CN107746048B - Nitrogen-doped graphene-based porous carbon material and preparation method and application thereof - Google Patents
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims abstract description 34
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
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- -1 and in addition Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
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Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/325—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups reduction by other means than indicated in C07C209/34 or C07C209/36
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention discloses a nitrogen-doped graphene-based porous carbon material and a preparation method and application thereof, wherein the preparation method of the nitrogen-doped graphene-based porous carbon material comprises the following steps: 1) mixing graphite oxide, soluble sugar or/and derivatives thereof and water, ultrasonically stripping and dispersing, adding N, N' -dicyclohexylcarbodiimide to prepare a mixed solution, and fully reacting; 2) transferring the reaction liquid obtained in the step 1) into a hydrothermal reaction kettle, carrying out hydrothermal carbonization reaction, centrifuging, washing a solid product with water, and drying. The nitrogen-doped graphene-based porous carbon material is prepared from graphite oxide, soluble sugar or/and derivatives thereof and N, N' -dicyclohexylcarbodiimide, mainly comprises carbon materials, is low in cost, and has the advantages of light weight, environmental friendliness and the like. Meanwhile, the preparation method is simple and easy to implement, mild in condition, easy to obtain raw materials, good in preparation repeatability, high in activity when used as a catalyst for catalytic reduction of nitrobenzene, and good in application prospect.
Description
Technical Field
The invention relates to a nitrogen-doped graphene-based porous carbon material and a preparation method and application thereof.
Background
With the rapid development of industrialization, the increasing energy demand and environmental crisis make extensive researchers focus on developing low-price, green and environment-friendly materials. Biomass is a renewable resource for preparing functional carbon materials, typically saccharides are used as an organic compound widely distributed in nature, and can be simply converted into carbon materials by a hydrothermal method, so that the biomass is an ideal source for preparing the carbon materials. The carbon catalyst/carrier with high efficiency and long service life has extremely high application value, so the synthesis and development of the high-efficiency carbon catalyst/carrier are always important subjects in the field of catalysis. The main problems of the carbon catalysts prepared by direct carbonization, hydrothermal treatment and other methods of biomass-derived saccharides are poor catalytic efficiency and stability.
With the progress of research on carbon materials, carbon materials such as fullerene, carbon nanotube, graphene, etc. have been used to prepare carbon catalysts or as supports for metal catalysts. Graphene is a polymer made of carbon atoms in sp2The honeycomb two-dimensional carbon material formed by the hybridization mode has extremely high specific surface area (which can reach 2630m theoretically2In/g) has great advantages in catalytic reactions. The surface and the edge of the graphene oxide have rich oxygen-containing functional groups, so that the functionalization is easily realized by means of doping and the like, and the graphene oxide has great development potential in the field of catalysis. However, problems of how to realize controllable functionalization and easy agglomeration of graphene and graphene oxide need to be solved, which directly cause the reduction of catalytic activity of the catalyst, and in addition, materials such as graphene are expensive, so that the graphene-based carbon catalyst cannot be widely popularized and used so far.
Disclosure of Invention
The invention aims to provide a nitrogen-doped graphene-based porous carbon material and a preparation method thereof by controlling the morphological structure of graphene oxide and the carbonization process of saccharides on the graphene oxide, and the nitrogen-doped graphene-based porous carbon material is used as a catalyst for catalyzing nitrobenzene reduction.
The technical scheme adopted by the invention is as follows:
a preparation method of a nitrogen-doped graphene-based porous carbon material comprises the following steps:
1) mixing graphite oxide, soluble sugar or/and derivatives thereof and water, ultrasonically stripping and dispersing, adding N, N' -dicyclohexylcarbodiimide to prepare a mixed solution, and fully reacting;
2) transferring the reaction liquid obtained in the step 1) into a hydrothermal reaction kettle, carrying out hydrothermal carbonization reaction, centrifuging, washing the solid product with water, and drying to obtain the nitrogen-doped graphene-based porous carbon material.
The graphite oxide in the step 1) is prepared by the following method: mixing concentrated sulfuric acid, phosphoric acid and graphite powder, adding potassium permanganate, reacting at 45-55 ℃ for 10-15H, adding ice cakes and H2O2Mixing, centrifuging, washing the obtained precipitate with water, hydrochloric acid and anhydrous ethanol, and drying.
The concentration of the graphite oxide in the mixed solution in the step 1) is 1-10 mg/m L.
The concentration of the soluble sugar or/and the derivative thereof in the mixed solution in the step 1) is 5-100 mg/m L.
The soluble sugar in the step 1) is at least one of glucose, mannose, arabinose, xylose, lyxose, galactose, fructose, maltose, sucrose and lactose, and the derivative of the soluble sugar is sugar alcohol, sugar acid or deoxysugar corresponding to the soluble sugar.
The concentration of the N, N' -dicyclohexylcarbodiimide in the mixed solution in the step 1) is 4-40 mg/m L.
The reaction in the step 1) is carried out at 75-95 ℃, and the reaction time is 1-5 h.
The hydrothermal carbonization reaction in the step 2) is carried out at 160-240 ℃, and the reaction time is 6-24 h.
The invention has the beneficial effects that: the nitrogen-doped graphene-based porous carbon material is prepared from graphite oxide, soluble sugar or/and derivatives thereof and N, N' -dicyclohexylcarbodiimide, mainly comprises carbon materials, is low in cost, and has the advantages of light weight, environmental friendliness and the like. Meanwhile, the preparation method is simple and easy to implement, mild in condition, easy to obtain raw materials, good in preparation repeatability, high in activity when used as a catalyst for catalytic reduction of nitrobenzene, and good in application prospect.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) image of the nitrogen-doped graphene-based porous carbon material of example 1.
Detailed Description
A preparation method of a nitrogen-doped graphene-based porous carbon material comprises the following steps:
1) mixing graphite oxide, soluble sugar or/and derivatives thereof and water, ultrasonically stripping and dispersing, adding N, N' -dicyclohexylcarbodiimide to prepare a mixed solution, and fully reacting;
2) transferring the reaction liquid obtained in the step 1) into a hydrothermal reaction kettle, carrying out hydrothermal carbonization reaction, centrifuging, washing the solid product with water, and drying to obtain the nitrogen-doped graphene-based porous carbon material.
Preferably, the graphite oxide in the step 1) is prepared by the following method: mixing concentrated sulfuric acid, phosphoric acid and graphite powder, adding potassium permanganate, reacting at 45-55 ℃ for 10-15H, adding ice cakes and H2O2Mixing, centrifuging, washing the obtained precipitate with water, hydrochloric acid and anhydrous ethanol, and drying.
Preferably, the concentrated sulfuric acid, the phosphoric acid, the graphite powder, the potassium permanganate, the ice block and the H2O2The addition ratio of (A) is 180m L, (17-23) m L, (1.3-1.7) g, (7-11) g, (180-220) m L, (3-7) m L.
Preferably, the concentration of the graphite oxide in the mixed solution in the step 1) is 1-10 mg/m L.
Further preferably, the concentration of the graphite oxide in the mixed solution in the step 1) is 2-9 mg/m L.
Preferably, the concentration of the soluble sugar or/and the derivative thereof in the mixed solution in the step 1) is 5-100 mg/m L.
Further preferably, the concentration of the soluble sugar or/and the derivative thereof in the mixed solution in the step 1) is 8-26 mg/m L.
Preferably, the soluble sugar in step 1) is at least one of glucose, mannose, arabinose, xylose, lyxose, galactose, fructose, maltose, sucrose and lactose, and the derivative of the soluble sugar is a sugar alcohol, sugar acid or deoxy sugar corresponding to the soluble sugar.
Preferably, the ultrasonic power is 100W and the time is 0.5-2 h when the ultrasonic peeling dispersion is carried out in the step 1).
Preferably, the concentration of the N, N' -dicyclohexylcarbodiimide in the mixed solution in the step 1) is 4-40 mg/m L.
Further preferably, the concentration of N, N' -dicyclohexylcarbodiimide in the mixed solution in the step 1) is 4-18 mg/m L.
Preferably, the reaction in the step 1) is carried out at 75-95 ℃, and the reaction time is 1-5 h.
Preferably, the hydrothermal carbonization reaction in the step 2) is carried out at 160-240 ℃, and the reaction time is 6-24 h.
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a preparation method of a nitrogen-doped graphene-based porous carbon material comprises the following steps:
1) mixing 0.40g of graphite oxide, 0.90g of glucose and 70m of L deionized water, ultrasonically (100W) stripping and dispersing for 0.5h, then adding 0.62g N, N '-dicyclohexylcarbodiimide to obtain a mixed solution (wherein the concentration of the graphite oxide is 5.71mg/m L, the concentration of the glucose is 12.9mg/m L, and the concentration of the N, N' -dicyclohexylcarbodiimide is 8.85mg/m L), and carrying out reflux reaction at 90 ℃ for 4 h;
2) transferring the reaction solution obtained in the step 1) into a hydrothermal reaction kettle, reacting for 15h at 190 ℃, centrifuging, washing the solid product with water for 5 times, and vacuum-drying at 60 ℃ to obtain the nitrogen-doped graphene-based porous carbon material (black powder), wherein a Scanning Electron Microscope (SEM) of the nitrogen-doped graphene-based porous carbon material is shown in FIG. 1.
Example 2:
a preparation method of a nitrogen-doped graphene-based porous carbon material comprises the following steps:
1) mixing 0.40g of graphite oxide, 1.80g of sucrose and 70m of L deionized water, ultrasonically (100W) stripping and dispersing for 1h, then adding 0.62g N, N '-dicyclohexylcarbodiimide to obtain a mixed solution (wherein the concentration of the graphite oxide is 5.71mg/m L, the concentration of the sucrose is 25.7mg/m L, and the concentration of the N, N' -dicyclohexylcarbodiimide is 8.85mg/m L), and carrying out reflux reaction at 90 ℃ for 5 h;
2) transferring the reaction liquid obtained in the step 1) into a hydrothermal reaction kettle, reacting for 12 hours at 200 ℃, centrifuging, washing the solid product with water for 5 times, and drying in vacuum at 60 ℃ to obtain the nitrogen-doped graphene-based porous carbon material (black powder).
Example 3:
a preparation method of a nitrogen-doped graphene-based porous carbon material comprises the following steps:
1) mixing 0.60g of graphite oxide, 0.90g of fructose and 70m of L deionized water, ultrasonically (100W) stripping and dispersing for 0.5h, then adding 1.24g N, N '-dicyclohexylcarbodiimide to obtain a mixed solution (wherein the concentration of the graphite oxide is 8.57mg/m L, the concentration of the fructose is 12.9mg/m L, and the concentration of the N, N' -dicyclohexylcarbodiimide is 17.7mg/m L), and carrying out reflux reaction at 90 ℃ for 4 h;
2) transferring the reaction liquid obtained in the step 1) into a hydrothermal reaction kettle, reacting for 12 hours at 200 ℃, centrifuging, washing the solid product with water for 5 times, and drying in vacuum at 60 ℃ to obtain the nitrogen-doped graphene-based porous carbon material (black powder).
Example 4:
a preparation method of a nitrogen-doped graphene-based porous carbon material comprises the following steps:
1) mixing 0.20g of graphite oxide, 0.60g of glucose and 70m of L deionized water, ultrasonically (100W) stripping and dispersing for 0.5h, then adding 0.31g N, N '-dicyclohexylcarbodiimide to obtain a mixed solution (wherein the concentration of the graphite oxide is 2.86mg/m L, the concentration of the glucose is 8.57mg/m L, and the concentration of the N, N' -dicyclohexylcarbodiimide is 4.42mg/m L), and carrying out reflux reaction at 90 ℃ for 3 h;
2) transferring the reaction liquid obtained in the step 1) into a hydrothermal reaction kettle, reacting for 10 hours at 190 ℃, centrifuging, washing the solid product with water for 5 times, and drying in vacuum at 60 ℃ to obtain the nitrogen-doped graphene-based porous carbon material (black powder).
Example 1EThe graphite oxide in the step 4 is prepared by mixing 180m L concentrated sulfuric acid, 20m L phosphoric acid and 1.5g crystalline flake graphite powder, slowly adding 9.0g potassium permanganate, reacting at 50 ℃ for 12H, then adding 200g ice blocks and 5m L H with the mass fraction of 30%2O2The components are evenly mixed and centrifuged, and the obtained precipitate is washed by 100m L deionized water, 100m L mass percent of hydrochloric acid with the mass fraction of 30 percent and 100m L absolute ethyl alcohol respectively and dried for 24 hours at the temperature of 60 ℃.
Application example:
the nitrogen-doped graphene-based porous carbon material prepared in example 1 is used as a catalyst to catalyze and reduce nitrobenzene to prepare aniline, and the specific operation is as follows: uniformly mixing 20mg of nitrogen-doped graphene-based porous carbon material, 1.2g of nitrobenzene and 3.4g of hydrazine hydrate with the mass fraction of 80%, and carrying out reflux reaction at 100 ℃ for 4 hours to obtain the aniline.
The obtained aniline is detected and analyzed by a gas chromatograph (anisole is used as an internal standard substance), the conversion rate of nitrobenzene and the aniline selectivity obtained by calculation reach 100 percent, and the nitrogen-doped graphene-based porous carbon material shows good catalytic activity.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (3)
1. A preparation method of a nitrogen-doped graphene-based porous carbon material is characterized by comprising the following steps: the method comprises the following steps:
1) mixing 0.40g of graphite oxide, 0.90g of glucose and 70m of L deionized water, ultrasonically stripping and dispersing for 0.5h, adding 0.62g N, N' -dicyclohexylcarbodiimide to obtain a mixed solution, and carrying out reflux reaction for 4h at 90 ℃;
2) transferring the reaction liquid obtained in the step 1) into a hydrothermal reaction kettle, reacting for 15h at 190 ℃, centrifuging, washing the solid product with water for 5 times, and drying in vacuum at 60 ℃ to obtain the nitrogen-doped graphene-based porous carbon material.
2. The nitrogen-doped graphene-based porous carbon material prepared by the method of claim 1.
3. Use of the nitrogen-doped graphene-based porous carbon material prepared by the method of claim 1 as a catalyst.
Priority Applications (1)
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| Hierarchical Metal-Free Nitrogen-Doped Porous Graphene/Carbon Composites as an Efficient Oxygen Reduction Reaction Catalyst;Bao Men et al.;《ACS Appl. Mater. Interfaces》;20151228;第1415-1423页 * |
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