CN107649166B - Preparation method of porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst - Google Patents
Preparation method of porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst Download PDFInfo
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- 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
-
- 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
- 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
- B01J35/647—2-50 nm
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a preparation method of a porous nitrogen-phosphorus double-doped carbon-oxygen reduction electrode catalytic material, which comprises the steps of carrying out hydrothermal reaction on white beech mushroom and ultrapure water at 180 ℃ for 24 hours, cooling to room temperature, and drying product slurry to obtain a material A; dropwise adding an ammonia water solution into a zinc chloride water solution to obtain a mixed double-activator solution B, immersing the material A in the mixed double-activator solution B, uniformly mixing, and drying to obtain a material C; heating the material C from room temperature to 300 ℃ for 2h after 60min, heating to 700-; and adding the material D into an acid solution, soaking for 12h, washing with high-purity water until the filtrate is neutral, and drying at 105 ℃ for 6h to obtain the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst. The specific surface area of the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst prepared by the invention is 1075.311m2The catalyst has the advantages of excellent oxygen reduction catalytic performance, methanol interference resistance and carbon monoxide poisoning resistance, and the average pore diameter is 2.587 nm.
Description
Technical Field
The invention belongs to the technical field of synthesis of porous heteroatom doped carbon materials, and particularly relates to a preparation method of a porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst.
Background
The heteroatom doped carbon material is favored by the majority of researchers due to low cost, high oxygen reduction catalytic activity, strong methanol interference resistance and good long-term stability. Single heteroatom non-metallic carbon based catalysts were the first to attract attention. Since the 2009 deliming et al reported that nitrogen-doped carbon nanotubes have excellent oxygen reduction catalytic activity, nitrogen-doped carbon materials have become one of the most studied monatomic doped carbons to date. In addition, other single heteroatom (B, S, P, and F) doped carbon materials are also being increasingly prepared and studied. In recent years, after single-atom doping is proved to be effective in improving the catalytic activity of carbon materials, the development of diatomic doped carbon as a high-efficiency non-metal electrocatalyst becomes a new research hotspot. At present, some reports say that the double doping of nitrogen and phosphorus heteroatoms can further improve the electrocatalytic activity of the nonmetal catalyst, but such reports and related patents are relatively few. Patent publication No. CN106807427A discloses a method for preparing a metal-embedded nitrogen-phosphorus double-doped carbon material by using agar as a carbon source, Ethylene Diamine Tetra Methyl Phosphate (EDTMPA) as a nitrogen source and a phosphorus source, and a transition metal salt as a precursor and a pore-forming agent, but the method has a long implementation procedure and an outstanding oxygen reduction catalytic activity.
Disclosure of Invention
The invention solves the technical problem of providing a preparation method of a porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst with a novel activation method and low synthesis cost.
The invention adopts the following technical scheme for solving the technical problems, and the preparation method of the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst is characterized by comprising the following specific processes:
(1) placing a dried and clean biomass precursor white beech mushroom and ultrapure water into a high-pressure reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 24 hours, naturally cooling to room temperature after the reaction is finished, and drying product slurry in the high-pressure reaction kettle to obtain a material A;
(2) dropwise adding an ammonia water solution with the mass concentration of 25% into a zinc chloride water solution to react to obtain a mixed double-activator solution B simultaneously containing zinc hydroxide and zinc chloride, immersing the material A into the mixed double-activator solution B, uniformly mixing, and drying to obtain a material C;
(3) transferring the material C to a porcelain boat, placing the porcelain boat in a tube furnace, raising the temperature from room temperature to 300 ℃ for 2h after 60min under the protection of inert gas, raising the temperature to 700-1000 ℃ at the temperature raising rate of 10 ℃/min for 2h, and naturally cooling to room temperature to obtain a material D;
(4) and transferring the material D into a reaction vessel, adding an acid solution to soak for 12h, washing with high-purity water until the filtrate is neutral, and drying at 105 ℃ for 6h to obtain the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst.
Further preferably, the feeding ratio of the white beech mushroom and the ultrapure water in the step (1) is 1g to 10 mL.
Further preferably, the feeding ratio of the ammonia water solution and the zinc chloride water solution in the step (2) meets N (NH)3·H2O）：n（ZnCl2）=1:1。
Further preferably, the inert gas in step (3) is one or more of nitrogen or argon.
Further preferably, the acidic solution in the step (4) is a hydrochloric acid solution with a molar concentration of 2 mol/L.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, zinc hydroxide and zinc chloride are introduced as a mixed double activator, so that the specific surface area and the pore area of the carbon material are increased, more active sites are exposed, and the oxygen reduction catalytic activity of the carbon material is increased;
2. according to the invention, the biomass precursor is induced to dope nitrogen into the carbon skeleton, so that the formation of more active sites is promoted, and the electrochemical performance of the prepared carbon material is enhanced;
3. according to the invention, the biomass precursor is induced to dope phosphorus element into the nitrogen-doped carbon material, so that more active sites are further formed, and the electrochemical performance of the prepared carbon material is enhanced;
4. the specific surface area of the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst prepared by the invention is 1075.311m2The catalyst has the advantages of excellent oxygen reduction catalytic performance, methanol interference resistance and carbon monoxide poisoning resistance, and is characterized by/g, the average pore diameter of 2.587nm, the nitrogen content of 1.82At percent and the phosphorus content of 0.45At percent.
Drawings
FIG. 1 is a transmission electron microscope image of the porous N-P double-doped C-O reduction catalyst prepared in example 2;
FIG. 2 is a full X-ray photoelectron spectrum of the porous N-P double-doped C-O reduction catalyst prepared in example 2;
FIG. 3 is an X-ray diffraction pattern of the porous N-P double-doped C-O reduction catalyst prepared in examples 1-7;
FIG. 4 is a Raman spectrum of the porous N-P double doped C-O reduction catalyst prepared in examples 1-7;
FIG. 5 is a graph showing the pore size distribution of the porous NPC double-doped C/O reduction catalyst prepared in example 2;
FIG. 6 is a linear sweep voltammogram of the porous nitrogen phosphorus double-doped carbon-oxygen reduction catalyst prepared in examples 1-7;
fig. 7 is a cyclic voltammogram of the porous nitrogen phosphorus double-doped carbon-oxygen reduction catalyst prepared in example 2.
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) Placing 3g of dry and clean biomass precursor white beech mushroom and 30mL of ultrapure water in a high-pressure reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 24 hours, naturally cooling to room temperature after the reaction is finished, and then placing product slurry in the high-pressure reaction kettle in a blast drying oven, and drying at 80 ℃ for 10 hours to obtain a material A;
(2) adding ammonia water solution (0.011 mol NH) with mass concentration of 25%3·H2O) was added dropwise to an aqueous zinc chloride solution (0.022 mol ZnCl)2) The mixed double activator solution B1 containing zinc hydroxide and zinc chloride is obtained by reaction, 1g of the material A is immersed in the mixed double activator solution B1 and uniformly mixed, and then the mixture is placed in a blast drying oven to be dried for 10 hours at 105 ℃ to obtain a material C1, namely the carbonization pretreatment process is completed;
(3) transferring the material C1 to a porcelain boat, placing the porcelain boat in a tube furnace, heating the porcelain boat to 300 ℃ from room temperature for 2h after 60min under the protection of nitrogen gas with the flow rate of 100mL/min, heating the porcelain boat to 900 ℃ at the heating rate of 10 ℃/min, keeping the porcelain boat for 2h, and then naturally cooling the porcelain boat to room temperature to obtain a material D1;
(4) and transferring the material D1 to a reaction container, adding 100mL of hydrochloric acid solution with the molar concentration of 2mol/L, soaking for 12h, washing with high-purity water until the filtrate is neutral, and then placing in an air-blast drying oven to dry for 6h at 105 ℃ to obtain the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst E1.
Example 2
(1) Adding ammonia water solution (0.022 mol NH) with the mass concentration of 25%3·H2O) was added dropwise to an aqueous zinc chloride solution (0.022 mol ZnCl)2) The mixed double activator solution B2 containing zinc hydroxide and zinc chloride is obtained by reaction, 1g of the material A is immersed in the mixed double activator solution B2 and uniformly mixed, and then the mixture is placed in a blast drying oven to be dried for 10 hours at 105 ℃ to obtain a material C2, namely the carbonization pretreatment process is completed;
(2) transferring the material C2 to a porcelain boat, placing the porcelain boat in a tube furnace, heating the porcelain boat to 300 ℃ from room temperature for 2h after 60min under the protection of nitrogen gas with the flow rate of 100mL/min, heating the porcelain boat to 900 ℃ at the heating rate of 10 ℃/min, keeping the porcelain boat for 2h, and then naturally cooling the porcelain boat to room temperature to obtain a material D2;
(3) and transferring the material D2 to a reaction container, adding 100mL of hydrochloric acid solution with the molar concentration of 2mol/L, soaking for 12h, washing with high-purity water until the filtrate is neutral, and then placing in a forced air drying oven to dry for 6h at 105 ℃ to obtain the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst E2 (E2-900).
Example 3
(1) An ammonia water solution (0.033 mol NH) with a mass concentration of 25 percent3·H2O) was added dropwise to an aqueous zinc chloride solution (0.022 mol ZnCl)2) The mixed double activator solution B3 containing zinc hydroxide and zinc chloride is obtained by reaction, 1g of the material A is immersed in the mixed double activator solution B3 and uniformly mixed, and then the mixture is placed in a blast drying oven to be dried for 10 hours at 105 ℃ to obtain a material C3, namely the carbonization pretreatment process is completed;
(2) transferring the material C3 to a porcelain boat, placing the porcelain boat in a tube furnace, heating the porcelain boat to 300 ℃ from room temperature for 2h after 60min under the protection of nitrogen gas with the flow rate of 100mL/min, heating the porcelain boat to 900 ℃ at the heating rate of 10 ℃/min, keeping the porcelain boat for 2h, and then naturally cooling the porcelain boat to room temperature to obtain a material D3;
(3) and transferring the material D3 to a reaction container, adding 100mL of hydrochloric acid solution with the molar concentration of 2mol/L, soaking for 12h, washing with high-purity water until the filtrate is neutral, and then placing in an air-blast drying oven to dry for 6h at 105 ℃ to obtain the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst E3.
Example 4
(1) An ammonia solution (0.044 mol NH) with a mass concentration of 25 percent is added3·H2O) was added dropwise to an aqueous zinc chloride solution (0.022 mol ZnCl)2) The mixed double activator solution B4 containing zinc hydroxide and zinc chloride is obtained by reaction, 1g of the material A is immersed in the mixed double activator solution B4 and uniformly mixed, and then the mixture is placed in a blast drying oven to be dried for 10 hours at 105 ℃ to obtain a material C4, namely the carbonization pretreatment process is completed;
(2) transferring the material C4 to a porcelain boat, placing the porcelain boat in a tube furnace, heating the porcelain boat to 300 ℃ from room temperature for 2h after 60min under the protection of nitrogen gas with the flow rate of 100mL/min, heating the porcelain boat to 900 ℃ at the heating rate of 10 ℃/min, keeping the porcelain boat for 2h, and then naturally cooling the porcelain boat to room temperature to obtain a material D4;
(3) and transferring the material D4 to a reaction container, adding 100mL of hydrochloric acid solution with the molar concentration of 2mol/L, soaking for 12h, washing with high-purity water until the filtrate is neutral, and then placing in an air-blast drying oven to dry for 6h at 105 ℃ to obtain the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst E4.
Example 5
(1) Transferring the material C2 to a porcelain boat, placing the porcelain boat in a tube furnace, heating the porcelain boat to 300 ℃ from room temperature for 2h after 60min under the protection of nitrogen gas with the flow rate of 100mL/min, heating the porcelain boat to 700 ℃ at the heating rate of 10 ℃/min, keeping the porcelain boat for 2h, and then naturally cooling the porcelain boat to room temperature to obtain a material D2-700;
(2) and transferring the material D2-700 to a reaction container, adding 100mL of hydrochloric acid solution with the molar concentration of 2mol/L, soaking for 12h, washing with high-purity water until the filtrate is neutral, and then placing in a forced air drying oven to dry for 6h at 105 ℃ to obtain the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst E2-700.
Example 6
(1) Transferring the material C2 to a porcelain boat, placing the porcelain boat in a tube furnace, heating the porcelain boat to 300 ℃ from room temperature for 2h after 60min under the protection of nitrogen gas with the flow rate of 100mL/min, heating the porcelain boat to 800 ℃ at the heating rate of 10 ℃/min, keeping the porcelain boat for 2h, and then naturally cooling the porcelain boat to room temperature to obtain a material D2-800;
(2) and transferring the material D2-800 to a reaction container, adding 100mL of hydrochloric acid solution with the molar concentration of 2mol/L, soaking for 12h, washing with high-purity water until the filtrate is neutral, and then placing in a forced air drying oven to dry for 6h at 105 ℃ to obtain the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst E2-800.
Example 7
(1) Transferring the material C2 to a porcelain boat, placing the porcelain boat in a tube furnace, heating the porcelain boat to 300 ℃ from room temperature for 2h after 60min under the protection of nitrogen gas with the flow rate of 100mL/min, heating the porcelain boat to 1000 ℃ at the heating rate of 10 ℃/min, keeping the porcelain boat for 2h, and then naturally cooling the porcelain boat to room temperature to obtain a material D2-1000;
(2) and transferring the material D2-1000 to a reaction container, adding 100mL of hydrochloric acid solution with the molar concentration of 2mol/L, soaking for 12h, washing with high-purity water until the filtrate is neutral, and then placing in a forced air drying oven to dry for 6h at 105 ℃ to obtain the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst E2-1000.
Example 8
Weighing a certain amount of E2 sample which is ground into powder by using an electronic balance, uniformly mixing the E2 sample with 5wt% of Nafion and high-purity water, and then carrying out ultrasonic treatment for several minutes to finally obtain a uniform ink-shaped solution; in the ultrasonic process, aluminum oxide polishing powder is used for polishing the surface of a glassy carbon electrode to be bright and free of any stain and scratch, then the glassy carbon electrode is placed in an ultrasonic instrument for ultrasonic treatment for a few minutes, and finally an eyeball is used for drying the surface of the electrode for later use; and (3) moving a proper amount of the ultrasonically-treated ink-like active substance by using a liquid transfer device, dripping the ultrasonically-treated ink-like active substance on the glassy carbon electrode, and then airing at room temperature to finish the preparation of the working electrode. Working electrodes for E1, E3, E4, E2-700, E2-800 and E2-1000 samples were prepared in the same manner and used for comparison with the E2 sample. All electrochemical tests used a three-electrode system. In the Linear Sweep Voltammetry (LSV) test, the working electrode was a 4mm diameter glassy carbon electrode coated with a certain volume and concentration of active material (the above prepared ink-like active material), the reference electrode was an Hg/HgO electrode, the counter electrode was a platinum sheet electrode, the electrolyte was 0.1mol/L aqueous potassium hydroxide solution and saturated with oxygen or nitrogen in advance, the sweep rate was 10mV/s, the rotation rates were 400rpm, 625rpm, 900rpm, 1225rpm, 1600rpm and 2025rpm, respectively, and the sweep range was-0.8V-0.4V. In the Cyclic Voltammetry (CV) test, the working electrode was a 3mm diameter glassy carbon electrode coated with a volume of active material (the prepared ink-like active material described above) at a concentration, the reference electrode was still a Hg/HgO electrode, the counter electrode was still a platinum plate electrode, the electrolyte was still 0.1mol/L aqueous potassium hydroxide solution and was previously saturated with oxygen or nitrogen, the scan rate was still 10mV/s during the test, and the sweep range was-0.8V-0.2V.
The catalytic performance of the samples in all examples is shown in FIG. 6, the initial potentials of the E1, E2(E2-900), E3, E4, E2-700, E2-800 and E2-1000 samples under the polar scanning curve of the rotating disk electrode obtained at a rotation speed of 1600rpm are 0.060V, 0.085V, 0.080V, 0.041V, 0.036V, 0.050V and 0.055V, respectively, as shown in FIG. 7, the peak potential is-0.027V for the cyclic voltammogram of the E2 sample obtained in example 2.
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 (6)
1. A preparation method of a porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst is characterized by comprising the following specific steps:
(1) placing a dried and clean biomass precursor white beech mushroom and ultrapure water into a high-pressure reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 24 hours, naturally cooling to room temperature after the reaction is finished, and drying product slurry in the high-pressure reaction kettle to obtain a material A;
(2) dropwise adding an ammonia water solution with the mass concentration of 25% into a zinc chloride water solution to react to obtain a mixed double-activator solution B simultaneously containing zinc hydroxide and zinc chloride, immersing the material A into the mixed double-activator solution B, uniformly mixing, and drying to obtain a material C;
(3) transferring the material C to a porcelain boat, placing the porcelain boat in a tube furnace, raising the temperature from room temperature to 300 ℃ for 2h after 60min under the protection of inert gas, raising the temperature to 700-1000 ℃ at the temperature raising rate of 10 ℃/min for 2h, and naturally cooling to room temperature to obtain a material D;
(4) and transferring the material D into a reaction vessel, adding an acid solution to soak for 12h, washing with high-purity water until the filtrate is neutral, and drying at 105 ℃ for 6h to obtain the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst.
2. The preparation method of the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst according to claim 1, characterized by comprising the following steps: in the step (1), the feeding ratio of the white beech mushroom to the ultrapure water is 1g:10 mL.
3. The preparation method of the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst according to claim 1, characterized by comprising the following steps: the feeding ratio of the ammonia water solution and the zinc chloride water solution in the step (2) meets N (NH)3·H2O）：n（ZnCl2）=1:1。
4. The preparation method of the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst according to claim 1, characterized by comprising the following steps: and (3) the inert gas in the step (3) is one or more of nitrogen and argon.
5. The preparation method of the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst according to claim 1, characterized by comprising the following steps: the acid solution in the step (4) is hydrochloric acid solution with the molar concentration of 2 mol/L.
6. The preparation method of the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst according to claim 1, characterized by comprising the following steps:
(1) placing 3g of dry and clean biomass precursor white beech mushroom and 30mL of ultrapure water in a high-pressure reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 24 hours, naturally cooling to room temperature after the reaction is finished, and then placing product slurry in the high-pressure reaction kettle in a blast drying oven, and drying at 80 ℃ for 10 hours to obtain a material A;
(2) will contain 0.022mol of NH3·H2Dropwise adding an ammonia water solution with the mass concentration of O being 25% into a solution containing 0.022mol of ZnCl2The zinc chloride aqueous solution is reacted to obtain a mixed double activator solution B2 containing zinc hydroxide and zinc chloride, 1g of the material A is immersed in the mixed double activator solution B2 and uniformly mixed, and then the mixture is placed in a forced air drying oven to be dried for 10 hours at 105 ℃ to obtain a material C2;
(3) transferring the material C2 to a porcelain boat, placing the porcelain boat in a tube furnace, heating the porcelain boat to 300 ℃ from room temperature for 2h after 60min under the protection of nitrogen gas with the flow rate of 100mL/min, heating the porcelain boat to 900 ℃ at the heating rate of 10 ℃/min, keeping the porcelain boat for 2h, and then naturally cooling the porcelain boat to room temperature to obtain a material D2;
(4) transferring the material D2 to a reaction container, adding 100mL of hydrochloric acid solution with the molar concentration of 2mol/L, soaking for 12h, washing with high-purity water until the filtrate is neutral, then placing in a forced air drying oven, and drying at 105 ℃ for 6h to obtain the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst E2, wherein the specific surface area of the porous nitrogen-phosphorus double-doped carbon-oxygen reduction catalyst E2 is 1075.311m2In g, the average pore diameter was 2.587 nm.
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| CN109012729A (en) * | 2018-08-13 | 2018-12-18 | 河南师范大学 | A kind of preparation method of porous nitrogen fluorine codope carbon oxygen reduction catalyst |
| CN109167077B (en) * | 2018-09-13 | 2022-05-17 | 大连海事大学 | Phosphorus-doped porous carbon-oxygen reduction catalyst and preparation method and application thereof |
| CN109841858B (en) * | 2019-03-27 | 2020-10-30 | 华中科技大学 | Method for preparing biochar-based oxygen reduction reaction catalyst by using bean dregs and product |
| CN110048134A (en) * | 2019-05-27 | 2019-07-23 | 河南师范大学 | A kind of universality method preparing porous nitrogen fluorine codope carbon oxygen reduction catalyst |
| CN110424069B (en) * | 2019-08-11 | 2021-07-23 | 武汉中科先进技术研究院有限公司 | Biomass-based carbon nitrogen phosphorus composite fiber material and preparation method thereof |
| CN113522334A (en) * | 2021-06-29 | 2021-10-22 | 河南师范大学 | Method for synthesizing shaddock peel derived porous nitrogen-doped carbon-based oxygen reduction catalyst |
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