises one or more of glucose, fructose, sucrose, maltose, starch, cellulose, ribose and lactose.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108232158A (en) * | 2018-01-04 | 2018-06-29 | 湖北文理学院 | A kind of preparation method of order mesoporous Co/CMK composite Nanos negative material |
| CN108840370A (en) * | 2018-07-04 | 2018-11-20 | 山东建筑大学 | A kind of transition metal oxide/N doping ordered mesoporous carbon composite material and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108232158A (en) * | 2018-01-04 | 2018-06-29 | 湖北文理学院 | A kind of preparation method of order mesoporous Co/CMK composite Nanos negative material |
| CN108840370A (en) * | 2018-07-04 | 2018-11-20 | 山东建筑大学 | A kind of transition metal oxide/N doping ordered mesoporous carbon composite material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| MARIA LEZANSKA ET AL.: "Synthesis and characterization of carbonaceous replicas of multilayered vesicular siliceous materials", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| YONG YANG ET AL.: "Direct synthesis of nitrogen-doped mesoporous carbons for acetylene hydrochlorination", 《CHINESE JOURNAL OF CATALYSIS 》 * |
| YUNFENG LU ET AL.: "Aerosol-assisted self-assembly of mesostructured spherical nanoparticles", 《NATURE》 * |
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