CN110773222A - Universal preparation method and application of hierarchical pore nitrogen-doped carbon catalyst based on double-pore-foaming agent synthesis - Google Patents
Universal preparation method and application of hierarchical pore nitrogen-doped carbon catalyst based on double-pore-foaming agent synthesis Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004088 foaming agent Substances 0.000 title claims abstract description 14
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- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 52
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- 239000002808 molecular sieve Substances 0.000 claims abstract description 17
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- 239000011148 porous material Substances 0.000 claims abstract description 16
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- SRRLDCNCJFKVFJ-UHFFFAOYSA-J disodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate;cobalt(2+) Chemical compound [Na+].[Na+].[Co+2].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O SRRLDCNCJFKVFJ-UHFFFAOYSA-J 0.000 claims abstract description 9
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- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- -1 disodium tetraethyl cobalt tetraacetate Chemical compound 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/643—Pore diameter less than 2 nm
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- B01J35/64—Pore diameter
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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Abstract
The invention discloses a universal preparation method and application of a hierarchical pore nitrogen-doped carbon catalyst based on double pore-foaming agent synthesis. Mixing the biomass chitosan, ethylene diamine tetraacetic acid disodium cobalt salt and a molecular sieve SBA-15 with water, and drying to obtain a material A; heating the material A from room temperature to 300 ℃ for 60min under the protection of inert gas, then heating to 800 ℃ at the heating rate of 10 ℃/min for 120min, and naturally cooling to room temperature to obtain a material B; and adding the material B into an acid solution, soaking for 12h, washing with high-purity water until the filtrate is neutral, and drying at 40-60 ℃ for 12h to obtain the target product, namely the hierarchical porous nitrogen-doped carbon catalyst. The specific surface area of the multi-level pore nitrogen-doped carbon catalyst prepared by the invention is 661-925m2/g, and the catalyst contains a large number of micropores and mesopores, and the catalyst can be used as a cathode material to be applied to an electro-Fenton system, can efficiently degrade organic pollutants, does not cause secondary pollution in the using process, and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of synthesis of porous carbon materials, and particularly relates to a universal preparation method and application of a hierarchical pore nitrogen-doped carbon catalyst synthesized based on a double pore-foaming agent.
Background
Energy crisis and environmental pollution are two major problems of global nature, hinder the development of social aspects. With the development of science and technology, the quantity of artificially synthesized refractory organic matters is increased. Meanwhile, in the industrial production process, organic pollutants which have high biotoxicity and are extremely difficult to be degraded by microorganisms are also discharged into rivers, soil and other natural world, which seriously harms the living environment of people and animals and plants. Therefore, the treatment problem of refractory organic pollutants is receiving more and more attention.
The electro-Fenton process uses an oxygen reduction process to generate hydrogen peroxide in situ at the cathode, followed by H
2O
2With Fe
2+The Fenton reaction is carried out to generate a strong oxidant, namely OH, which can attack organic pollutants without selectivity to degrade the organic pollutants into carbon dioxide and water, thereby achieving the purposes of degrading the pollutants and purifying the water quality. Compared with other oxidation technologies, the electro-Fenton technology has the advantages of low cost, mild reaction conditions, high treatment speed, simple reaction device, thorough degradation, no secondary pollutants and the like, and is a novel, efficient and environment-friendly advanced electrochemical oxidation technology. In order to expose more active sites in the catalytic material and thus improve its catalytic performance, a templating agent is often added. Commonly used templating agents include hard and soft template porogens. The molecular sieve SBA-15 serving as a traditional hard template pore-foaming agent can construct a highly ordered, uniform and well-dispersed pore structure on the surface of a carbon material, but the preparation cost of the pore-foaming agent is high. In order to compensate for the above-mentioned drawbacks, researchers have also tried to prepare porous carbon materials using a soft template method. Among many soft template agents, disodium ethylene diamine tetraacetate cobalt salt is widely applied due to the characteristics of adjustable pore-forming size, more defect sites and low price, but the synthesized carbon material has poor orderliness and nonuniform distribution. Based on the above, the invention uses ethylenediamineThe disodium tetraethyl cobalt tetraacetate (EDTA-2 Na-Co) and the molecular sieve SBA-15 are combined to prepare the cathode material for the electro-Fenton system, which has the advantages of highly ordered pore structure, adjustable pore size and low cost.
Disclosure of Invention
The invention solves the technical problem of providing a universal preparation method and application of a hierarchical pore nitrogen-doped carbon catalyst synthesized based on double pore-forming agents, wherein the hierarchical pore nitrogen-doped carbon catalyst has an ordered pore structure and adjustable pore size, is low in cost and is environment-friendly.
The invention adopts the following technical scheme for solving the technical problems, and the universal preparation method of the hierarchical pore nitrogen-doped carbon catalyst based on double pore-foaming agent synthesis is characterized by comprising the following specific processes:
step S1: mixing the biomass chitosan, ethylene diamine tetraacetic acid disodium cobalt salt (EDTA-2 Na-Co) and molecular sieve SBA-15 with water, stirring for 2 hours by using a magnetic stirrer, fully mixing uniformly, and drying to obtain a material A;
step S2: transferring the material A obtained in the step S1 to a nickel boat, placing the nickel boat in a tube furnace, raising the temperature from room temperature to 300 ℃ for 60min after 60min under the protection of inert gas, raising the temperature to 800 ℃ at a heating rate of 10 ℃/min for 120min, and naturally cooling to room temperature to obtain a material B;
step S3: transferring the material B obtained in the step S2 into a container, adding an acid solution to soak for 12h, washing with high-purity water until the filtrate is neutral, and drying at 40-60 ℃ for 12h to obtain the target product, namely the hierarchical porous nitrogen-doped carbon catalyst, wherein the specific surface area of the hierarchical porous nitrogen-doped carbon catalyst is 661-925m
2And/g, and contains a large number of micropores and mesopores.
Further preferably, the feeding mass ratio of the biomass chitosan, the ethylene diamine tetraacetic acid disodium cobalt salt and the molecular sieve SBA-15 is 1:0.5-3.5: 0.5-3.5.
Further preferably, the feeding mass ratio of the biomass chitosan, the ethylene diamine tetraacetic acid disodium cobalt salt and the molecular sieve SBA-15 is 1:2.5: 2.5.
Further preferably, the inert gas is one or more of nitrogen or argon.
More preferably, the acidic solution is a 10wt% hydrofluoric acid solution.
Further preferably, the universal preparation method of the hierarchical pore nitrogen-doped carbon catalyst based on double-pore-foaming agent synthesis is characterized by comprising the following specific steps:
step S1: mixing 1g of biomass chitosan, 2.5g of EDTA-2Na-Co and 2.5g of molecular sieve SBA-15 with water, stirring for 2 hours by using a magnetic stirrer, fully mixing uniformly, and drying to obtain a material A;
step S2: transferring the material A obtained in the step S1 to a nickel boat, placing the nickel boat in a tube furnace, heating the material A to 300 ℃ from room temperature for 60min under the protection of nitrogen gas with the flow rate of 100mL/min, keeping the temperature for 60min, heating the material A to 800 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 120min, and naturally cooling the material A to room temperature to obtain a material B;
step S3: and (4) transferring the material B obtained in the step S2 to a 100mL beaker, adding an acidic solution to soak for 12h, washing with high-purity water until the filtrate is neutral, and drying at 40 ℃ for 12h in a forced air drying oven to obtain the multi-stage pore nitrogen-doped carbon catalyst C, wherein the multi-stage pore nitrogen-doped carbon catalyst C is used as a cathode material of an electro-Fenton system and is used for degrading 50mL of 15mg/L malachite green solution, and the time for complete degradation is 60 min.
The hierarchical pore nitrogen-doped carbon catalyst is used as a cathode material in an electro-Fenton system for efficiently degrading organic pollutants in a water body.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method simultaneously introduces ethylene diamine tetraacetic acid disodium cobalt salt (EDTA-2 Na-Co) and the molecular sieve SBA-15 as template agents, wherein the molecular sieve SBA-15 solid is used as a pore-forming agent, and a highly ordered, uniform and well-dispersed pore structure can be manufactured on the surface of a carbon material; the ethylene diamine tetraacetic acid disodium cobalt salt (EDTA-2 Na-Co) solid is used as a pore-forming agent, so that a large number of micropores and mesopores can be generated in the carbon material, the specific surface area and pore volume of the carbon material are increased, more active sites are exposed, the catalytic degradation activity of the material is enhanced, and the preparation process of the multilevel pore nitrogen-doped carbon catalyst is simple and has strong universality;
2. the specific surface area of the hierarchical porous nitrogen-doped carbon catalyst prepared by the method is 661-925m
2The cathode material is used as a cathode material applied to an electro-Fenton system, can efficiently degrade organic pollutants, does not cause secondary pollution in the using process, and is environment-friendly.
Drawings
FIG. 1 is a field emission scanning electron micrograph of a multi-level pore nitrogen-doped carbon catalyst prepared according to example 4;
FIG. 2 is an X-ray diffraction pattern of the carbon catalysts prepared in examples 1-4;
FIG. 3 is a graph of nitrogen desorption and pore size distribution of the multi-level pore nitrogen-doped carbon catalyst prepared in example 4;
FIG. 4 is a Raman spectrum of the carbon catalysts prepared in examples 1-4;
fig. 5 is a graph showing the time period for degradation of malachite green by the carbon catalysts prepared in examples 1-6.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.
Example 1
(1) Fully and uniformly mixing 1g of biomass chitosan and water, and drying to obtain a material A1;
(2) transferring the material A1 to a nickel boat, placing the nickel boat in a tube furnace, raising the temperature from room temperature to 300 ℃ for 60min through 60min under the protection of nitrogen gas with the flow rate of 100mL/min, raising the temperature to 800 ℃ at the temperature raising rate of 10 ℃/min for 120min, and then naturally cooling to room temperature to obtain a material B1;
(3) transferring the material B1 to a 100mL beaker, adding an acidic solution to soak for 12h, washing with high-purity water until the filtrate is neutral, and drying in an air-blast drying oven at 40 ℃ for 12h to obtain a carbon catalyst C1;
(4) the prepared carbon catalyst C1 is used as a cathode material of an electro-Fenton system for degrading 50mL of malachite green solution with the concentration of 15mg/L, and the time for complete degradation is 120 min.
Example 2
(1) Mixing 1g of biomass chitosan and 2.5g of EDTA-2Na-Co with water, stirring for 2 hours by using a magnetic stirrer, fully and uniformly mixing, and drying to obtain a material A2;
(2) transferring the material A2 to a porcelain boat, placing the porcelain boat in a tube furnace, raising the temperature from room temperature to 300 ℃ for 60min through 60min under the protection of nitrogen gas with the flow rate of 100mL/min, raising the temperature to 800 ℃ at the temperature raising rate of 10 ℃/min for 120min, and naturally cooling to room temperature to obtain a material B2;
(3) transferring the material B2 to a 100mL beaker, adding an acidic solution to soak for 12h, washing with high-purity water until the filtrate is neutral, and drying in an air-blast drying oven at 40 ℃ for 12h to obtain a carbon catalyst C2;
(4) the prepared carbon catalyst C2 is used as a cathode material of an electro-Fenton system for degrading 50mL of malachite green solution with the concentration of 15mg/L, and the time for complete degradation is 90 min.
Example 3
(1) Mixing 1g of biomass chitosan and 2.5g of molecular sieve SBA-15 with water, stirring for 2 hours by using a magnetic stirrer, fully mixing uniformly, and drying to obtain a material A3;
(2) transferring the material A3 to a nickel boat, placing the nickel boat in a tube furnace, raising the temperature from room temperature to 300 ℃ for 60min through 60min under the protection of nitrogen gas with the flow rate of 100mL/min, raising the temperature to 800 ℃ at the temperature raising rate of 10 ℃/min for 120min, and then naturally cooling to room temperature to obtain a material B3;
(3) transferring the material B3 to a 100mL beaker, adding an acidic solution to soak for 12h, washing with high-purity water until the filtrate is neutral, and drying in an air-blast drying oven at 40 ℃ for 12h to obtain a carbon catalyst C3;
(4) the prepared carbon catalyst C3 is used as a cathode material of an electro-Fenton system for degrading 50mL of malachite green solution with the concentration of 15mg/L, and the time for complete degradation is 80 min.
Example 4
(1) Mixing 1g of biomass chitosan, 0.5g of EDTA-2Na-Co and 0.5g of molecular sieve SBA-15 with water, stirring for 2 hours by using a magnetic stirrer, fully mixing uniformly, and drying to obtain a material A4;
(2) transferring the material A4 to a nickel boat, placing the nickel boat in a tube furnace, raising the temperature from room temperature to 300 ℃ for 60min through 60min under the protection of nitrogen gas with the flow rate of 100mL/min, raising the temperature to 800 ℃ at the temperature raising rate of 10 ℃/min for 120min, and then naturally cooling to room temperature to obtain a material B4;
(3) transferring the material B4 to a 100mL beaker, adding an acidic solution to soak for 12h, washing with high-purity water until the filtrate is neutral, and drying in an air-blast drying oven at 40 ℃ for 12h to obtain a hierarchical-pore nitrogen-doped carbon catalyst C4;
(4) the prepared hierarchical porous nitrogen-doped carbon catalyst C4 is used as a cathode material of an electro-Fenton system for degrading 50mL of malachite green solution with the concentration of 15mg/L, and the time for complete degradation is 75 min.
Example 5
(1) Mixing 1g of biomass chitosan, 2.5g of EDTA-2Na-Co and 2.5g of molecular sieve SBA-15 with water, stirring for 2 hours by using a magnetic stirrer, fully mixing uniformly, and drying to obtain a material A5;
(2) transferring the material A5 to a nickel boat, placing the nickel boat in a tube furnace, raising the temperature from room temperature to 300 ℃ for 60min through 60min under the protection of nitrogen gas with the flow rate of 100mL/min, raising the temperature to 800 ℃ at the temperature raising rate of 10 ℃/min for 120min, and then naturally cooling to room temperature to obtain a material B5;
(3) transferring the material B5 to a 100mL beaker, adding an acidic solution to soak for 12h, washing with high-purity water until the filtrate is neutral, and drying in an air-blast drying oven at 40 ℃ for 12h to obtain a hierarchical-pore nitrogen-doped carbon catalyst C5;
(4) the prepared hierarchical porous nitrogen-doped carbon catalyst C5 is used as a cathode material of an electro-Fenton system for degrading 50mL of malachite green solution with the concentration of 15mg/L, and the time for complete degradation is 60 min.
Example 6
(1) Mixing 1g of biomass chitosan, 3.5g of EDTA-2Na-Co and 3.5g of molecular sieve SBA-15 with water, stirring for 2 hours by using a magnetic stirrer, fully mixing uniformly, and drying to obtain a material A6;
(2) transferring the material A6 to a nickel boat, placing the nickel boat in a tube furnace, raising the temperature from room temperature to 300 ℃ for 60min through 60min under the protection of nitrogen gas with the flow rate of 100mL/min, raising the temperature to 800 ℃ at the temperature raising rate of 10 ℃/min for 120min, and then naturally cooling to room temperature to obtain a material B6;
(3) transferring the material B6 to a 100mL beaker, adding an acidic solution to soak for 12h, washing with high-purity water until the filtrate is neutral, and drying in an air-blast drying oven at 40 ℃ for 12h to obtain a hierarchical-pore nitrogen-doped carbon catalyst C6;
(4) the prepared hierarchical porous nitrogen-doped carbon catalyst C6 is used as a cathode material of an electro-Fenton system for degrading 50mL of malachite green solution with the concentration of 15mg/L, and the time for complete degradation is 80 min.
The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.
Claims (7)
1. A universal preparation method of a hierarchical pore nitrogen-doped carbon catalyst based on double pore-foaming agent synthesis is characterized by comprising the following specific steps:
step S1: mixing the biomass chitosan, ethylene diamine tetraacetic acid disodium cobalt salt (EDTA-2 Na-Co) and molecular sieve SBA-15 with water, stirring for 2 hours by using a magnetic stirrer, fully mixing uniformly, and drying to obtain a material A;
step S2: transferring the material A obtained in the step S1 to a nickel boat, placing the nickel boat in a tube furnace, raising the temperature from room temperature to 300 ℃ for 60min after 60min under the protection of inert gas, raising the temperature to 800 ℃ at a heating rate of 10 ℃/min for 120min, and naturally cooling to room temperature to obtain a material B;
step S3: will step withTransferring the material B obtained in the step S2 to a container, adding an acid solution to soak for 12h, washing with high-purity water until the filtrate is neutral, and drying at 40-60 ℃ for 12h to obtain the target product, namely the hierarchical porous nitrogen-doped carbon catalyst, wherein the specific surface area of the hierarchical porous nitrogen-doped carbon catalyst is 661-925m
2And/g, and contains a large number of micropores and mesopores.
2. The universal preparation method of the hierarchical pore nitrogen-doped carbon catalyst based on double-pore-foaming agent synthesis, according to claim 1, is characterized in that: the feeding mass ratio of the biomass chitosan, the ethylene diamine tetraacetic acid disodium cobalt salt and the molecular sieve SBA-15 is 1:0.5-3.5: 0.5-3.5.
3. The universal preparation method of the hierarchical pore nitrogen-doped carbon catalyst based on double-pore-foaming agent synthesis, according to claim 1, is characterized in that: the feeding mass ratio of the biomass chitosan to the ethylene diamine tetraacetic acid disodium cobalt salt to the molecular sieve SBA-15 is 1:2.5: 2.5.
4. The universal preparation method of the hierarchical pore nitrogen-doped carbon catalyst based on double-pore-foaming agent synthesis, according to claim 1, is characterized in that: the inert gas is one or more of nitrogen or argon.
5. The universal preparation method of the hierarchical pore nitrogen-doped carbon catalyst based on double-pore-foaming agent synthesis, according to claim 1, is characterized in that: the acid solution is a 10wt% hydrofluoric acid solution.
6. The universal preparation method of the hierarchical pore nitrogen-doped carbon catalyst based on double-pore-foaming agent synthesis according to claim 1, which is characterized by comprising the following specific steps:
step S1: mixing 1g of biomass chitosan, 2.5g of EDTA-2Na-Co and 2.5g of molecular sieve SBA-15 with water, stirring for 2 hours by using a magnetic stirrer, fully mixing uniformly, and drying to obtain a material A;
step S2: transferring the material A obtained in the step S1 to a nickel boat, placing the nickel boat in a tube furnace, heating the material A to 300 ℃ from room temperature for 60min under the protection of nitrogen gas with the flow rate of 100mL/min, keeping the temperature for 60min, heating the material A to 800 ℃ at the heating rate of 10 ℃/min, keeping the temperature for 120min, and naturally cooling the material A to room temperature to obtain a material B;
step S3: and (4) transferring the material B obtained in the step S2 to a 100mL beaker, adding an acidic solution to soak for 12h, washing with high-purity water until the filtrate is neutral, and drying at 40 ℃ for 12h in a forced air drying oven to obtain the multi-stage pore nitrogen-doped carbon catalyst C, wherein the multi-stage pore nitrogen-doped carbon catalyst C is used as a cathode material of an electro-Fenton system and is used for degrading 50mL of 15mg/L malachite green solution, and the time for complete degradation is 60 min.
7. The hierarchical porous nitrogen-doped carbon catalyst prepared by the method according to any one of claims 1 to 6 is used as a cathode material in an electro-Fenton system for efficiently degrading organic pollutants in water.
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