CN115304061A - Sulfur-nitrogen co-doped carbon material and preparation method and application thereof - Google Patents
Sulfur-nitrogen co-doped carbon material and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 239000002028 Biomass Substances 0.000 claims abstract description 36
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 29
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- 229910052799 carbon Inorganic materials 0.000 claims abstract description 26
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 7
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- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
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- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
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- 238000009489 vacuum treatment Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
- C01B32/348—Metallic compounds
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Abstract
The invention belongs to the technical field of adsorption materials, and particularly relates to a sulfur-nitrogen co-doped carbon material and a preparation method and application thereof. The invention provides a preparation method of a sulfur-nitrogen co-doped carbon material, which comprises the following steps: and mixing biomass carbon and the potassium equilin sulfonate, and carrying out heat treatment to obtain the sulfur-nitrogen co-doped carbon material. According to the invention, the kalium equinesulfonate is used as an activating agent and a sulfur and nitrogen co-doping reagent to prepare the sulfur and nitrogen co-doping carbon material, the required raw materials are simple and easy to obtain, various raw materials are not required to be added, and the preparation method is simple and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of adsorption materials, and particularly relates to a sulfur-nitrogen co-doped carbon material and a preparation method and application thereof.
Background
The porous carbon material has the advantages of low cost, high stability, high porosity and the like, and is widely applied to different research fields. The carbon material is modified by doping with nitrogen, sulfur, boron, phosphorus and other elements. The nitrogen and sulfur co-doped carbon material has wide application research in the aspects of electrocatalysis, energy storage and conversion, gas adsorption and the like.
Nitrogen and sulfur CO-doped carbon material as CO 2 When the adsorbent is used, the basic nitrogen-containing group and the oxidizing sulfur-containing group on the surface of the carbon material can be combined with CO 2 Produce strong interaction and improve CO 2 The adsorption performance of (3).
The common preparation method of the nitrogen and sulfur co-doped carbon material is a chemical activation method, and the nitrogen and sulfur co-doped carbon material is obtained by mixing biomass carbon, a nitrogen source, a sulfur source and a pore-forming agent or an activating agent and then carrying out high-temperature treatment. For example, chinese patent publication No. CN103072972A discloses a nitrogen and sulfur co-doped carbon material, in which pyrrole is used as a biomass carbon and nitrogen source, sulfuric acid is used as an acid catalyst and a sulfur source, mesoporous silica molecular sieves SBA-15 and KIT-6 are used as templates, and the nitrogen and sulfur co-doped carbon material is prepared by combining an incipient wetness impregnation method and a high-temperature pyrolysis technology. The above method requires addition of various raw materials and the preparation process is complicated.
Disclosure of Invention
The invention aims to provide a sulfur-nitrogen co-doped carbon material, and a preparation method and application thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a preparation method of a sulfur-nitrogen co-doped carbon material, which comprises the following steps:
and mixing biomass carbon and the potassium equilin sulfonate, and carrying out heat treatment to obtain the sulfur-nitrogen co-doped carbon material.
Preferably, the mass ratio of the biomass carbon to the potassium marinoethanesulfonate is 1:1 to 5.
Preferably, the temperature of the heat treatment is 600-900 ℃, and the heat preservation time is 1-2 h;
the heat treatment is carried out in a protective atmosphere.
Preferably, the preparation method of the biomass carbon comprises the following steps:
and carbonizing the biomass raw material to obtain the biomass carbon.
Preferably, the biomass raw material comprises one or more of chitosan, cellulose, agar, lignin, starch, gelatin, sucrose and glucose.
Preferably, the carbonization treatment includes a hydrothermal carbonization treatment or a solid-phase carbonization treatment.
Preferably, the temperature of the hydrothermal carbonization treatment is 160-220 ℃, and the heat preservation time is 1-6 h.
Preferably, the temperature of the solid-phase carbonization treatment is 400-600 ℃, and the heat preservation time is 1-2 h.
The invention also provides a sulfur-nitrogen co-doped carbon material prepared by the preparation method in the technical scheme, wherein the doping percentage content of sulfur in the sulfur-nitrogen co-doped carbon material is 3.0-9.0 wt%; the doping percentage content of nitrogen is 3.0-6.0 wt%.
The invention also provides application of the sulfur-nitrogen co-doped carbon material in the technical scheme as a gas adsorbent.
The invention provides a preparation method of a sulfur-nitrogen co-doped carbon material, which comprises the following steps: and mixing biomass carbon and the potassium equilin sulfonate, and carrying out heat treatment to obtain the sulfur-nitrogen co-doped carbon material. According to the invention, the kalium malinelette is used as an activator and a sulfur and nitrogen co-doping reagent, thermal decomposition products generated in the heat treatment process of the kalium malinelette generate oxidation-reduction reaction with biomass carbon, the biomass carbon is corroded to form a porous structure, and meanwhile, the sulfur and nitrogen co-doping of a carbon material is realized, so that the sulfur and nitrogen co-doping carbon material can be directly prepared; the preparation method provided by the invention has the advantages that the required raw materials are simple and easy to obtain, various raw materials are not required to be added, the preparation method is simple, and the preparation method is suitable for industrial production. Meanwhile, the sulfur-nitrogen co-doped carbon material obtained by the invention has excellent adsorption performance on carbon dioxide.
Drawings
FIG. 1 is an SEM image of a sulfur-nitrogen co-doped carbon material obtained in example 1;
FIG. 2 is a TEM image of the sulfur-nitrogen co-doped carbon material obtained in example 1;
FIG. 3 is an XPS test N1s spectrogram of the sulfur-nitrogen co-doped carbon material obtained in example 1;
FIG. 4 is an XPS test N1s spectrum of the sulfur-nitrogen co-doped carbon material obtained in example 2;
FIG. 5 is an XPS test N1s spectrogram of the sulfur-nitrogen co-doped carbon material obtained in example 3;
FIG. 6 is an XPS test S2p spectrum of the sulfur-nitrogen co-doped carbon material obtained in example 1;
FIG. 7 is an XPS test S2p spectrum of the sulfur-nitrogen co-doped carbon material obtained in example 2;
FIG. 8 is an XPS test S2p spectrum of the sulfur-nitrogen co-doped carbon material obtained in example 3;
FIG. 9 is a nitrogen elution profile of the sulfur-nitrogen co-doped carbon material obtained in examples 2 and 3;
FIG. 10 is a carbon dioxide adsorption isotherm of the sulfur-nitrogen-codoped carbon materials obtained in examples 1 to 3 at 25 ℃.
Detailed Description
The invention provides a preparation method of a sulfur-nitrogen co-doped carbon material, which comprises the following steps:
and mixing biomass carbon and the potassium equilin sulfonate, and then carrying out heat treatment to obtain the sulfur-nitrogen co-doped carbon material.
In the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.
In the present invention, the method for producing biomass carbon preferably includes the steps of:
and carbonizing the biomass raw material to obtain the biomass carbon.
In the invention, the biomass raw material preferably comprises one or more of chitosan, cellulose, agar, lignin, starch, gelatin, sucrose and glucose; when the biomass material is preferably two or more selected from the above-mentioned choices, the present invention does not specifically limit the proportion of the specific material, and the specific material may be mixed at any proportion.
In the present invention, the carbonization treatment preferably includes a hydrothermal carbonization treatment or a solid-phase carbonization treatment.
In the invention, the temperature of the hydrothermal carbonization treatment is preferably 160-220 ℃, more preferably 170-210 ℃, and more preferably 180-200 ℃; the holding time is preferably 1 to 6 hours, more preferably 2 to 5 hours, and still more preferably 3 to 4 hours. In the present invention, the hydrothermal carbonization treatment is preferably performed in a hydrothermal reaction vessel.
In a specific embodiment of the present invention, the hydrothermal carbonization treatment preferably comprises:
mixing the biomass raw material with water, and placing the obtained mixture in a hydrothermal reaction kettle for hydrothermal carbonization treatment.
In the present invention, the mass ratio of the water to the biomass raw material is preferably 100:5 to 20, more preferably 100:10 to 15, more preferably 100:12 to 13.
The mixing process is not particularly limited in the present invention, and may be performed by a process known to those skilled in the art.
After the hydrothermal carbonization treatment is finished, the method also preferably comprises the step of carrying out post-treatment on the obtained carbonized material liquid; the post-treatment preferably comprises filtering, washing and drying in sequence. The filtration process is not particularly limited in the present invention, and may be performed by a process known to those skilled in the art. In the present invention, the number of washing with water is preferably 2 to 3. In the present invention, the drying temperature is preferably 100 to 120 ℃, and more preferably 100 to 110 ℃; the time is preferably 4 to 6 hours, more preferably 5 hours. In the present invention, the water in the product after water washing can be removed by drying.
In the present invention, the temperature of the solid phase carbonization treatment is preferably 400 to 600 ℃, more preferably 420 to 580 ℃, and even more preferably 450 to 550 ℃; the heating rate of heating to the solid-phase carbonization treatment temperature is preferably 5 to 15 ℃/min, and more preferably 8 to 10 ℃/min; the holding time is preferably 1 to 2 hours. In the present invention, the solid-phase carbonization treatment is preferably performed in a protective atmosphere; the protective atmosphere is preferably nitrogen or argon. In the present invention, the solid-phase carbonization treatment is preferably performed in a tube furnace.
In a specific embodiment of the present invention, the solid phase carbonization treatment preferably comprises:
and (3) putting the biomass raw material into a tubular furnace, heating in a protective atmosphere, and carrying out solid-phase carbonization treatment.
In the present invention, the flow rate of the protective atmosphere in the tube furnace is preferably 60mL/min.
After the solid phase carbonization treatment is completed, the present invention preferably further comprises cooling the obtained product. In the present invention, the cooling is preferably performed by natural cooling to room temperature in a nitrogen atmosphere.
In the present invention, the mass ratio of the biomass carbon to the potassium marinoethanesulfonate is preferably 1:1 to 5, more preferably 1:2 to 4, more preferably 1 to 3.
In the present invention, the potassium marinoethanesulfonate is preferably mixed in the form of an aqueous solution of potassium marinoethanesulfonate.
In the present invention, the method for preparing the aqueous solution of potassium equisetate preferably comprises the steps of:
and mixing the potassium equisetlate with water to obtain the potassium equisetlate aqueous solution.
In the present invention, the mass ratio of the potassium equisetate to water is preferably 1:5 to 15, more preferably 1:7 to 12, more preferably 1:9 to 10. In the present invention, the temperature of the mixing is preferably 20 to 30 ℃, and more preferably 25 to 28 ℃. In a specific embodiment of the present invention, the mixing is specifically performed at room temperature. In the present invention, the mixing is preferably performed under stirring. The stirring parameters are not particularly limited in the present invention, and those known to those skilled in the art can be used. In the present invention, the stirring time is preferably 2 hours.
In the present invention, the mixing of the biomass carbon and the potassium marinoethanesulfonate is preferably performed under stirring conditions. The stirring conditions of the present invention are not particularly limited, and those known to those skilled in the art can be used.
After the mixing is complete, the present invention also preferably includes drying the resulting product. In the present invention, the drying temperature is preferably 100 to 120 ℃, and more preferably 105 to 110 ℃; the time is preferably 4 to 5 hours.
In the present invention, the temperature of the heat treatment is preferably 600 to 900 ℃, more preferably 650 to 850 ℃, and more preferably 700 to 800 ℃; the heating rate for heating to the heat treatment temperature is preferably 1 to 15 ℃/min, more preferably 5 to 10 ℃/min, and even more preferably 6 to 8 ℃/min; the holding time is preferably 1 to 2 hours. In the present invention, the heat treatment is preferably performed in a protective atmosphere; the protective atmosphere is preferably nitrogen or argon. In the present invention, the heat treatment is preferably performed in a tube furnace.
In a specific embodiment of the present invention, the heat treatment process is preferably:
and (3) putting the mixture of the biomass carbon and the potassium marinoethanesulfonate into a tube furnace, heating in a protective atmosphere, and carrying out heat treatment.
In the present invention, the flow rate of the protective atmosphere in the tube furnace is preferably 60mL/min.
After the heat treatment is finished, the invention also preferably comprises the step of carrying out post-treatment on the obtained material; the post-treatment preferably comprises cooling, washing and drying in sequence.
In the present invention, the cooling is preferably performed by natural cooling to room temperature. In the present invention, the washing preferably includes acid washing and water washing in this order. The pickling and washing processes are not particularly limited in the present invention, and may be performed by a process known to those skilled in the art. In the present invention, the acidic agent used for the acid washing is preferably a hydrochloric acid solution. In the present invention, the mass concentration of the hydrochloric acid solution is preferably 5 to 20wt%, and more preferably 8 to 10wt%. The frequency of the water washing is not particularly limited, and the pH value of the water washing material is only required to be washed to be neutral.
In the present invention, the drying temperature is preferably 100 to 120 ℃, and more preferably 110 to 115 ℃; the time is preferably 4 to 5 hours.
The invention also provides the sulfur-nitrogen co-doped carbon material prepared by the preparation method in the technical scheme. In the invention, the doping percentage content of sulfur in the sulfur-nitrogen co-doped carbon material is preferably 3.0-9.0 wt%, more preferably 4.0-9.0 wt%, and even more preferably 5.0-7.0 wt%. In the invention, the doping percentage of nitrogen in the sulfur-nitrogen co-doped carbon material is preferably 3.0-6.0 wt%, more preferably 3.5-5.5 wt%, and even more preferably 4.0-5.0 wt%.
In the invention, the specific surface area of the sulfur-nitrogen co-doped carbon material is preferably 1300-1600 m 2 A more preferable range is 1400 to 1500m 2 /g。
In the present invention, the sulfur-nitrogen co-doped carbon material preferably includes a microporous structure and a mesoporous structure.
The invention also provides application of the sulfur-nitrogen co-doped carbon material in the technical scheme as a gas adsorbent. The invention is not limited to the specific embodiments of the application, which can be carried out in a manner known to those skilled in the art.
For further illustration of the present invention, the following detailed description will be made with reference to the accompanying drawings and examples to provide a carbon material co-doped with sulfur and nitrogen, and a preparation method and application thereof, which should not be construed as limiting the scope of the present invention.
Example 1
Dissolving 5.0g of sucrose in 50mL of water, placing the obtained mixed solution in a hydrothermal reaction kettle, carrying out hydrothermal carbonization treatment at 200 ℃, and preserving heat for 6 hours; filtering the obtained carbonized material liquid, washing the precipitate obtained by filtering with deionized water for 3 times, and drying at 100 ℃ for 4 hours to obtain biomass carbon;
dissolving 1.0g of potassium marinoethanesulfonate in 15mL of deionized water to obtain a potassium marinoethanesulfonate aqueous solution, adding 1.0g of the obtained biomass carbon, stirring at room temperature for 2 hours, and drying the obtained mixture at 100 ℃ for 5 hours;
placing the dried mixture in a tubular furnace, introducing nitrogen into the tubular furnace at a flow rate of 60mL/min, heating to 600 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere for heat treatment, and keeping the temperature for 2h;
after the heat treatment is finished, naturally cooling to room temperature, carrying out acid washing on the obtained product by adopting a hydrochloric acid solution with the mass concentration of 10wt%, and then washing with water until the pH value of the product is neutral; and drying the product after water washing at 100 ℃ for 4h to obtain the sulfur-nitrogen co-doped carbon material.
Example 2
Dissolving 5.0g of sucrose in 50mL of water, placing the obtained mixed solution in a hydrothermal reaction kettle, carrying out hydrothermal carbonization treatment at 200 ℃, and keeping the temperature for 6h; filtering the obtained carbonized material liquid, washing the precipitate obtained by filtering with deionized water for 3 times, and drying at 100 ℃ for 4 hours to obtain biomass carbon;
dissolving 2.0g of potassium marinoethanesulfonate in 15mL of deionized water to obtain a potassium marinoethanesulfonate aqueous solution, adding 1.0g of the obtained biomass carbon, stirring at room temperature for 2 hours, and drying the obtained mixture at 100 ℃ for 5 hours;
placing the dried mixture in a tubular furnace, introducing nitrogen into the tubular furnace at a flow rate of 60mL/min, heating to 700 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, carrying out heat treatment, and keeping the temperature for 2h;
after the heat treatment is finished, naturally cooling to room temperature, carrying out acid washing on the obtained product by adopting a hydrochloric acid solution with the mass concentration of 10wt%, and then washing with water until the pH value of the product is neutral; and drying the product washed by water at 100 ℃ for 4 hours to obtain the sulfur-nitrogen co-doped carbon material.
Example 3
Placing agar in a tubular furnace, introducing nitrogen into the tubular furnace at a flow rate of 60mL/min, heating to 500 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere for carbonization, preserving heat for 2h, and naturally cooling to room temperature to obtain biomass carbon;
dissolving 3.0g of potassium marinoethanesulfonate in 15mL of deionized water to obtain a potassium marinoethanesulfonate aqueous solution, adding 1.0g of the obtained biomass carbon, stirring at room temperature for 2 hours, and drying the obtained mixture at 100 ℃ for 5 hours;
placing the dried mixture in a tubular furnace, introducing nitrogen into the tubular furnace at a flow rate of 60mL/min, heating to 700 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere for heat treatment, and keeping the temperature for 2 hours;
after the heat treatment is finished, naturally cooling to room temperature, carrying out acid washing on the obtained product by adopting a hydrochloric acid solution with the mass concentration of 10wt%, and then washing with water until the pH value of the product is neutral; and drying the product after water washing at 100 ℃ for 4h to obtain the sulfur-nitrogen co-doped carbon material.
Performance test
Test example 1
Scanning electron microscope detection is carried out on the sulfur-nitrogen co-doped carbon material obtained in the example 1, and an SEM image is shown in figure 1, and it can be seen from figure 1 that the sulfur-nitrogen co-doped carbon material obtained in the example presents an irregular morphology.
Test example 2
The transmission electron microscope detection is performed on the sulfur-nitrogen co-doped carbon material obtained in example 1, and the obtained TEM image is shown in fig. 2, and as can be seen from fig. 2, the sulfur-nitrogen co-doped carbon material obtained in this example contains rich pore structures, which indicates that potassium equilinate has a significant activation effect at high temperature, so that a developed pore structure is formed in the carbon material.
Test example 3
X-ray photoelectron spectroscopy tests were performed on the sulfur-nitrogen co-doped carbon materials obtained in examples 1 to 3, and XPS charts obtained are shown in FIGS. 3 to 8;
fig. 3 to 5 are N1s spectrograms of the sulfur-nitrogen co-doped carbon material, wherein fig. 3 is example 1, fig. 4 is example 2, and fig. 5 is example 3; from fig. 3 to 5, it can be seen that nitrogen doping is achieved in the carbon material after the activation treatment of the potassium equilin sulfonate; the doping percentage contents of nitrogen in the sulfur-nitrogen co-doped carbon material obtained in examples 1 to 3 were 3.1wt%, 4.3wt%, and 5.2wt%, respectively;
FIGS. 6 to 8 are S2p spectrograms of sulfur-nitrogen co-doped carbon materials, wherein FIG. 6 is example 1, FIG. 7 is example 2, and FIG. 8 is example 3; from fig. 6 to 8, it can be seen that sulfur doping is achieved in the carbon material after the activation treatment of the potassium equilin sulfonate; the doping contents of sulfur in the sulfur-nitrogen co-doped carbon materials obtained in examples 1 to 3 were 3.2wt%, 5.7wt%, and 8.2wt%, respectively.
Test example 4
Nitrogen gas adsorption and desorption tests are carried out on the sulfur-nitrogen co-doped carbon materials obtained in the embodiments 2 and 3, the test method is a static volume method adsorption test, and the test result is shown in fig. 9; as can be seen from fig. 9, after the activation treatment of the potassium equisetate, the obtained carbon material has rich pore structures;
specific surface areas of the sulfur-nitrogen co-doped carbon materials obtained in examples 2 and 3 were 1391m, respectively 2 G and 1502m 2 The/g shows that the sulfur-nitrogen co-doped carbon material obtained by the invention has a rich pore structure.
Test example 5
Testing the carbon dioxide adsorption characteristics of the sulfur-nitrogen co-doped carbon material obtained in the examples 1 to 3;
the test method comprises the following steps:
(1) Adding 100mg of carbon material to be tested into a test sample chamber, heating to 250 ℃, and carrying out vacuum degassing treatment for 3h;
(2) Setting the environment temperature of the test sample chamber to be 25 ℃, gradually increasing the pressure of the carbon dioxide from a vacuum state, and measuring the adsorption capacity under each equilibrium pressure until the equilibrium pressure reaches 1.0bar, thereby obtaining a complete carbon dioxide adsorption isotherm;
(3) After the carbon dioxide adsorption test is finished, the sample chamber is heated to 100 ℃ for vacuum treatment, and carbon dioxide desorption is finished.
The results of the carbon dioxide adsorption test obtained are shown in fig. 10. As can be seen from FIG. 10, when the adsorption temperature is 25 ℃, the carbon dioxide adsorption amounts of the sulfur-nitrogen co-doped carbon materials obtained in examples 1 to 3 are 3.11mmol/g, 3.03mmol/g and 2.83mmol/g, respectively, under the pressure condition of 1 bar; the test results show that the carbon material obtained by using the kalium equiseti as an activating agent and a nitrogen and sulfur CO-doping reagent has CO resistance 2 Has good adsorption capacity.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. The preparation method of the sulfur-nitrogen co-doped carbon material is characterized by comprising the following steps of:
and mixing biomass carbon and the potassium equilin sulfonate, and then carrying out heat treatment to obtain the sulfur-nitrogen co-doped carbon material.
2. The preparation method according to claim 1, wherein the mass ratio of the biomass carbon to the potassium marinoethanesulfonate is 1:1 to 5.
3. The preparation method according to claim 2, wherein the temperature of the heat treatment is 600-900 ℃, and the holding time is 1-2 h;
the heat treatment is carried out in a protective atmosphere.
4. The method for producing biomass carbon according to claim 1, comprising the steps of:
and carbonizing the biomass raw material to obtain the biomass carbon.
5. The method according to claim 4, wherein the biomass material comprises one or more of chitosan, cellulose, agar, lignin, starch, gelatin, sucrose and glucose.
6. The production method according to claim 4 or 5, characterized in that the carbonization treatment includes a hydrothermal carbonization treatment or a solid-phase carbonization treatment.
7. The preparation method according to claim 6, wherein the temperature of the hydrothermal carbonization treatment is 160-220 ℃ and the holding time is 1-6 h.
8. The method according to claim 6, wherein the temperature of the solid phase carbonization is 400 to 600 ℃ and the holding time is 1 to 2 hours.
9. The carbon material co-doped with sulfur and nitrogen prepared by the preparation method of any one of claims 1 to 8, wherein the sulfur content in the carbon material co-doped with sulfur is 3.0 to 9.0wt%; the doping percentage content of nitrogen is 3.0-6.0 wt%.
10. Use of the sulfur-nitrogen co-doped carbon material as claimed in claim 9 as a gas adsorbent.
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