CN114956040A - Nitrogen-oxygen doped graded porous carbon material, preparation method and application - Google Patents
Nitrogen-oxygen doped graded 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, wherein the preparation method comprises the following steps: step 1: carrying out ultrasonic treatment on the organic matter containing nitrogen and oxygen, and drying; activating in an alkali solution, and washing to obtain an alkali-activated organic matter; step 2: preserving the heat of the organic matter obtained in the step 1 for 15-60 min at the temperature of 300-500 ℃ in an inert atmosphere; then cooling to 100-200 ℃, introducing air atmosphere, and cooling to obtain pre-oxidized organic matters; and step 3: preserving the temperature of the pre-oxidized organic matter obtained in the step 2 for 15-60 min at the temperature of 300-500 ℃ in an inert atmosphere; then, preserving heat for 1-4 hours at 700-1000 ℃, and cooling to obtain a nitrogen-oxygen doped hierarchical porous carbon material; the preparation method has the advantages of simple steps, low cost, simple and easily obtained raw materials, easy realization of large-scale batch production and convenient industrial 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.
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 nitrogen-oxygen heteroatom doping of the carbon material can effectively improve the physical and chemical properties such as surface wettability and conductivity of the carbon material, and attracts people's attention.
At present, three common methods for introducing nitrogen and oxygen elements into a carbon material are available, namely, the carbon material carbonized at high temperature is directly subjected to post-treatment such as pre-oxidation by using nitrogen-containing substances such as ammonia gas and the like. Secondly, the mixture of organic matter and nitrogen-oxygen containing compound is used for carbonization treatment. Thirdly, directly utilizing nitrogen-oxygen containing organic matters to carry out carbonization treatment; the third method is relatively simple and does not require the introduction of additional nitrogen oxygen heteroatoms in the carbon source. For example, patent No. 2017109952117 discloses a method for preparing a multi-level pore nitrogen-oxygen doped carbon supercapacitor electrode material, which is to mix and carbonize yolk, which is a biomass carbon source, and trisodium trithiocyanate, activate and carbonize KOH, and activate and carbonize acid, so as to obtain a multi-level pore nitrogen-oxygen doped carbon with a large number of micropores, mesopores, and macropores and a high specific surface area, and can be used as a supercapacitor electrode material. However, the method has complex steps, high energy consumption and cost and is difficult to prepare on a large scale. The patent number 2021111905727 discloses a preparation method and application of heteroatom self-doped biomass porous carbon, which comprises subjecting Spirodela sophorae to ultrasonic treatment and ball milling treatment, performing hydrothermal preoxidation, KOH activation and carbonization, and CO 2 And (4) activating and washing with hydrochloric acid to obtain the heteroatom self-doping biomass porous carbon. The method has good application prospect in the field of sewage purification, but the method has complex preparation process and long preparation period.
In conclusion, the existing preparation methods generally have the problems of complex preparation steps, long time consumption and the like. At present, the existing activation method can greatly reduce the content of doped heteroatoms in the carbon material while increasing the specific surface area. In the carbonization process of a plurality of organic matters, the nitrogen source is easily decomposed into gas, the utilization rate of the nitrogen source is low, and the content of nitrogen atoms in the obtained carbon material is low.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a nitrogen-oxygen doped graded porous carbon material which is simple in preparation method and can improve the 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 a template, does not need to introduce other nitrogen sources and oxygen sources, and has low cost of used raw materials. By optimizing the process conditions of the pretreatment process, the thermal stability of nitrogen-containing species is enhanced by promoting crosslinking while the pore is etched by the activating agent, 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 matter containing nitrogen and oxygen, and drying; activating in an alkali solution, and washing to obtain an alkali-activated organic matter;
step 2: preserving the heat of the organic matter obtained in the step 1 for 15-60 min at the temperature of 300-500 ℃ in an inert atmosphere; then cooling to 100-200 ℃, introducing air atmosphere, and cooling to obtain pre-oxidized organic matters;
and 3, step 3: preserving the temperature of the pre-oxidized organic matter obtained in the step 2 for 15-60 min at the temperature of 300-500 ℃ in an inert atmosphere; and then, preserving heat for 1-4 hours at 700-1000 ℃, and cooling to obtain the nitrogen-oxygen doped hierarchical porous carbon material.
Further, in the step 1, the nitrogen-oxygen containing organic matter is a mixture formed by mixing one or more than two of urea, dicyandiamide, melamine formaldehyde foam, polyurethane foam, polyacrylonitrile, butyronitrile and polyphosphazene in any proportion.
Further, the ultrasonic process in step 1 is as follows: firstly, secondary water is adopted for ultrasonic treatment for 15-60 min, and then ultrasonic treatment is carried out 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 step 2 and step 3 is an argon atmosphere or a nitrogen atmosphere.
A nitrogen-oxygen doped hierarchical porous carbon material is characterized in that the porous carbon material is of 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 (ii) a The carbon material contains 60 to 95 at% of carbon element, 1 to 20 at% of nitrogen element, and 1 to 20 at% of oxygen element.
The porous carbon material is used for preparing a super capacitor, an electrolytic water hydrogen evolution and oxygen evolution catalytic electrode, a lithium ion electrode, a sodium ion electrode, a potassium ion electrode, an electromagnetic shielding and absorbing agent, an oil-water separation absorbing agent and a seawater desalination agent.
The beneficial effects of the invention are:
(1) according to the invention, the organic matter containing nitrogen and oxygen is used as the carbon source and the nitrogen source at the same time, a subsequent complex heteroatom doping process is not needed, and nitrogen and oxygen heteroatoms are effectively doped in the preparation process and are uniformly distributed;
(2) in the carbonization process, more thermally stable nitrogen sources in organic matters are retained in the carbon material by alkali activation and pre-oxidation, the utilization rate of the nitrogen sources is high, and the content of nitrogen atoms 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 richer;
(3) the content of nitrogen and oxygen heteroatoms doped in the carbon material is controllable, the pore structure and the defect degree are controllable, and the physical and chemical properties such as the specific surface area of the carbon material are favorably improved; the obtained carbon material can be used for supercapacitor electrode materials, electrolytic water hydrogen evolution and oxygen evolution catalytic electrode materials, electromagnetic shielding and absorbing materials, oil-water separation adsorbents and seawater desalination materials;
(4) the preparation method has simple steps, low cost, simple and easily obtained raw materials, is easy to realize large-scale batch production, and is convenient for industrial application and popularization.
Drawings
FIG. 1 is a flow chart of the preparation of nitrogen-oxygen doped hierarchical porous carbon material.
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 pore size distribution curve of the porous carbon material obtained in example 1 of the present invention.
FIG. 7 is an X-ray photoelectron spectrum of the 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 is further described with reference to the following figures and specific embodiments.
A preparation method of a nitrogen-oxygen doped graded porous carbon material is shown in figure 1 and comprises the following steps:
step 1: ultrasonically treating the nitrogen-oxygen containing organic matter, cleaning soluble impurities after ultrasonic treatment, and then drying; activating in an alkali solution, and washing (washing with deionized water until the filtrate is neutral) to obtain an alkali-activated organic matter; the nitrogen-oxygen containing organic matter is one or a mixture of two or more of urea, dicyandiamide, melamine formaldehyde foam, polyurethane foam, polyacrylonitrile, butyronitrile and polyphosphazene which are mixed in any proportion. The ultrasonic process is as follows: firstly, carrying out ultrasonic treatment for 15-60 min by using secondary water, and then carrying out ultrasonic treatment for 15-60 min in absolute ethyl alcohol. 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: preserving the heat of the organic matter obtained in the step (1) for 15-60 min at 300-500 ℃ in an 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.
And step 3: preserving the temperature of the pre-oxidized organic matter obtained in the step 2 for 15-60 min at the temperature of 300-500 ℃ in an inert atmosphere; and then, preserving heat for 1-4 hours 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 is a hierarchical porous structure, contains rich micropores and mesoporous structures and has a high specific surface area. The carbon material has a BET specific surface area of 500 to 2500m 2 g -1 (ii) a The carbon material contains 60 to 95 at% of carbon element, 1 to 20 at% of nitrogen element, and 1 to 20 at% of oxygen element.
The porous carbon material is used for preparing a super capacitor, an electrolytic water hydrogen evolution and oxygen evolution catalytic electrode, a lithium ion electrode, a sodium ion electrode, a potassium ion electrode, an electromagnetic shielding and absorbing agent, an oil-water separation absorbing agent and a seawater desalination agent.
The instrument used for material characterization in this example was:
scanning electron microscope: the model is H-7650, and the manufacturer is Hitachi; transmission electron microscope: the model is S-4800Hitachi, and the manufacturer is Hitachi; specific surface area and porosity analyzer: the model is BELSORP MAXII, and the manufacturer is Mickelber, Japan. X-ray photoelectron spectroscopy: the model is K-Alpha, and the manufacturer is American Saimer Feishell science and technology.
Example 1
The nitrogen-oxygen doped hierarchical porous carbon material is prepared according to the following method:
step 1: respectively placing the melamine formaldehyde foam in secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning off soluble impurities, and drying to obtain a clean melamine formaldehyde foam raw material; and (3) soaking the dried melamine foam material in 5mol/L NaOH solution at 65 ℃ for 30min, washing the melamine foam material 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 tubular furnace for calcination, preserving the 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 pre-oxidized melamine formaldehyde foam.
And step 3: and (3) carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step (2) for 30min at the temperature of 400 ℃ under the protection of inert atmosphere, then carbonizing for 2h at the temperature of 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 is prepared according to the following method:
step 1: respectively placing the melamine formaldehyde foam in secondary water and absolute ethyl alcohol for ultrasonic treatment for 15min, cleaning off soluble impurities, and drying to obtain a clean melamine formaldehyde foam raw material; and (3) soaking the dried melamine foam material in 1mol/L KOH solution at 40 ℃ for 15min, washing the melamine foam material 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 tubular furnace for calcination, preserving the 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 pre-oxidized melamine formaldehyde foam.
And step 3: and (3) carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step (2) for 30min at the temperature of 400 ℃ under the protection of inert atmosphere, then carbonizing for 2h at the temperature of 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 is prepared according to the following method:
step 1: respectively placing the melamine formaldehyde foam in secondary water and absolute ethyl alcohol for ultrasonic treatment for 60min, cleaning off soluble impurities, and drying to obtain a clean melamine formaldehyde foam raw material; and (3) soaking the dried melamine foam material in 6mol/L LiOH solution at 90 ℃ for 60min, washing the melamine foam material with deionized water until the filtrate is neutral, and drying to obtain LiOH activated melamine formaldehyde foam.
Step 2: and (2) transferring the activated melamine formaldehyde foam obtained in the step (1) to a tubular furnace for calcination, preserving the heat for 30min at 400 ℃ in an inert atmosphere, then cooling to 150 ℃, introducing air atmosphere, and naturally cooling to room temperature to obtain the pre-oxidized melamine formaldehyde foam.
And step 3: and (3) carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step (2) for 30min at the temperature of 400 ℃ under the protection of inert atmosphere, then carbonizing for 2h at the temperature of 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 is prepared according to the following method:
step 1: respectively placing the melamine formaldehyde foam in secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning off soluble impurities, and drying to obtain a clean melamine formaldehyde foam raw material; and (3) soaking the dried melamine foam material in 1mol/L KOH solution at 40 ℃ for 60min, washing the melamine foam material 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 tubular furnace for calcination, preserving the heat for 30min at 400 ℃ in an inert atmosphere, then cooling to 50 ℃, introducing an air atmosphere, and naturally cooling to room temperature to obtain pre-oxidized melamine formaldehyde foam.
And step 3: and (3) carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step (2) for 30min at the temperature of 400 ℃ under the protection of inert atmosphere, then carbonizing for 2h at the temperature of 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 is prepared according to the following method:
step 1: respectively placing the melamine formaldehyde foam in secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning off soluble impurities, and drying to obtain a clean melamine formaldehyde foam raw material; and (3) soaking the dried melamine foam material in 6mol/L LiOH solution at 90 ℃ for 15min, washing with deionized water until the filtrate is neutral, and drying to obtain LiOH activated melamine formaldehyde foam.
Step 2: transferring the activated melamine formaldehyde foam obtained in the step 1 into a tubular furnace for calcination, preserving the heat for 30min at 400 ℃ in an inert atmosphere, then cooling to 200 ℃, introducing an air atmosphere, and naturally cooling to room temperature to obtain pre-oxidized melamine formaldehyde foam.
And step 3: and (3) carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step (2) for 30min at the temperature of 400 ℃ under the protection of inert atmosphere, then carbonizing for 2h at the temperature of 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 is prepared according to the following method:
step 1: respectively placing the melamine formaldehyde foam in secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning off soluble impurities, and drying to obtain a clean melamine formaldehyde foam raw material; and (3) soaking the dried melamine foam material in 1mol/L NaOH solution at 65 ℃ 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 tubular furnace for calcination, keeping the temperature for 15min at 300 ℃ in an inert atmosphere, then cooling to 50 ℃, introducing an air atmosphere, and naturally cooling to room temperature to obtain pre-oxidized melamine formaldehyde foam.
And step 3: and (3) carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step (2) for 15min at the temperature of 300 ℃ under the protection of inert atmosphere, then carbonizing for 2h at the temperature of 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 is prepared according to the following method:
step 1: respectively placing the melamine formaldehyde foam in secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning off soluble impurities, and drying to obtain a clean melamine formaldehyde foam raw material; and (3) soaking the dried melamine foam material in 6mol/L NaOH solution at 65 ℃ 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 tubular furnace for calcination, preserving the heat for 60min at 500 ℃ in an inert atmosphere, then cooling to 150 ℃, introducing an air atmosphere, and naturally cooling to room temperature to obtain pre-oxidized melamine formaldehyde foam.
And step 3: and (3) carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step (2) for 60min at 500 ℃ under the protection of inert atmosphere, then 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 is prepared according to the following method:
step 1: respectively placing the melamine formaldehyde foam in secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning off soluble impurities, and drying to obtain a clean melamine formaldehyde foam raw material; and (3) soaking the dried melamine foam material in 3mol/L NaOH solution at 65 ℃ 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 tubular furnace for calcination, preserving the heat for 60min at 400 ℃ in an inert atmosphere, then cooling to 150 ℃, introducing an air atmosphere, and naturally cooling to room temperature to obtain pre-oxidized melamine formaldehyde foam.
And step 3: and (3) carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step (2) for 30min at the temperature of 400 ℃ under the protection of inert atmosphere, then carbonizing for 1h at the temperature of 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 is prepared according to the following method:
step 1: respectively placing the melamine formaldehyde foam in secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning off soluble impurities, and drying to obtain a clean melamine formaldehyde foam raw material; and (3) soaking the dried melamine foam material in 3mol/L KOH solution at 65 ℃ for 30min, washing the melamine foam material 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 tubular furnace for calcination, keeping the temperature for 15min at 400 ℃ in an inert atmosphere, then cooling to 150 ℃, introducing an air atmosphere, and naturally cooling to room temperature to obtain pre-oxidized melamine formaldehyde foam.
And step 3: and (3) carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step (2) for 15min at the temperature of 400 ℃ under the protection of inert atmosphere, then carbonizing for 4h at the temperature of 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 is prepared according to the following method:
step 1: respectively placing the melamine formaldehyde foam in secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning off soluble impurities, and drying to obtain a clean melamine formaldehyde foam raw material; and (3) soaking the dried melamine foam material in 3mol/L KOH solution at 65 ℃ for 30min, washing the melamine foam material 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 tubular furnace for calcination, keeping the temperature for 15min at 400 ℃ in an inert atmosphere, then cooling to 150 ℃, introducing an air atmosphere, and naturally cooling to room temperature to obtain pre-oxidized melamine formaldehyde foam.
And step 3: and (3) carbonizing the pre-oxidized melamine formaldehyde foam obtained in the step (2) for 15min at the temperature of 400 ℃ under the protection of inert atmosphere, then carbonizing for 2h at the temperature of 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 is prepared according to the following method:
step 1: respectively placing the polyurethane foam into secondary water and absolute ethyl alcohol for ultrasonic treatment for 30min, cleaning soluble impurities, and drying to obtain a clean polyurethane foam raw material; and (3) soaking the dried polyurethane foam material in 5mol/L NaOH solution at 60 ℃ for 30min, washing with deionized water until the filtrate is neutral, and drying to obtain NaOH-activated polyurethane foam.
Step 2: and (3) transferring the activated polyurethane foam obtained in the step (1) to a tubular furnace for calcination, preserving the 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 pre-oxidized polyurethane foam.
And step 3: and (3) carbonizing the preoxidized polyurethane foam obtained in the step (2) for 30min at the temperature of 400 ℃ under the protection of inert atmosphere, then carbonizing for 2h at the temperature of 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 contains abundant micropores and mesopores.
Fig. 4 is a TEM image of the nitrogen-oxygen doped graded 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 existence of topological defects.
Fig. 5 is a nitrogen adsorption and desorption curve of the nitrogen-oxygen doped graded porous carbon material obtained in example 1. It can be seen from the figure that the specific surface area of the carbon material is up to 1033.6m 2 g -1 . FIG. 6 is a pore size distribution curve of the nitrogen-oxygen doped graded porous carbon material obtained in example 1. It can be seen from the figure that the pore diameter of the carbon material is mainly distributed at 3nm or less.
FIG. 7 is an X-ray photoelectron total spectrum of the nitrogen-oxygen doped graded 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 present invention successfully dopes nitrogen and oxygen heteroatoms into the porous carbon material.
Fig. 8 is an SEM image of the nitrogen-oxygen doped graded porous carbon material obtained in example 4, and it can be seen from the figure that the carbon material has a three-dimensional porous cross-linked structure, a swelling structure is formed on the surface of the skeleton, and a small amount of pore structures can be observed.
The preparation method has the advantages of simple steps, low cost, simple and easily obtained raw materials, low price, easy realization of large-scale batch production and convenient industrial application and popularization. Compared with the existing synthesis method of the nitrogen-oxygen doped carbon material, the method selects the organic matter 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 nitrogen and oxygen heteroatoms can be effectively doped in the preparation process, and the distribution is uniform. The alkali activation is beneficial to promoting the crosslinking of amino groups in the organic matter, so that the thermal stability of nitrogen species in the raw material is enhanced, and the content of nitrogen atoms in the obtained carbon material is higher. An abundant oxygen-containing functional group is introduced through pre-oxidation and is easily released in a gas form in a pyrolysis process, so that the carbon material has an abundant pore structure. Meanwhile, the increase of the content of the heteroatom is beneficial to enhancing the defect degree of the carbon material. The carbon material has controllable content of nitrogen and oxygen heteroatoms doped in the carbon material, adjustable pore structure and defect degree, is beneficial to improving physical and chemical properties such as specific surface area of the carbon material, and can be applied to electrode materials of super capacitors, electrolytic water hydrogen evolution and 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 (8)
1. A preparation method of a nitrogen-oxygen doped hierarchical porous carbon material is characterized by comprising the following steps:
step 1: carrying out ultrasonic treatment on the organic matter containing nitrogen and oxygen, and drying; activating in an alkali solution, and washing to obtain an alkali-activated organic matter;
step 2: preserving the heat of the organic matter obtained in the step 1 for 15-60 min at the temperature of 300-500 ℃ in an inert atmosphere; then cooling to 100-200 ℃, introducing air atmosphere, and cooling to obtain pre-oxidized organic matters;
and step 3: preserving the temperature of the pre-oxidized organic matter obtained in the step 2 for 15-60 min at the temperature of 300-500 ℃ in an inert atmosphere; and then, preserving heat for 1-4 hours at 700-1000 ℃, and cooling to obtain the nitrogen-oxygen doped hierarchical porous carbon material.
2. The method for preparing a nitrogen-oxygen doped graded porous carbon material according to claim 1, wherein the nitrogen-oxygen containing organic substance in step 1 is a mixture formed by mixing one or two or more of urea, dicyandiamide, melamine formaldehyde foam, polyurethane foam, polyacrylonitrile, butyronitrile and polyphosphazene in any proportion.
3. The method for preparing the nitrogen-oxygen doped graded porous carbon material according to claim 1, wherein the ultrasonic process in the step 1 is as follows: firstly, carrying out ultrasonic treatment for 15-60 min by using secondary water, and then carrying out ultrasonic treatment for 15-60 min in absolute ethyl alcohol.
4. The method for preparing a nitrogen-oxygen doped graded porous carbon material according to claim 1, wherein 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.
5. The method for preparing a nitrogen-oxygen doped graded porous carbon material according to claim 4, wherein the activation temperature in the step 1 is 40-90 ℃, and the activation time is 15-60 min.
6. The method for preparing a nitrogen-oxygen doped graded porous carbon material according to claim 1, wherein the inert atmosphere in the steps 2 and 3 is an argon atmosphere or a nitrogen atmosphere.
7. The nitrogen-oxygen doped graded porous carbon material obtained by the preparation method according to any one of claims 1 to 6,the porous carbon material is of 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 (ii) a The carbon material contains 60 to 95 at% of carbon element, 1 to 20 at% of nitrogen element, and 1 to 20 at% of oxygen element.
8. The use of the nitrogen and oxygen doped hierarchical porous carbon material as claimed in claim 7, wherein the porous carbon material is used for preparing super capacitors, electrolytic water hydrogen evolution and oxygen evolution catalytic electrodes, lithium ion electrodes, sodium ion electrodes, potassium ion electrodes, electromagnetic shielding and absorbing agents, oil-water separation adsorbents and seawater desalination agents.
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| CN116116449A (en) * | 2023-01-17 | 2023-05-16 | 四川大学 | Nitrogen-doped biochar-based bio-oil upgrading catalyst and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116116449A (en) * | 2023-01-17 | 2023-05-16 | 四川大学 | Nitrogen-doped biochar-based bio-oil upgrading catalyst and preparation method and application thereof |
| CN116116449B (en) * | 2023-01-17 | 2024-05-17 | 四川大学 | Nitrogen-doped biochar-based bio-oil upgrading catalyst and preparation method and application thereof |
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