CN114956040B - Nitrogen-oxygen doped hierarchical porous carbon material, preparation method and application - Google Patents
Nitrogen-oxygen doped hierarchical porous carbon material, preparation method and application Download PDFInfo
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Abstract
The invention discloses a nitrogen-oxygen doped hierarchical porous carbon material, a preparation method and application thereof, comprising the following steps: step 1: carrying out ultrasonic treatment on the organic matters containing nitrogen and oxygen, and drying; placing the mixture in alkali solution for activation, and washing to obtain alkali activated organic matters; step 2: the organic matters obtained in the step 1 are kept at the temperature of 300-500 ℃ for 15-60 min in inert atmosphere; then cooling to 100-200 ℃, introducing air atmosphere, and cooling to obtain pre-oxidized organic matters; step 3: the preoxidized organic matters obtained in the step 2 are kept at the temperature of 300-500 ℃ for 15-60 min in inert atmosphere; then preserving heat for 1-4 h at 700-1000 ℃ and cooling to obtain the nitrogen-oxygen doped hierarchical porous carbon material; the preparation method has the advantages of simple steps, low cost, simple and easily available raw materials, easy realization of large-scale batch production and convenient industrialized application and popularization.
Description
Technical Field
The invention relates to the technical field of porous carbon materials, in particular to a nitrogen-oxygen doped graded porous carbon material, a preparation method and application thereof.
Background
The porous carbon material has the characteristics of low price, adjustable pore structure, good conductivity, chemical structure stability, high specific surface area and the like. The method has wide application in the fields of carbon dioxide adsorption, super capacitors, electrolytic water, secondary batteries, electromagnetic shielding and absorption, seawater evaporation, oil-water separation and the like. The surface wettability, conductivity and other physical and chemical properties of the carbon material can be effectively improved by doping the carbon material with nitrogen and oxygen heteroatoms, and the carbon material has attracted a great deal of attention.
At present, three common methods exist for introducing nitrogen and oxygen elements into carbon materials, namely, directly using nitrogen-containing substances such as ammonia gas and the like to perform post-treatment such as pre-oxidation and the like on the carbon materials carbonized at high temperature. And secondly, carbonizing the mixture of the organic matters and the nitrogen-oxygen-containing compound. Thirdly, directly carbonizing treatment by utilizing the nitrogen-oxygen-containing organic matters; the third method is relatively simple and does not require the introduction of additional nitrogen-oxygen heteroatoms into the carbon source. For example, patent No. 2017109952117, a preparation method of a multistage Kong Dan oxygen doped carbon supercapacitor electrode material, which is a multistage Kong Dan oxygen doped carbon containing a large number of micropores, mesopores and macropores and having a high specific surface area and capable of being used for a supercapacitor electrode material, is obtained by a method of mixing and carbonizing biomass carbon source yolk and trisodium thiocyanate, activating and carbonizing by KOH, and activating and carbonizing by acid. But the method has complex steps,High energy consumption and cost, and is difficult to prepare on a large scale. 2021111905727, a preparation method and application of heteroatom self-doped biomass porous carbon, which comprises the steps of carrying out ultrasonic treatment and ball milling treatment on Japanese pagodatree leaf and duckweed, and carrying out hydrothermal pre-oxidation, KOH activation carbonization and CO treatment 2 And (5) activating and washing with hydrochloric acid to obtain the heteroatom self-doped biomass porous carbon. The method has good application prospect in the field of sewage purification, but the preparation process is complex, and the preparation period is long.
In summary, the existing preparation method generally has the problems of complex preparation steps, long time consumption and the like. At present, the existing activation method can greatly reduce the content of the doped hetero atoms in the carbon material while improving the specific surface area. In the carbonization process, a nitrogen source is easily decomposed into gas, the nitrogen source utilization rate is low, and the nitrogen atom content in the obtained carbon material is low.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a nitrogen-oxygen doped hierarchical porous carbon material which is simple in preparation method and capable of improving nitrogen content, and a preparation method and application thereof. The method takes nitrogen-oxygen organic matters with abundant reserves and low cost as carbon sources, adopts alkali activation, pre-oxidation treatment and pyrolysis processes, has simple preparation process, does not need to use templates, does not need to introduce other nitrogen sources and oxygen sources, and has low cost of the used raw materials. Through optimizing the technological conditions of the pretreatment process, the heat stability of nitrogen-containing species is enhanced by promoting crosslinking while the activator etches the pores, and the nitrogen content of the carbon material is increased.
The technical scheme adopted by the invention is as follows:
the preparation method of the nitrogen-oxygen doped hierarchical porous carbon material is characterized by comprising the following steps of:
step 1: carrying out ultrasonic treatment on the organic matters containing nitrogen and oxygen, and drying; placing the mixture in alkali solution for activation, and washing to obtain alkali activated organic matters;
step 2: the organic matters obtained in the step 1 are kept at the temperature of 300-500 ℃ for 15-60 min in inert atmosphere; then cooling to 100-200 ℃, introducing air atmosphere, and cooling to obtain pre-oxidized organic matters;
step 3: the preoxidized organic matters obtained in the step 2 are kept at the temperature of 300-500 ℃ for 15-60 min in inert atmosphere; then preserving heat for 1-4 h at 700-1000 ℃ and cooling to obtain the nitrogen-oxygen doped hierarchical porous carbon material.
Further, the nitrogen-oxygen-containing organic matter in the step 1 is one or a mixture formed by mixing two or more of urea, dicyandiamide, melamine formaldehyde foam, polyurethane foam, polyacrylonitrile, poly-butyronitrile and polyphosphazene according to any proportion.
Further, the ultrasonic process in the step 1 is as follows: firstly, adopting secondary water to carry out ultrasonic treatment for 15-60 min, and then carrying out ultrasonic treatment in absolute ethyl alcohol for 15-60 min.
Further, the alkali solution in the step 1 is one of NaOH, KOH and LiOH; the concentration of the alkali solution is 1-6 mol/L.
Further, the activation temperature in the step 1 is 40-90 ℃ and the activation time is 15-60 min.
Further, the inert atmosphere in the step 2 and the step 3 is an argon atmosphere or a nitrogen atmosphere.
The nitrogen-oxygen doped hierarchical porous carbon material has a hierarchical porous structure and contains abundant micropores and mesoporous structures; the BET specific surface area of the carbon material is 500-2500 m 2 g -1 The method comprises the steps of carrying out a first treatment on the surface of the The carbon material contains 60 to 95at% of carbon element, 1 to 20at% of nitrogen element and 1 to 20at% of oxygen element.
The application of the nitrogen-oxygen doped graded porous carbon material is that the porous carbon material is used for preparing super capacitors, electrolytic water hydrogen and oxygen evolution catalytic electrodes, lithium ion electrodes, sodium ion electrodes, potassium ion electrodes, electromagnetic shielding and absorbing agents, oil-water separation absorbing agents and sea water desalination agents.
The beneficial effects of the invention are as follows:
(1) The invention adopts the organic matter containing nitrogen and oxygen as the carbon source nitrogen source and the oxygen source at the same time, does not need the subsequent complex heteroatom doping process, realizes the effective doping of nitrogen and oxygen heteroatoms in the preparation process, and has even distribution;
(2) In the carbonization process, more heat-stable nitrogen sources in the organic matters are reserved in the carbon material by alkali activation and pre-oxidation, the nitrogen source utilization rate is high, and the nitrogen atom content in the obtained carbon material is high; the defect degree of the carbon material is enhanced through alkali activation and pre-oxidation, and the pore structure is more abundant;
(3) The carbon material has controllable content of nitrogen-oxygen hetero atoms doped, controllable pore structure and defect degree, and is favorable for improving the physical and chemical properties of the carbon material, such as specific surface area, and the like; the obtained carbon material can be used for super capacitor electrode materials, electrolytic water hydrogen evolution and oxygen evolution catalytic electrode materials, electromagnetic shielding and absorbing materials, oil-water separation adsorbents and sea water desalination materials;
(4) The preparation method has the advantages of simple steps, low cost, simple and easily available raw materials, easy realization of large-scale batch production and convenient industrialized application and popularization.
Drawings
FIG. 1 is a flow chart of the preparation of nitrogen-oxygen doped hierarchical porous carbon materials.
FIG. 2 is a schematic diagram of a nitrogen-oxygen doped graded porous carbon material.
FIG. 3 is an SEM image of a porous carbon material obtained in example 1 of the present invention.
Fig. 4 is a TEM image of the porous carbon material obtained in example 1 of the present invention.
Fig. 5 is a nitrogen adsorption/desorption curve of the porous carbon material obtained in example 1 of the present invention.
FIG. 6 is a graph showing pore size distribution of the porous carbon material obtained in example 1 of the present invention.
FIG. 7 is a total X-ray photoelectron spectrum of a porous carbon material obtained in example 1 of the present invention.
Fig. 8 is an SEM image of the porous carbon material obtained in example 4 of the present invention.
Detailed Description
The invention will be further described with reference to the drawings and specific examples.
A preparation method of a nitrogen-oxygen doped hierarchical porous carbon material is shown in fig. 1, and comprises the following steps:
step 1: ultrasonically treating the organic matters containing nitrogen and oxygen, cleaning soluble impurities after ultrasonic treatment, and then drying; placing the mixture in an alkali solution for activation, and washing the mixture (washing the mixture with deionized water until filtrate is neutral) to obtain alkali-activated organic matters; the organic matter containing nitrogen and oxygen is one or a mixture of two or more of urea, dicyandiamide, melamine formaldehyde foam, polyurethane foam, polyacrylonitrile, poly-butyronitrile and polyphosphazene in any proportion. The ultrasonic process is as follows: firstly, adopting secondary water to carry out ultrasonic treatment for 15-60 min, and then carrying out ultrasonic treatment in absolute ethyl alcohol for 15-60 min. The alkali solution is one of NaOH, KOH and LiOH; the concentration of the alkali solution is 1-6 mol/L. The activation temperature is 40-90 ℃ and the activation time is 15-60 min.
Step 2: the organic matters obtained in the step 1 are kept at the temperature of 300-500 ℃ for 15-60 min in inert atmosphere; then cooling to 50-200 ℃, introducing air atmosphere, and cooling to obtain pre-oxidized organic matters; the inert atmosphere is argon atmosphere or nitrogen atmosphere.
Step 3: the preoxidized organic matters obtained in the step 2 are kept at the temperature of 300-500 ℃ for 15-60 min in inert atmosphere; then preserving heat for 1-4 h at 700-1000 ℃ and cooling to obtain the nitrogen-oxygen doped hierarchical porous carbon material. The inert atmosphere is argon atmosphere or nitrogen atmosphere.
The nitrogen-oxygen doped hierarchical porous carbon material has a hierarchical porous structure, contains abundant micropores and mesoporous structures, and has a high specific surface area. The BET specific surface area of the carbon material is 500-2500 m 2 g -1 The method comprises the steps of carrying out a first treatment on the surface of the The carbon material contains 60-95 at% of carbon element, 1-20 at% of nitrogen element and 1-20 at% of oxygen element.
The application of the nitrogen-oxygen doped graded porous carbon material is that the porous carbon material is used for preparing super capacitors, electrolytic water hydrogen and oxygen evolution catalytic electrodes, lithium ion electrodes, sodium ion electrodes, potassium ion electrodes, electromagnetic shielding and absorbing agents, oil-water separation absorbing agents and sea water desalination agents.
The instruments used for material characterization in this example were:
scanning electron microscope: the model is H-7650, and the manufacturer is Hitachi company; transmission electron microscope: model S-4800Hitachi, manufacturer Hitachi; specific surface area and porosity analyzer: the model is BELSORP MAX II, and the manufacturer is Japanese Michael Bayer. X-ray photoelectron spectroscopy: the model is K-Alpha, and the manufacturer is Sieimer Feishul technology company in U.S.
Example 1
The nitrogen-oxygen doped hierarchical porous carbon material was prepared as follows:
step 1: respectively placing melamine formaldehyde foam into secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning soluble impurities, and drying to obtain a cleaned melamine formaldehyde foam raw material; and (3) placing the dried melamine foam material in a 5mol/L NaOH solution at 65 ℃ for soaking for 30min, washing with deionized water until the filtrate is neutral, and drying to obtain the NaOH-activated melamine formaldehyde foam.
Step 2: transferring the activated melamine formaldehyde foam obtained in the step 1 into a tube furnace for calcination, preserving heat for 30min at 400 ℃ in an inert atmosphere, then cooling to 150 ℃ and introducing an air atmosphere, and naturally cooling to room temperature to obtain the pre-oxidized melamine formaldehyde foam.
Step 3: carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step 2 for 30min at 400 ℃ under the protection of inert atmosphere, carbonizing for 2h at 900 ℃, and naturally cooling to room temperature to obtain the nitrogen-oxygen doped hierarchical porous carbon material.
Example 2
The nitrogen-oxygen doped hierarchical porous carbon material was prepared as follows:
step 1: respectively placing melamine formaldehyde foam into secondary water and absolute ethyl alcohol for ultrasonic treatment for 15min, cleaning soluble impurities, and drying to obtain a cleaned melamine formaldehyde foam raw material; and (3) placing the dried melamine foam material in a KOH solution with the concentration of 1mol/L at the temperature of 40 ℃ for soaking for 15min, washing with deionized water until the filtrate is neutral, and drying to obtain the KOH-activated melamine formaldehyde foam.
Step 2: transferring the activated melamine formaldehyde foam obtained in the step 1 into a tube furnace for calcination, preserving heat for 30min at 400 ℃ in an inert atmosphere, then cooling to 150 ℃ and introducing an air atmosphere, and naturally cooling to room temperature to obtain the pre-oxidized melamine formaldehyde foam.
Step 3: carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step 2 for 30min at 400 ℃ under the protection of inert atmosphere, carbonizing for 2h at 900 ℃, and naturally cooling to room temperature to obtain the nitrogen-oxygen doped hierarchical porous carbon material.
Example 3
The nitrogen-oxygen doped hierarchical porous carbon material was prepared as follows:
step 1: respectively placing melamine formaldehyde foam into secondary water and absolute ethyl alcohol for ultrasonic treatment for 60min, cleaning soluble impurities, and drying to obtain a cleaned melamine formaldehyde foam raw material; and (3) placing the dried melamine foam material in a 6mol/L LiOH solution at 90 ℃ for soaking for 60min, washing with deionized water until the filtrate is neutral, and drying to obtain the LiOH activated melamine formaldehyde foam.
Step 2: transferring the activated melamine formaldehyde foam obtained in the step 1 into a tube furnace for calcination, preserving heat for 30min at 400 ℃ in an inert atmosphere, then cooling to 150 ℃ and introducing an air atmosphere, and naturally cooling to room temperature to obtain the pre-oxidized melamine formaldehyde foam.
Step 3: carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step 2 for 30min at 400 ℃ under the protection of inert atmosphere, carbonizing for 2h at 900 ℃, and naturally cooling to room temperature to obtain the nitrogen-oxygen doped hierarchical porous carbon material.
Example 4
The nitrogen-oxygen doped hierarchical porous carbon material was prepared as follows:
step 1: respectively placing melamine formaldehyde foam into secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning soluble impurities, and drying to obtain a cleaned melamine formaldehyde foam raw material; and (3) placing the dried melamine foam material in a KOH solution with the concentration of 1mol/L at the temperature of 40 ℃ for soaking for 60min, washing with deionized water until the filtrate is neutral, and drying to obtain the KOH-activated melamine formaldehyde foam.
Step 2: transferring the activated melamine formaldehyde foam obtained in the step 1 into a tube furnace for calcination, preserving heat at 400 ℃ for 30min in an inert atmosphere, cooling to 50 ℃, introducing an air atmosphere, and naturally cooling to room temperature to obtain the pre-oxidized melamine formaldehyde foam.
Step 3: carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step 2 for 30min at 400 ℃ under the protection of inert atmosphere, carbonizing for 2h at 900 ℃, and naturally cooling to room temperature to obtain the nitrogen-oxygen doped hierarchical porous carbon material.
Example 5
The nitrogen-oxygen doped hierarchical porous carbon material was prepared as follows:
step 1: respectively placing melamine formaldehyde foam into secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning soluble impurities, and drying to obtain a cleaned melamine formaldehyde foam raw material; and (3) placing the dried melamine foam material in a 6mol/L LiOH solution at 90 ℃ for soaking for 15min, washing with deionized water until the filtrate is neutral, and drying to obtain the LiOH activated melamine formaldehyde foam.
Step 2: transferring the activated melamine formaldehyde foam obtained in the step 1 into a tube furnace for calcination, preserving heat for 30min at 400 ℃ in an inert atmosphere, then cooling to 200 ℃ and introducing an air atmosphere, and naturally cooling to room temperature to obtain the pre-oxidized melamine formaldehyde foam.
Step 3: carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step 2 for 30min at 400 ℃ under the protection of inert atmosphere, carbonizing for 2h at 900 ℃, and naturally cooling to room temperature to obtain the nitrogen-oxygen doped hierarchical porous carbon material.
Example 6
The nitrogen-oxygen doped hierarchical porous carbon material was prepared as follows:
step 1: respectively placing melamine formaldehyde foam into secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning soluble impurities, and drying to obtain a cleaned melamine formaldehyde foam raw material; and (3) placing the dried melamine foam material in a 1mol/L NaOH solution at 65 ℃ for soaking for 60min, washing with deionized water until the filtrate is neutral, and drying to obtain the NaOH-activated melamine formaldehyde foam.
Step 2: transferring the activated melamine formaldehyde foam obtained in the step 1 into a tube furnace for calcination, preserving heat at 300 ℃ for 15min in an inert atmosphere, cooling to 50 ℃, introducing an air atmosphere, and naturally cooling to room temperature to obtain the pre-oxidized melamine formaldehyde foam.
Step 3: carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step 2 for 15min at 300 ℃ under the protection of inert atmosphere, carbonizing for 2h at 900 ℃, and naturally cooling to room temperature to obtain the nitrogen-oxygen doped hierarchical porous carbon material.
Example 7
The nitrogen-oxygen doped hierarchical porous carbon material was prepared as follows:
step 1: respectively placing melamine formaldehyde foam into secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning soluble impurities, and drying to obtain a cleaned melamine formaldehyde foam raw material; and (3) placing the dried melamine foam material in a 6mol/L NaOH solution at 65 ℃ for soaking for 15min, washing with deionized water until the filtrate is neutral, and drying to obtain the NaOH-activated melamine formaldehyde foam.
Step 2: transferring the activated melamine formaldehyde foam obtained in the step 1 into a tube furnace for calcination, preserving heat at 500 ℃ for 60min in an inert atmosphere, cooling to 150 ℃, introducing an air atmosphere, and naturally cooling to room temperature to obtain the pre-oxidized melamine formaldehyde foam.
Step 3: carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step 2 for 60min at 500 ℃ under the protection of inert atmosphere, carbonizing for 2h at 900 ℃, and naturally cooling to room temperature to obtain the nitrogen-oxygen doped hierarchical porous carbon material.
Example 8
The nitrogen-oxygen doped hierarchical porous carbon material was prepared as follows:
step 1: respectively placing melamine formaldehyde foam into secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning soluble impurities, and drying to obtain a cleaned melamine formaldehyde foam raw material; and (3) placing the dried melamine foam material in a 3mol/L NaOH solution at 65 ℃ for soaking for 30min, washing with deionized water until the filtrate is neutral, and drying to obtain the NaOH-activated melamine formaldehyde foam.
Step 2: transferring the activated melamine formaldehyde foam obtained in the step 1 into a tube furnace for calcination, preserving heat at 400 ℃ for 60min in an inert atmosphere, cooling to 150 ℃ and introducing an air atmosphere, and naturally cooling to room temperature to obtain the pre-oxidized melamine formaldehyde foam.
Step 3: carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step 2 for 30min at 400 ℃ under the protection of inert atmosphere, carbonizing for 1h at 700 ℃, and naturally cooling to room temperature to obtain the nitrogen-oxygen doped hierarchical porous carbon material.
Example 9
The nitrogen-oxygen doped hierarchical porous carbon material was prepared as follows:
step 1: respectively placing melamine formaldehyde foam into secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning soluble impurities, and drying to obtain a cleaned melamine formaldehyde foam raw material; and (3) soaking the dried melamine foam material in a 3mol/L KOH solution for 30min at 65 ℃, washing with deionized water until the filtrate is neutral, and drying to obtain the KOH-activated melamine formaldehyde foam.
Step 2: transferring the activated melamine formaldehyde foam obtained in the step 1 into a tube furnace for calcination, preserving heat at 400 ℃ for 15min in an inert atmosphere, cooling to 150 ℃, introducing an air atmosphere, and naturally cooling to room temperature to obtain the pre-oxidized melamine formaldehyde foam.
Step 3: carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step 2 for 15min at 400 ℃ under the protection of inert atmosphere, carbonizing for 4h at 1000 ℃, and naturally cooling to room temperature to obtain the nitrogen-oxygen doped hierarchical porous carbon material.
Example 10
The nitrogen-oxygen doped hierarchical porous carbon material was prepared as follows:
step 1: respectively placing melamine formaldehyde foam into secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning soluble impurities, and drying to obtain a cleaned melamine formaldehyde foam raw material; and (3) soaking the dried melamine foam material in a 3mol/L KOH solution for 30min at 65 ℃, washing with deionized water until the filtrate is neutral, and drying to obtain the KOH-activated melamine formaldehyde foam.
Step 2: transferring the activated melamine formaldehyde foam obtained in the step 1 into a tube furnace for calcination, preserving heat at 400 ℃ for 15min in an inert atmosphere, cooling to 150 ℃, introducing an air atmosphere, and naturally cooling to room temperature to obtain the pre-oxidized melamine formaldehyde foam.
Step 3: carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step 2 for 15min at 400 ℃ under the protection of inert atmosphere, carbonizing for 2h at 800 ℃, and naturally cooling to room temperature to obtain the nitrogen-oxygen doped hierarchical porous carbon material.
Example 11
The nitrogen-oxygen doped hierarchical porous carbon material was prepared as follows:
step 1: respectively placing polyurethane foam into secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning soluble impurities, and drying to obtain a cleaned polyurethane foam raw material; and (3) placing the dried polyurethane foam material into a 5mol/L NaOH solution at 60 ℃ for soaking for 30min, washing with deionized water until the filtrate is neutral, and drying to obtain the NaOH activated polyurethane foam.
Step 2: transferring the activated polyurethane foam obtained in the step 1 into a tube furnace for calcination, preserving heat for 30min at 400 ℃ in an inert atmosphere, then cooling to 150 ℃, introducing an air atmosphere, and naturally cooling to room temperature to obtain the pre-oxidized polyurethane foam.
Step 3: carbonizing the pre-oxidized polyurethane foam obtained in the step 2 for 30min at 400 ℃ under the protection of inert atmosphere, carbonizing for 2h at 900 ℃, and naturally cooling to room temperature to obtain the nitrogen-oxygen doped hierarchical porous carbon material.
Fig. 3 is an SEM image of the nitrogen-oxygen doped hierarchical porous carbon material obtained in example 1, and it can be seen from the figure that the carbon material has a three-dimensional porous cross-linked structure, and the surface of the skeleton has abundant micropores and mesopores.
Fig. 4 is a TEM image of the nitrogen-oxygen doped hierarchical porous carbon material obtained in example 1, and it can be seen that the lattice structure of graphitized carbon of the carbon material and the presence of topological defects.
Fig. 5 is a graph showing the nitrogen adsorption/desorption curve of the nitrogen-oxygen doped hierarchical porous carbon material obtained in example 1. It can be seen from the figure that the specific surface area of the carbon material reaches 1033.6m at the highest 2 g -1 . FIG. 6 is a pore size distribution curve of the nitrogen-oxygen doped hierarchical porous carbon material obtained in example 1. It can be seen from the figure that the pore size of the carbon material is mainly distributed below 3 nm.
FIG. 7 is an X-ray photoelectron spectrum of a nitrogen-oxygen doped hierarchical porous carbon material obtained in example 1. From the figure, it can be seen that the carbon material contains C, N, O elements, and it can be seen that the method of the invention successfully dopes nitrogen-oxygen heteroatoms into the porous carbon material.
Fig. 8 is an SEM image of the nitrogen-oxygen doped hierarchical porous carbon material obtained in example 4, and it can be seen from the figure that the carbon material is a three-dimensional porous cross-linked structure, the surface of the skeleton has a bulge structure, and a small amount of pore structure can be observed.
The preparation method has the advantages of simple steps, low cost, simple and easily available raw materials, low cost, easy realization of large-scale batch production and convenient industrialized application and popularization. Compared with the existing synthesis method of the nitrogen-oxygen doped carbon material, the method selects the organic matters containing nitrogen and oxygen as the carbon source, the nitrogen source and the oxygen source at the same time, and does not need the subsequent complex heteroatom doping process. The effective doping of nitrogen-oxygen hetero atoms is realized in the preparation process, and the nitrogen-oxygen hetero atoms are uniformly distributed. The alkali activation is beneficial to promoting the amino groups in the organic matters to crosslink, so that the thermal stability of nitrogen species in the raw materials is enhanced, and the nitrogen atom content in the obtained carbon material is higher. The oxygen-containing functional groups are introduced in abundance by pre-oxidation, and are easily released in a gaseous form during pyrolysis, resulting in a carbon material having a rich pore structure. At the same time, the increase of the heteroatom content is beneficial to enhancing the defectivity of the carbon material. The carbon material has controllable nitrogen-oxygen heteroatom content, adjustable pore structure and defect degree, is favorable for improving the physical and chemical properties of the carbon material, such as specific surface area, and the like, and can be applied to super capacitor electrode materials, electrolytic water hydrogen evolution oxygen evolution catalytic electrode materials, lithium ion electrode materials, sodium ion electrode materials, potassium ion electrode materials, electromagnetic shielding and absorbing materials, oil-water separation adsorbents and seawater desalination materials.
Claims (7)
1. The preparation method of the nitrogen-oxygen doped hierarchical porous carbon material is characterized by comprising the following steps of:
step 1: carrying out ultrasonic treatment on the organic matters containing nitrogen and oxygen, and drying; placing the mixture in alkali solution for activation, and washing to obtain alkali activated organic matters; the organic matter containing nitrogen and oxygen is one or a mixture of two of melamine formaldehyde foam and polyurethane foam in any proportion;
step 2: the organic matters obtained in the step 1 are kept at the temperature of 300-500 ℃ for 15-60 min in inert atmosphere; then cooling to 100-200 ℃, introducing air atmosphere, and cooling to obtain pre-oxidized organic matters;
step 3: the preoxidized organic matters obtained in the step 2 are kept at the temperature of 300-500 ℃ for 15-60 min in inert atmosphere; then preserving heat for 1-4 h at 700-1000 ℃ and cooling to obtain the nitrogen-oxygen doped hierarchical porous carbon material.
2. The method for preparing a nitrogen-oxygen doped hierarchical porous carbon material according to claim 1, wherein the ultrasonic process in step 1 is as follows: firstly, adopting secondary water to carry out ultrasonic treatment for 15-60 min, and then carrying out ultrasonic treatment in absolute ethyl alcohol for 15-60 min.
3. The method for preparing a nitrogen-oxygen doped hierarchical porous carbon material according to claim 1, wherein the alkaline solution in the step 1 is one of NaOH, KOH and LiOH; the concentration of the alkali solution is 1-6 mol/L.
4. The method for preparing a nitrogen-oxygen doped hierarchical porous carbon material according to claim 3, wherein the activation temperature in the step 1 is 40-90 ℃ and the activation time is 15-60 min.
5. The method for preparing a nitrogen-oxygen doped hierarchical porous carbon material according to claim 1, wherein the inert atmosphere in the step 2 and the step 3 is an argon atmosphere or a nitrogen atmosphere.
6. The nitrogen-oxygen doped hierarchical porous carbon material obtained by any one of the preparation methods of claims 1 to 5, wherein the porous carbon material has a hierarchical porous structure and contains abundant micropores and mesoporous structures; the BET specific surface area of the carbon material is 500-2500 m 2 g -1 The method comprises the steps of carrying out a first treatment on the surface of the The carbon material contains 60 to 95at% of carbon element, 1 to 20at% of nitrogen element and 1 to 20at% of oxygen element.
7. The use of a nitrogen-oxygen doped graded porous carbon material according to claim 6, wherein the porous carbon material is used for the preparation of supercapacitors, electrolyzed water hydrogen evolution oxygen evolution catalytic electrodes, lithium ion electrodes, sodium ion electrodes, potassium ion electrodes, electromagnetic shielding and absorbents.
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| RU2017129363A (en) * | 2015-01-21 | 2019-02-21 | Юниверсите Де Страcбур | METHOD FOR PRODUCING HIGHLY DOPED BY NITROGEN MESOPOROUS CARBON COMPOSITES |
| CN111235698B (en) * | 2020-03-24 | 2022-09-23 | 北华大学 | Preparation method and application of nitrogen-doped porous carbon fiber material |
| CN112752496B (en) * | 2021-01-15 | 2022-01-14 | 西北工业大学 | Hollow nitrogen-doped nickel oxide/nickel/carbon composite material, preparation method and application |
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| CN102134068A (en) * | 2011-04-24 | 2011-07-27 | 大连理工大学 | Preparation method of graphitic carbon foam with high aperture ratio |
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