CN113277494A - Hollow mesoporous carbon material and preparation method and application thereof - Google Patents

Hollow mesoporous carbon material and preparation method and application thereof Download PDF

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CN113277494A
CN113277494A CN202110552645.6A CN202110552645A CN113277494A CN 113277494 A CN113277494 A CN 113277494A CN 202110552645 A CN202110552645 A CN 202110552645A CN 113277494 A CN113277494 A CN 113277494A
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carbon material
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CN113277494B (en
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顾栋
梁振金
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Wuhan University WHU
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Abstract

The invention discloses a hollow mesoporous carbon material and a preparation method and application thereof. The method provided by the invention comprises the following steps: selecting mesoporous silica rich in hydroxyl as a hard template, filling a carbon precursor into the silica template, then pyrolyzing the carbon precursor in an inert atmosphere or under a vacuum condition, and removing the silica template through hydrofluoric acid or a hot sodium hydroxide solution to obtain the hollow mesoporous carbon material with adjustable high surface area, large pore volume and pore diameter. The invention effectively solves the problems of complex preparation process, less selectivity of carbon precursor and the like of the traditional hollow mesoporous carbon material. More importantly, the invention develops a simple method for preparing a series of heteroatom-doped ordered hollow mesoporous carbon materials. The heteroatom-doped ordered hollow mesoporous carbon material has wide potential application.

Description

Hollow mesoporous carbon material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of a hollow mesoporous carbon material.
Background
Hollow mesoporous carbon materials, such as CMK-5, CMK-9, have high specific surface areas (2500 m)2G), large pore volume (2.0 cm)3/g) and adjustable pore size, etc., thus being widely applied to the aspects of energy storage and conversion, gas purification and separation, environmental management, etc. The initial hollow carbon material was prepared by a nano-casting method, but this method was usedThe preparation process of the hollow mesoporous carbon material is complex, and a carbon precursor which can be replaced is lacked.
Ordered mesoporous carbon materials doped with heteroatoms (such as boron, nitrogen, phosphorus or sulfur) are a very important class of materials, because such materials can be used as negative electrode materials of lithium, sodium and potassium ion batteries, good catalysts or catalyst carriers, and for adsorbing heavy metal ions in the environment. However, how to prepare hollow ordered mesoporous carbon materials with higher specific surface area, pore volume and heteroatom doping in a hollow structure is still a great challenge, and the success cases are very limited. At present, only two methods are needed for preparing the heteroatom-doped hollow mesoporous carbon material, namely a Chemical Vapor Deposition (CVD) method, researchers have prepared the nitrogen-doped hollow ordered mesoporous carbon material by the method, but the method has two problems: 1) metal ions used as a catalyst are difficult to completely remove, so that when the catalyst is used as a catalyst, the research on the active center of the catalyst is influenced; 2) this method is difficult to produce on a large scale. The other method is a nano-casting method, and the sulfur-doped hollow ordered mesoporous carbon material is obtained by using SBA-15 modified by aluminum ions as a template and 2-thiophenemethanol as a carbon precursor through carbonization and demoulding. However, the method is complicated in operation process and has a single carbon source.
Disclosure of Invention
In order to solve the technical problems, the invention provides a hollow mesoporous carbon material and a preparation method and application thereof.
The invention provides a simple preparation method of a hollow mesoporous carbon material capable of being produced in a large scale. The carbon source has wide adaptability (such as furfuryl alcohol, phenolic resin, 2-thiophene methanol, dopamine hydrochloride, tyrosine, pyrrole, pyridine and thiophene), and a series of hollow ordered mesoporous carbon materials doped with heteroatoms (such as nitrogen and sulfur) can be prepared by selecting different carbon sources. More importantly, the method is simple and convenient to operate and can be used for batch preparation.
The technical scheme provided by the invention is as follows:
in a first aspect, the present invention provides a method for preparing a hollow mesoporous carbon material, comprising the following steps:
1) dissolving a carbon precursor and a corresponding catalyst in a solvent, adding a mesoporous template rich in hydroxyl, uniformly stirring, heating for polymerization, and volatilizing the residual solvent after the polymerization is finished to obtain a compound of the polymerization precursor and the template;
2) pyrolyzing the compound of the polymerization precursor and the template at high temperature under inert atmosphere or vacuum condition, and then naturally cooling;
3) adding the product obtained in the step 2) into hydrofluoric acid or hot sodium hydroxide solution, and removing the silicon dioxide template;
4) and (3) drying the product obtained in the step 3) to remove the residual solvent, thus obtaining the hollow mesoporous carbon material.
Further, the silica template rich in hydroxyl is an ordered or disordered mesoporous silica template.
Still further, the hydroxyl-rich silica templates include SBA-15, KIT-6, FDU-12, MCF, MCM-41, and silica gel.
Further, the carbon precursor in the step 1) comprises furfuryl alcohol, phenolic resin, 2-thiophene methanol, dopamine hydrochloride, tyrosine, pyrrole, pyridine and thiophene.
Furthermore, in the step 1), dopamine hydrochloride or tyrosine serves as a precursor, the solution is hermetically stirred for 3 hours at the temperature of 50-90 ℃, and then the solvent is volatilized at the temperature of 50-90 ℃.
Furthermore, in the step 1), furfuryl alcohol, phenolic resin, 2-thiophene methanol, pyrrole, pyridine and thiophene are used as precursors, the polymerization temperature is 50-150 ℃, the specific temperature depends on the properties of the carbon precursors, and then the solvent is volatilized at 50-90 ℃.
Further, in the step 2), pyrolysis is carried out under nitrogen, argon or vacuum, and the pyrolysis temperature is 500-1200 ℃. The preferred pyrolysis temperature is 700-900 ℃.
Further, the solvent in the step 1) comprises water, ethanol, trimethylbenzene, 1, 2-dichlorobenzene and a mixed solution thereof; the solvent is determined according to the solubility of the carbon precursor.
Further, the step 1) catalyst comprises: oxalic acid, ferric nitrate, ferric chloride, cobalt nitrate, copper nitrate and corresponding hydrates; the catalyst determines whether addition or species of addition is required according to the catalytic properties of the carbon precursor.
Further, furfuryl alcohol, 2-thiophenemethanol, pyrrole, pyridine and thiophene as precursors require the use of the following catalysts: oxalic acid, ferric nitrate, ferric chloride, cobalt nitrate, copper nitrate and corresponding hydrates; dopamine hydrochloride, tyrosine or phenolic resin are used as precursors, and no catalyst is needed.
Further, in the step 3), the concentration of HF is 3-40 wt.%, and the concentration of the hot sodium hydroxide solution is 0.2-6.0 mol/L.
Further, in the step 4), the final product is obtained by freeze drying at-45 to-85 ℃ for 12 to 24 hours or drying in an oven at 50 to 90 ℃.
In a second aspect, the present invention provides a hollow mesoporous carbon material prepared using the method of the first aspect.
In a third aspect, the invention provides the hollow mesoporous carbon material of the second aspect as an anode material of an alkali metal ion battery and an application of the hollow mesoporous carbon material as a catalyst and a catalyst carrier.
The invention has the beneficial effects that:
1) according to the invention, silica rich in hydroxyl is used as a template, so that the hollow mesoporous carbon material with large specific surface area, large pore volume and adjustable pore diameter can be simply and effectively prepared. In particular, the highly ordered hollow mesoporous carbon material can be prepared by using the highly ordered mesoporous silica template.
2) The invention has wide range of applicable templates, is suitable for common SBA-15, KIT-6, MCF, FDU-12 and MCM-41, and is also suitable for commercial silica gel and the like.
3) The invention greatly widens the carbon source for preparing the hollow mesoporous carbon material.
4) The method can prepare the heteroatom-doped highly ordered mesoporous carbon material by a simple method.
5) The hollow mesoporous carbon material provided by the invention can be used as a negative electrode material, a catalyst and a catalyst carrier of an alkali metal ion battery, and has a great application prospect.
Drawings
FIG. 1 is a nitrogen adsorption-desorption graph of a hollow mesoporous carbon material prepared by using SBA-15 as a template and furfuryl alcohol as a carbon source.
FIG. 2 is a nitrogen adsorption-desorption graph of a hollow mesoporous carbon material prepared by using MCF as a template and furfuryl alcohol as a carbon source.
FIG. 3 is a TEM image of a hollow mesoporous carbon material prepared using MCF as a template and furfuryl alcohol as a carbon source.
FIG. 4 is a nitrogen adsorption-desorption graph of a hollow mesoporous carbon material prepared by using SBA-15 as a template and phenolic resin as a carbon source.
FIG. 5 is a TEM image of a hollow mesoporous carbon material prepared using SBA-15 as a template and phenolic resin as a carbon source.
FIG. 6 is a graph showing nitrogen adsorption-desorption curves of a hollow mesoporous carbon material prepared by using SBA-15 as a template and 2-thiophenemethanol as a carbon source.
FIG. 7 is a TEM image of a hollow mesoporous carbon material prepared by using SBA-15 as a template and dopamine hydrochloride as a carbon source.
FIG. 8 is a TEM image of a hollow mesoporous carbon material prepared using SBA-15 as a template and tyrosine as a carbon source.
FIG. 9 is a graph showing the cycle performance of a hollow mesoporous carbon material prepared using MCF as a template and furfuryl alcohol as a carbon source.
Detailed Description
The present invention will be described with reference to specific examples, but the present invention is not limited thereto.
The main steps for preparing the hollow mesoporous carbon material are as follows:
1) dissolving a carbon precursor and a corresponding catalyst in a solvent, adding a mesoporous template rich in hydroxyl, uniformly stirring, heating for polymerization, and volatilizing the residual solvent after the polymerization is finished to obtain a compound of the polymerization precursor and the template;
2) pyrolyzing the compound of the polymerization precursor and the template at high temperature under inert atmosphere or vacuum condition, and then naturally cooling;
3) adding the product obtained in the step 2) into hydrofluoric acid or hot sodium hydroxide solution, and removing the silicon dioxide template;
4) and (3) drying the product obtained in the step 3) to remove the residual solvent, thus obtaining the hollow mesoporous carbon material.
Example 1
25mg of oxalic acid dihydrate was dissolved in a mixed solution of 5mL of furfuryl alcohol and 5mL of mesitylene, and 0.75mL of the above solution was added dropwise to 0.5g of SBA-15 with a pipette, stirred well, sealed, and polymerized at 50 ℃ for 24 hours and then at 90 ℃ for 48 hours. After the polymerization was complete, the remaining solvent was evaporated at 60 ℃. And then putting the obtained powder into a tube furnace, heating to 300 ℃ at a heating rate of 1 ℃/min, then heating to 850 ℃ at a heating rate of 5 ℃/min, and pyrolyzing for 4h under the argon atmosphere. And after the furnace chamber is naturally cooled to the room temperature, adding the obtained powder into 15mL of 10 wt.% hydrofluoric acid aqueous solution, soaking for 12h, filtering, washing, and freeze-drying. (Note: hydrofluoric acid is strongly corrosive, and the specific surface area of the obtained carbon material is as high as 2180 m. the hydrofluoric acid is bottled by plastic bottles, and calcium chloride solution is added into filter bottles.)2Per g, pore volume up to 2.0cm3In terms of a pore size of 2.7nm and 5.6 nm. The nitrogen adsorption-desorption curve is shown in figure 1.
Example 2
25mg of oxalic acid dihydrate was dissolved in a mixed solution of 5mL of furfuryl alcohol and 5mL of mesitylene, and 1.15mL of the above solution was added dropwise to 0.5g of MCF using a pipette, stirred well, sealed, and polymerized at 50 ℃ for 24 hours, followed by polymerization at 90 ℃ for 48 hours. After the polymerization was complete, the remaining solvent was evaporated at 60 ℃. And then putting the obtained powder into a tube furnace, heating to 300 ℃ at a heating rate of 1 ℃/min, then heating to 850 ℃ at a heating rate of 5 ℃/min, and pyrolyzing for 4h under the argon atmosphere. And after the furnace chamber is naturally cooled to the room temperature, adding the obtained powder into 15mL of 10 wt.% hydrofluoric acid aqueous solution, soaking for 12h, filtering, washing, and freeze-drying. (Note: hydrofluoric acid is strongly corrosive, and the hydrofluoric acid is bottled in plastic bottles and filtered in filter bottlesAdding calcium chloride solution. ) The specific surface area of the obtained carbon material is up to 1440m2Per g, pore volume up to 4.0cm3A pore size of 4.7nm and 32 nm. The nitrogen adsorption-desorption graph is shown in fig. 2, and the transmission electron microscope graph is shown in fig. 3.
Example 3
2.1g of resol was weighed into a 25ml vial, and 2.25g of 1, 2-dichlorobenzene and 0.9g of absolute ethanol were further added, followed by stirring at room temperature for 10 min. Then 0.90mL of the above solution was added dropwise to 0.5g of SBA-15 with a pipette, stirred well, sealed and polymerized at 130 ℃ for 48 hours. After the polymerization was complete, the remaining solvent was evaporated at 60 ℃. And then putting the obtained powder into a tube furnace, heating to 300 ℃ at a heating rate of 2 ℃/min, then heating to 850 ℃ at a heating rate of 5 ℃/min, and pyrolyzing for 4h under the argon atmosphere. And after the furnace chamber is naturally cooled to the room temperature, adding the obtained powder into 15mL of 10 wt.% hydrofluoric acid aqueous solution, soaking for 12h, filtering, washing, and freeze-drying. (Note: hydrofluoric acid is strongly corrosive, and the specific surface area of the obtained carbon material is up to 1510 m. the hydrofluoric acid is bottled by plastic bottles, and calcium chloride solution is added into filter bottles.)2Per g, pore volume up to 2.1cm3In terms of a pore size of 2.7nm and 4.8 nm. The nitrogen adsorption-desorption graph is shown in fig. 4, and the transmission electron microscope graph is shown in fig. 5.
Example 4
20mg of ferric nitrate nonahydrate was weighed and added to a small vial, followed by addition of 0.2mL of anhydrous ethanol and 0.8mL of 1, 2-dichlorobenzene, followed by stirring at room temperature, and after the ferric nitrate nonahydrate was completely dissolved, 1mL of 2-thiophenemethanol was added and stirred at room temperature for 30 min. Then 0.75mL of the above solution was added dropwise to 0.5g of SBA-15 using a pipette gun, stirred well, sealed and polymerized at 120 ℃ for 48 hours. After the polymerization was complete, the remaining solvent was evaporated at 60 ℃. And then putting the obtained powder into a tube furnace, heating to 300 ℃ at a heating rate of 2 ℃/min, then heating to 850 ℃ at a heating rate of 5 ℃/min, and pyrolyzing for 4h under the argon atmosphere. After the furnace chamber is naturally cooled to room temperature, the obtained powder is added into 15mL of 10 wt.% hydrofluoric acid aqueous solutionSoaking for 12 hr, filtering, washing, and freeze drying. (Note: hydrofluoric acid is strongly corrosive, and the specific surface area of the obtained carbon material is up to 1380 m. after the hydrofluoric acid is bottled in a plastic bottle and calcium chloride solution is added into a filter flask.)2Per g, pore volume up to 1.7cm3A pore diameter of 3.0nm and 3.9 nm. The nitrogen adsorption-desorption curve is shown in figure 6.
Example 5
650mg dopamine hydrochloride was weighed into a 50mL beaker, followed by 5mL deionized water and 5mL absolute ethanol. Dopamine hydrochloride was dissolved by stirring at room temperature, followed by addition of 0.5g of SBA-15. After sealing, the mixture was stirred for 3h in a 70 ℃ water bath and then left to stir until the solution became viscous, after which the beaker was transferred to a 50 ℃ oven and stirred until the solution was completely evaporated. Then the obtained powder is placed in a tube furnace, the quartz tube is pumped to a vacuum idle state, and then the temperature is raised to 200 ℃ at the temperature raising speed of 2 ℃/min and kept for 12h at the temperature. Then the temperature is raised to 850 ℃ at the temperature raising speed of 5 ℃/min, and the pyrolysis is carried out for 4h at the temperature. (note: vacuum state is maintained during pyrolysis) after the furnace chamber is naturally cooled to room temperature, the obtained powder is added into 15mL of 10 wt.% hydrofluoric acid aqueous solution, and after soaking for 12 hours, the powder is filtered, washed and then freeze-dried. (Note: hydrofluoric acid is strongly corrosive, and the specific surface area of the obtained carbon material is up to 1420 m. the hydrofluoric acid is bottled by plastic bottle, and calcium chloride solution is added into a filter flask.)2Per g, pore volume up to 1.6cm3In terms of a pore size of 2.7nm and 4.2 nm. A transmission electron micrograph thereof is shown in FIG. 7.
Example 6
750mg of tyrosine was weighed into a 50mL beaker, followed by 5mL of deionized water and 5mL of absolute ethanol and 650 μ L of concentrated hydrochloric acid (37 wt.%). The tyrosine was dispersed by stirring at room temperature, followed by the addition of 0.5g of SBA-15. After sealing, the mixture was stirred for 3h in a 70 ℃ water bath and then left to stir until the solution became viscous, after which the beaker was transferred to a 70 ℃ oven and stirred until the solution was completely evaporated. Then the obtained powder is put into a tube furnace, the quartz tube is pumped to a vacuum idle state, and then the temperature is raised to 200 ℃ at the temperature raising speed of 2 ℃/min and is kept at the temperatureAnd keeping for 12 h. Then the temperature is raised to 850 ℃ at the temperature raising speed of 5 ℃/min, and the pyrolysis is carried out for 4h at the temperature. (note: vacuum state is maintained during pyrolysis) after the furnace chamber is naturally cooled to room temperature, the obtained powder is added into 15mL of 10 wt.% hydrofluoric acid aqueous solution, and after soaking for 12 hours, the powder is filtered, washed and then freeze-dried. (Note: hydrofluoric acid is strongly corrosive, and the specific surface area of the obtained carbon material is up to 1190 m. the hydrofluoric acid is bottled by plastic and the calcium chloride solution is added into a filter flask.)2Per g, pore volume up to 1.3cm3In terms of a pore size of 2.7nm and 4.7 nm. The transmission electron microscope image thereof is shown in FIG. 8.
Example 7
The prepared hollow mesoporous carbon material is subjected to electrochemical performance tests, such as cycle life, coulombic efficiency, alternating current impedance and the like under different current densities, and the reason for the excellent electrochemical performance is analyzed.
The preparation method of the button-type lithium ion battery of CR 2025 using the hollow mesoporous carbon material prepared in example 2 is as follows:
1) the active material, acetylene black and Polytetrafluoroethylene (PVDF) were added to the corresponding mass of the hollow mesoporous carbon material obtained in example 2, the acetylene black and the PVDF in a 5mL weighing bottle at a mass ratio of 8:1: 1. Then dropwise adding N-methyl pyrrolidone into a weighing bottle, and stirring at room temperature overnight to uniformly mix the substances;
2) uniformly coating the mixture for coating obtained in the step 1) on a copper foil, and then carrying out vacuum drying at the temperature of 80 ℃ for 12h to obtain a pole piece with the surface containing active substances; then cutting the pole piece into a circular pole piece with the diameter of 12mm, and obtaining the mass of the active substance on the pole piece by utilizing a difference method;
transferring a pole piece with the surface containing active substances into a vacuum glove box to complete the assembly of the button cell, wherein the PE diaphragm is a cell diaphragm, the lithium piece is a counter electrode, the pole piece with the surface containing active substances is a working electrode, assembling the working electrode, the diaphragm, the counter electrode, a gasket and a cell shell into a CR 2025 button cell in the glove box, sealing the button cell by using a sealing machine, and finally preparing the button cellAnd standing the prepared button cell for 12h at normal temperature to activate the cell, thus finishing the preparation of the CR 2025 button type sodium ion battery. FIG. 9 shows a graph of cycle performance, from which it can be seen that the carbon material prepared in example 2 is at 1A g-1Has high specific capacity and excellent cycling stability at the current density of (2).
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.

Claims (10)

1. A preparation method of a hollow mesoporous carbon material comprises the following steps:
1) dissolving a carbon precursor and a corresponding catalyst in a solvent, adding a mesoporous template rich in hydroxyl, uniformly stirring, heating for polymerization, and volatilizing the residual solvent after the polymerization is finished to obtain a composite of the polymerization precursor and the template;
2) pyrolyzing the polymerization precursor and the template compound at high temperature under inert atmosphere or vacuum condition, and then naturally cooling;
3) adding the product obtained in the step 2) into hydrofluoric acid or hot sodium hydroxide solution, and removing the silicon dioxide template;
4) and (3) drying the product obtained in the step 3) to remove the residual solvent, thus obtaining the hollow mesoporous carbon material.
2. The method of claim 1, wherein the hydroxyl-rich silica template is an ordered or disordered mesoporous silica template comprising SBA-15, KIT-6, FDU-12, MCF, MCM-41, and silica gel.
3. The method of claim 1, wherein: the carbon precursor in the step 1) comprises furfuryl alcohol, phenolic resin, 2-thiophene methanol, dopamine hydrochloride, tyrosine, pyrrole, pyridine and thiophene.
4. The method of claim 3, wherein: in the step 1), dopamine hydrochloride or tyrosine serves as a precursor, the solution is hermetically stirred for 3 hours at the temperature of 50-90 ℃, and then the solvent is volatilized at the temperature of 50-90 ℃.
5. The method of claim 3, wherein: in the step 1), furfuryl alcohol, phenolic resin, 2-thiophene methanol, pyrrole, pyridine and thiophene are used as precursors, the polymerization temperature is 50-150 ℃, and then the solvent is volatilized at 50-90 ℃.
6. The method of claim 1, wherein: the step 1) catalyst comprises: oxalic acid, ferric nitrate, ferric chloride, cobalt nitrate, copper nitrate and corresponding hydrates; the catalyst determines whether addition or the type of addition is needed according to the catalytic characteristics of the carbon precursor.
7. The method of claim 1, wherein: and 2) pyrolyzing the mixture under nitrogen, argon or vacuum at the pyrolysis temperature of 500-1200 ℃.
8. The method of claim 1, wherein: the solvent in the step 1) comprises water, ethanol, trimethylbenzene, 1, 2-dichlorobenzene and a mixed solution thereof; the solvent is determined according to the solubility of the carbon precursor.
9. A hollow mesoporous carbon material characterized by: prepared by the process of any one of claims 1 to 8.
10. Use of the hollow mesoporous carbon material of claim 9 as a negative electrode material for alkali metal ion batteries and as a catalyst and catalyst support.
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