CN113148999B - Preparation method of porous graphitized carbon material - Google Patents
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- CN113148999B CN113148999B CN202110374300.6A CN202110374300A CN113148999B CN 113148999 B CN113148999 B CN 113148999B CN 202110374300 A CN202110374300 A CN 202110374300A CN 113148999 B CN113148999 B CN 113148999B
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Abstract
A preparation method of a porous graphitized carbon material relates to the carbon material. Preparing sol particles with PCS as a shell and polynuclear carbon-based iron derivatives as cores by taking low-molecular-weight polycarbosilane and carbonyl iron as raw materials and decalin as a reaction solvent; mixing sol particles with asphalt in decalin solution, and removing a solvent through reduced pressure distillation to obtain a polynuclear carbon-based iron derivative wrapped by the asphalt; oxidizing and crosslinking at high temperature, pyrolyzing to carbonize asphalt, and simultaneously converting polynuclear carbon-based iron derivatives of the inner core into inorganic metal compounds through organic-inorganic conversion; and etching by hydrofluoric acid to remove the internal metal silicide, so as to obtain the hollow porous graphitized carbon material. The raw materials used are low in price, and the using method is easy to amplify and prepare; the particle size of the polynuclear carbonyl iron@PCS sol particles is regulated and controlled by regulating and controlling the reaction conditions, so that the pore size and graphitization degree of the carbon material are regulated and controlled, and the pore diameter and graphitization of the material are controlled.
Description
Technical Field
The invention relates to a carbon material, in particular to a preparation method of a porous graphitized carbon material by taking pitch as a carbon source and iron-containing sol particles as templates and catalysts.
Background
The porous carbon not only has the advantages of high specific surface area, high electron transmission capacity, excellent stability, environmental friendliness, low preparation cost, easiness in modification, flexible structure and the like, but also has great research value and application prospect in the fields of energy storage, catalysis, water treatment, sensors, and the like, and is widely focused by researchers.
Porous carbon can be synthesized by a variety of methods including chemical activation, physical activation, pyrolysis of metal organic framework compounds, carbonization of supercritical drying conditions to synthesize organic aerogels, hard template methods, and soft template methods. However, porous carbon materials with uniform pore sizes are mainly synthesized by a template method.
The synthesis of the mesoporous material by the hard template method is realized by assembling and growing the precursor in the mesoporous pore canal of the hard template, and is a simple, convenient and effective method. The soft template method is to spontaneously assemble the surfactant and the precursor into a compound with an ordered mesostructure through the synergistic effects of ionic bond, hydrogen bond, van der Waals force and the like between the surfactant, the block copolymer and the precursor, and remove the surfactant to obtain the porous material.
However, the conventional hard template method is time consuming and causes disadvantages such as increased cost; the mesoporous carbon material obtained by the soft template method has relatively low pore size, and limits the application of the mesoporous carbon material in adsorption and separation of biomacromolecules such as protein, amino acid and the like. It is an important direction to find a simple and feasible method for preparing porous carbon materials with adjustable pore diameters, which is more beneficial to operation.
Porous carbon materials with graphitized pore walls are more conductive than conventional mesoporous carbon. Has important application in super capacitor, fuel cell and biological sensor. However, it is difficult to synthesize a carbon material having both a high specific surface area and a good graphite structure. In order to achieve the purpose, an easily graphitizable carbon source is generally selected as a precursor, and the graphitization of carbon is realized by using an ultra-high temperature. Ryoo and the like are synthesized for the first time through high-pressure in-situ graphitization by taking polycyclic aromatic hydrocarbon as a precursor of carbon. (Kim t.w., park l.s., ryoo r.a. angel. Chem. Int. Ed.2003, 42:4375-4379.) pinnavia et al synthesized highly conductive graphitized porous carbon materials using aromatic compounds such as naphthalene, anthracene, and pyrene as carbon sources (KimC.H., leeD.K., pinnavaiaT.J.Langmuir.2004, 20:5157-5159). Another approach is to use a metal catalyst to catalyze the graphitization of the hard carbon material at a lower temperature. Co ion exchange with Lu or the like 2+ Is introduced into the mixed structure of the oligomeric phenolic resin/CTAB, and is catalyzed and carbonized to obtain the porous carbon material with highly graphitized pore walls (LuA.H., liW.C., salabasE.L., spliethofF.B., schiithF.Chem.Mater.2006, 18:2086-2094).
The above-mentioned various methods for preparing the porous carbon material provide various choices for preparing the porous carbon material, which has important significance for preparing the porous carbon material. Meanwhile, the defects that the pore size is not easy to adjust, graphitization is difficult to realize synchronously and the like are also present. In addition, the method has the defects of difficult amplification preparation, unfavorable industrial production and the like, thereby limiting the popularization and application of the method.
The porous graphitized carbon material is prepared by using sol particles with uniform and adjustable particle size and Fe as templates and catalysts and using asphalt as a carbon source. The pore diameter of the porous carbon is regulated and controlled by controlling the particle diameter of sol particles, and meanwhile, the porous graphitized carbon material with controllable and adjustable pore diameter is obtained in one step at a lower carbonization temperature by utilizing the catalysis of Fe.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the preparation method of the porous graphitized carbon material, which takes asphalt with low price and high carbonization yield as a carbon source, takes sol particles containing Fe as a template and a catalyst, comprises the steps of blending, pyrolysis, etching and the like, has controllable and adjustable aperture, is easy to realize large-scale preparation and has low cost.
The invention comprises the following steps:
1) Preparing sol particles with PCS as a shell and polynuclear carbon-based iron derivatives as cores (polynuclear carbonyl iron@PCS) by taking low molecular weight polycarbosilane (LPCS) and carbonyl iron as raw materials and decalin as a reaction solvent;
2) Mixing the sol particles obtained in the step 1) with asphalt in decalin solution, and removing the solvent through reduced pressure distillation to obtain an asphalt-coated polynuclear carbon-based iron derivative;
3) Oxidizing and crosslinking the polynuclear carbon-based iron derivative wrapped by the asphalt obtained in the step 2) at a high temperature, pyrolyzing the asphalt to carbonize the asphalt, and simultaneously converting the polynuclear carbon-based iron derivative of the inner core through organic-inorganic conversion to generate an inorganic metal compound;
4) And (3) etching the sample obtained in the step (3) by hydrofluoric acid to remove the internal metal silicide, thereby preparing the hollow porous graphitized carbon material.
In step 1), the PCS selects PCS with low molecular weight, which is a byproduct of preparing silicon carbide fiber; the reverse ofThe solvent is selected from decalin, the particle size of the sol is changed by PCS and Fe (CO) 5 、C 10 H 18 The mass ratio of the raw materials is (0.5-3) to 1 to 40; the reaction temperature is 150-200 ℃ and the reaction time is 2-24 hours to regulate and control;
in step 2), the asphalt may be asphalt having a softening point of 160 to 300 ℃; the ratio of the asphalt to the synthesized sample in the step 1) can be 1-10:1; the porous hollow structure of the final synthetic carbon material can be regulated and controlled by regulating the proportion of asphalt to the synthetic sample in the step 1);
in the step 3), the temperature of the oxidative crosslinking can be 150-300 ℃, and the time of the oxidative crosslinking can be 0.5-20 h; the pyrolysis temperature can be 600-1800 ℃, and the pyrolysis time can be 30-360 min.
In the step 4), the concentration of the hydrofluoric acid can be 5-20%, and the etching time can be adjusted between 30min and 150min.
Compared with the prior art, the invention has the following outstanding advantages:
1. the raw materials are low in price (PCS with low molecular weight is a byproduct of preparing silicon carbide fiber, carbonyl iron and asphalt are low-cost industrial raw materials), and the using method is easy to prepare in an amplifying way;
2. the particle size of the polynuclear carbonyl iron@PCS sol particles is regulated and controlled by regulating and controlling the reaction conditions, so that the pore size and graphitization degree of the carbon material are regulated and controlled, and the pore diameter and graphitization of the material are controlled.
Drawings
Fig. 1 is a TEM image of the porous graphitized carbon obtained in example 3.
Detailed Description
The invention will be further illustrated by the following examples in conjunction with the accompanying drawings.
Example 1:
1) By reacting polydimethylsilane [ Si (CH) 3 ) 2 ] n Heating at 450deg.C under high purity nitrogen for 15 hr, converting into PCS by Kumula rearrangement, and distilling under reduced pressure at 300deg.C to collect low molecular weight LPCS fraction (transparent semi-viscous liquid at room temperature);
2) And (3) installing a reflux device, vacuumizing, introducing high-purity argon, and repeating the steps three times. Subsequently, while argon was being introduced, 5g of Fe (CO) was added to a 500mL three-necked round bottom flask in sequence 5 2.5g LPCS,200mL decalin, under vigorous stirring, reflux at 150℃for 24h to give a black iron sol;
3) 30g of bitumen with a softening point of 150℃120ml of iron sol and 100ml of decalin are introduced into a 500ml three-necked round-bottomed flask and the mixture is refluxed with vigorous stirring for 2h. The solvent was then removed by distillation under reduced pressure. Drying the product in a vacuum oven at 80 ℃ for 48 hours;
4) Grinding the sample obtained in step 3) at 200cm 3 In the flowing dry air at a heating rate of 1 ℃/min to 120 ℃, and then at a heating rate of 10 ℃/h to a final temperature of 160 ℃ and preserving heat for 20h. And then heating to 600 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere for pyrolysis for 5 hours to obtain the carbon-coated iron-containing ceramic nanoparticle.
5) And (3) etching the sample obtained in the step (4) by 5% hydrofluoric acid for 150min to obtain the hollow porous carbon material.
Example 2:
1) Step 1) as in example 1;
2) And (3) installing a reflux device, vacuumizing, introducing high-purity argon, and repeating the steps three times. Subsequently, while argon was being introduced, 5g of Fe (CO) was added to a 500mL three-necked round bottom flask in sequence 5 5g LPCS,200mL decalin, under vigorous stirring, reflux at 170℃for 18h to give a black iron sol;
3) 15g of bitumen with a softening point of 220℃120mL of iron sol and 100mL of decalin are introduced into a 500mL three-necked round-bottomed flask and the mixture is refluxed for 2h with vigorous stirring. The solvent was then removed by distillation under reduced pressure. Drying the product in a vacuum oven at 80 ℃ for 48 hours;
4) Grinding the sample obtained in step 3) at 200cm 3 In the flowing dry air at a heating rate of 1 ℃/min to 120 ℃, and then at a heating rate of 10 ℃/h to a final temperature of 180 ℃ and preserving heat for 15h. Then pyrolyzing for 4 hours in nitrogen atmosphere at a heating rate of 5 ℃/min to 800 ℃ to obtain the carbon packageWrapped iron-containing ceramic nanoparticles;
5) And (3) etching the sample obtained in the step (4) by 8% hydrofluoric acid for 100min to obtain the hollow porous carbon material.
Example 3:
1) Step 1) as in example 1;
2) And (3) installing a reflux device, vacuumizing, introducing high-purity argon, and repeating the steps three times. Subsequently, while argon was being introduced, 5g of Fe (CO) was added to a 500mL three-necked round bottom flask in sequence 5 5g LPCS,200mL decalin, under vigorous stirring, reflux at 170℃for 18h to give a black iron sol;
3) 15g of bitumen with a softening point of 240℃120mL of iron sol and 100mL of decalin are introduced into a 500mL three-necked round-bottomed flask and the mixture is refluxed for 2h with vigorous stirring. The solvent was then removed by distillation under reduced pressure. Drying the product in a vacuum oven at 80 ℃ for 48 hours;
4) Grinding the sample obtained in step 3) at 200cm 3 In the flowing dry air at a heating rate of 1 ℃/min to 120 ℃, and then at a heating rate of 10 ℃/h to a final temperature of 200 ℃ and preserving heat for 15h. Then heating to 1000 ℃ at a heating rate of 5 ℃/min in nitrogen atmosphere for pyrolysis for 2 hours to obtain carbon-coated iron-containing ceramic nanoparticles;
5) And (3) etching the sample obtained in the step (4) by 8% hydrofluoric acid for 100min to obtain the hollow porous carbon material.
Fig. 1 is a TEM image of the porous graphitized carbon obtained in example 3.
Example 4:
1) Step 1) as in example 1;
2) And (3) installing a reflux device, vacuumizing, introducing high-purity argon, and repeating the steps three times. Subsequently, while argon was being introduced, 5g of Fe (CO) was added to a 500mL three-necked round bottom flask in sequence 5 10g LPCS,200ml decalin, under vigorous stirring, reflux at 190℃for 10h to give a black iron sol;
3) 10g of bitumen with a softening point of 260℃120mL of iron sol and 100mL of decalin are introduced into a 500mL three-necked round-bottomed flask and the mixture is refluxed for 2h with vigorous stirring. The solvent was then removed by distillation under reduced pressure. Drying the product in a vacuum oven at 80 ℃ for 48 hours;
4) Grinding the sample obtained in step 3) at 200cm 3 In the flowing dry air at a heating rate of 1 ℃/min to 120 ℃, and then at a heating rate of 10 ℃/h to a final temperature of 230 ℃ and preserving heat for 15h. Then heating to 1300 ℃ at a heating rate of 5 ℃/min in nitrogen atmosphere for pyrolysis for 2 hours to obtain carbon-coated iron-containing ceramic nanoparticles;
5) And (3) etching the sample obtained in the step (4) by 10% hydrofluoric acid for 100min to obtain the hollow porous carbon material.
Example 5:
1) Step 1) as in example 1;
2) And (3) installing a reflux device, vacuumizing, introducing high-purity argon, and repeating the steps three times. Subsequently, while argon was being introduced, 5g of Fe (CO) was added to a 500mL three-necked round bottom flask in sequence 5 15g LPCS,200mL decalin, under vigorous stirring, refluxing at 200℃for 2h to give a black iron sol;
3) 5g of bitumen with a softening point of 300℃120mL of iron sol and 100mL of decalin are introduced into a 500mL three-necked round-bottomed flask and the mixture is refluxed for 2h with vigorous stirring. The solvent was then removed by distillation under reduced pressure. Drying the product in a vacuum oven at 80 ℃ for 48 hours;
4) Grinding the sample obtained in step 3) at 200cm 3 In the flowing dry air at a heating rate of 1 ℃/min to 120 ℃, and then at a heating rate of 10 ℃/h to a final temperature of 260 ℃ and preserving heat for 15h. Then heating to 1600 ℃ at a heating rate of 5 ℃/min in nitrogen atmosphere for pyrolysis for 1h to obtain carbon-coated iron-containing ceramic nanoparticles;
5) And (3) etching the sample obtained in the step (4) by 15% hydrofluoric acid for 50min to obtain the hollow porous carbon material.
Example 6:
1) Step 1) as in example 1;
2) And (3) installing a reflux device, vacuumizing, introducing high-purity argon, and repeating the steps three times. Subsequently, while argon was being introduced, 5g of Fe (CO) was added to a 500mL three-necked round bottom flask in sequence 5 10g LPCS,200mL decalin, under vigorous stirring, reflux at 200℃for 2h to give a black iron sol;
3) 5g of bitumen with a softening point of 270℃120mL of iron sol and 100mL of decalin are introduced into a 500mL three-necked round-bottomed flask and the mixture is refluxed for 2h with vigorous stirring. The solvent was then removed by distillation under reduced pressure. Drying the product in a vacuum oven at 80 ℃ for 48 hours;
4) Grinding the sample obtained in step 3) at 200cm 3 In the flowing dry air at a heating rate of 1 ℃/min to 120 ℃, and then at a heating rate of 10 ℃/h to a final temperature of 300 ℃ and preserving heat for 15h. Then in nitrogen atmosphere, heating to 1800 ℃ at a heating rate of 5 ℃/min for pyrolysis for 30min to obtain carbon-coated iron-containing ceramic nanoparticles;
5) And (3) etching the sample obtained in the step (4) by 20% hydrofluoric acid for 30min to obtain the hollow porous carbon material.
Claims (8)
1. The preparation method of the porous graphitized carbon material is characterized by comprising the following steps of:
1) Preparing sol particles with PCS as a shell and polynuclear carbon-based iron derivatives as cores by taking low-molecular-weight polycarbosilane and carbonyl iron as raw materials and decalin as a reaction solvent; the particle size of the sol particles is changed by PCS, fe (CO) 5 、C 10 H 18 The mass ratio of the raw materials is (0.5-3) to 1 to 40; the reaction temperature is 150-200 ℃ and the reaction time is 2-24 hours to regulate and control;
2) Mixing the sol particles obtained in the step 1) with asphalt in decalin solution, and removing the solvent through reduced pressure distillation to obtain an asphalt-coated polynuclear carbon-based iron derivative;
3) Oxidizing and crosslinking the polynuclear carbon-based iron derivative wrapped by the asphalt obtained in the step 2) at a high temperature, pyrolyzing the asphalt to carbonize the asphalt, and simultaneously converting the polynuclear carbon-based iron derivative of the inner core through organic-inorganic conversion to generate an inorganic metal compound;
4) And (3) etching the sample obtained in the step (3) by hydrofluoric acid to remove the internal metal silicide, thereby preparing the hollow porous graphitized carbon material.
2. The method of claim 1, wherein in step 1), the PCS selects a PCS having a low molecular weight.
3. The method for preparing a porous graphitized carbon material as claimed in claim 1, wherein in the step 2), the pitch is a pitch having a softening point of 160 to 300 ℃.
4. The method for preparing a porous graphitized carbon material according to claim 1, wherein in the step 2), the ratio of pitch to sol particles is 1-10:1; the porous hollow structure of the final synthetic carbon material is regulated and controlled by regulating the proportion of asphalt to sol particles.
5. The method of preparing a porous graphitized carbon material as claimed in claim 1, wherein in the step 3), the temperature of the oxidative crosslinking is 150 to 300 ℃ and the time of the oxidative crosslinking is 0.5 to 20 hours.
6. The method for preparing a porous graphitized carbon material as claimed in claim 1, wherein in the step 3), the pyrolysis temperature is 600 to 1800 ℃ and the pyrolysis time is 30 to 360 minutes.
7. The method of claim 1, wherein in step 4), the hydrofluoric acid concentration is 5% to 20%.
8. The method of claim 1, wherein in step 4), the etching time is 30 to 150 minutes.
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