CN111185218A - Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst and preparation method thereof - Google Patents
Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229920001661 Chitosan Polymers 0.000 claims abstract description 55
- 239000013082 iron-based metal-organic framework Substances 0.000 claims abstract description 49
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000032050 esterification Effects 0.000 claims abstract description 15
- 238000005886 esterification reaction Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000004471 Glycine Substances 0.000 claims abstract description 12
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 78
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 238000010438 heat treatment Methods 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 23
- 238000001816 cooling Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000012153 distilled water Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 15
- 239000012265 solid product Substances 0.000 claims description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- 239000013110 organic ligand Substances 0.000 claims description 11
- -1 (p-carboxyphenyl) amino Chemical group 0.000 claims description 10
- 239000007983 Tris buffer Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 4
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 abstract description 51
- 239000003575 carbonaceous material Substances 0.000 abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 abstract description 28
- 239000001301 oxygen Substances 0.000 abstract description 28
- 239000011148 porous material Substances 0.000 abstract description 8
- 150000001869 cobalt compounds Chemical class 0.000 abstract description 7
- 239000002086 nanomaterial Substances 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 239000012921 cobalt-based metal-organic framework Substances 0.000 abstract description 5
- 238000005087 graphitization Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000011258 core-shell material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229910052963 cobaltite Inorganic materials 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B01J35/33—
-
- 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
-
- B01J35/50—
-
- B01J35/60—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
Abstract
The invention relates to the technical field of oxygen reduction catalysts, and discloses a Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst and a preparation method thereof, wherein the Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst comprises the following formula raw materials: fe-based MOFs, hydroxyethylidene diphosphonic acid, chitosan, glycine, an esterification catalyst, a composite alkali catalyst and a condensing agent. According to the Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst and the preparation method thereof, N/P Co-doping enables a carbon material to form rich pore channels and a large number of mesoporous structures, so that the formation of active sites and the medium transmission of oxygen reduction reaction are facilitated, a core-shell nano structure with a cobalt compound coated by a porous carbon material has a richer morphology structure, so that the catalyst has better mass transfer performance, the cobalt compound formed after the Co-based MOFs with the nano structure are calcined is uniformly loaded into the pore channels of the porous carbon material, the graphitization degree of the carbon material is improved by the cobalt compound, the conductivity of the carbon material is increased, and the forward progress of the oxygen reduction reaction is promoted.
Description
Technical Field
The invention relates to the technical field of oxygen reduction catalysts, in particular to a Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst and a preparation method thereof.
Background
In daily life and industrial production, people mainly obtain energy by burning fossil energy, but the global warming, energy exhaustion, environmental pollution and other problems brought about have become more and more serious, so the novel energy conversion device and the energy storage equipment become research hotspots with their unique advantages, the fuel cell is taken as a novel energy conversion device, the anode reaction thereof can convert the chemical energy of specific fuel into electric energy through the electrochemical catalysis process, thereby realizing the conversion of energy, in the whole process of realizing the energy conversion by electrocatalysis, the fuel cell is more environment-friendly because of no participation of the traditional fossil fuel combustion process, in order to ensure the normal energy conversion of the fuel cell, and meanwhile, in order to reduce cost, the cathode reaction thereof is usually an Oxygen Reduction Reaction (ORR).
At present, a platinum-carbon catalyst and an electrode material thereof are generally used for a cathode Oxygen Reduction Reaction (ORR) of a fuel cell to promote the oxygen reduction reaction, but the precious metal Pt is rare in content and expensive, so that the cost of the fuel cell is greatly increased, the electrochemical stability of the platinum catalytic material is generally poor, the platinum catalytic material gradually loses activity in a long-time cell electrolysis process, and in addition, the Fe-N-C catalyst also has good catalytic ability to promote the oxygen reduction reaction, but the Fe-N-C catalyst is easy to agglomerate in an electrolyte, so that active sites are reduced, and the graphitization degree of the carbon material of the catalyst is low, so that the electrical conductivity of the carbon material is low, the transmission and diffusion of electrons in the oxygen reduction reaction are inhibited, and the reaction rate of the oxygen reduction reaction is reduced.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst and a preparation method thereof, solves the problems that the conventional oxygen reduction catalyst is easy to agglomerate and reduces active sites, and simultaneously solves the problems that the carbon material in the catalyst is not graphitized so as to cause poor conductivity of the catalyst and reduce the transmission and diffusion rates of electrons in the oxygen reduction reaction.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst and a preparation method thereof comprise the following formula raw materials in parts by weight: 6-21 parts of Fe-based MOFs, 20-22 parts of hydroxyethylidene diphosphonic acid, 22-25 parts of chitosan, 14-16 parts of glycine, 1-3 parts of esterification catalyst, 12-15 parts of composite alkali catalyst and 10-13 parts of condensing agent.
Preferably, the esterification catalyst is p-toluenesulfonic acid.
Preferably, the composite base catalyst is 4-dimethylaminopyridine and potassium carbonate, and the molar ratio of the two substances is 1: 1.2-1.8.
Preferably, the condensing agent is 1-hydroxy-7-azobenzotriazole.
Preferably, the preparation method of the Fe-based MOFs comprises the following steps:
(1) adding Co (NO) into a mixed solvent of distilled water and absolute ethyl alcohol with the volume ratio of 1:2-43)2·6H2O and an organic ligand 2,4, 6-tris [ (p-carboxyphenyl) amino group]1,3, 5-triazine, and placing the solution in an ultrasonic processor for ultrasonic dispersion treatment for 1-2 h.
(2) Transferring the solution into a reaction kettle, heating to 240 ℃ for reaction for 4-6h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with a proper amount of anhydrous ethanol and distilled water in sequence, and fully drying to prepare the Fe-based MOFs.
Preferably, said Co (NO)3)2·6H2O and an organic ligand 2,4, 6-tris [ (p-carboxyphenyl) amino group]The molar ratio of the substances of-1, 3, 5-triazine is 1: 1.5-2.5.
Preferably, the preparation method of the Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst comprises the following steps:
(1) adding a sulfuric acid solution into an ethylene glycol solvent to adjust the pH value of the solution to 3-4, sequentially adding 22-25 parts of chitosan, 14-16 parts of glycine and 1-3 parts of esterification catalyst p-toluenesulfonic acid, transferring the solution into a reaction kettle, heating to 140 ℃ and 150 ℃, and reacting for 10-15 h.
(2) Cooling the reaction kettle to room temperature, adding a proper amount of sodium hydroxide, adjusting the pH value of the solution to 7, sequentially adding 20-22 parts of hydroxyethylidene diphosphonic acid, 12-15 parts of composite base catalyst and 10-13 parts of condensing agent, heating the reaction kettle to 140 ℃, and reacting for 25-30 h.
(3) And cooling the reaction kettle to room temperature, removing the solvent from the solution by a high-speed centrifuge, washing the solid product by using a proper amount of absolute ethyl alcohol and distilled water in sequence, and fully drying to obtain the phosphate-amidated chitosan.
(4) Adding 6-21 parts of Fe-based MOFs and the phosphate-amidated chitosan prepared in the step (1) into absolute ethyl alcohol, placing the solution into an ultrasonic treatment instrument, heating to 40-50 ℃, wherein the ultrasonic frequency is 20-28KHz, performing ultrasonic dispersion treatment for 2-3h, filtering the solution to remove the solvent, and fully drying to obtain the phosphate-amidated chitosan-coated Fe-based MOFs.
(5) Putting the phosphate-amidated chitosan coated Fe-based MOFs prepared in the step (4) into a crucible, adding a proper amount of ammonia water, putting the crucible into an atmosphere resistance furnace, and introducing high-purity N2The temperature rise rate is 5-10 ℃, the calcination is carried out for 6-8h at 950-980 ℃, and the annealing is carried out for 2-3h at 950-980 ℃ to prepare the Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
according to the Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst and the preparation method thereof, a porous carbon material is prepared by calcining phosphate ester-amidated chitosan, N/P Co-doping enables rich pore channels to be formed inside the carbon material, a large number of mesoporous structures to be formed on the surface, and the carbon material is enabled to form a large specific surface area, so that rich active sites are provided, meanwhile, the rich pore channels and the large number of mesoporous structures are beneficial to formation of the active sites and medium transmission of oxygen reduction reaction, forward proceeding of the oxygen reduction reaction is promoted, P doping is achieved, electron supply capacity of the carbon material is enhanced, electrocatalytic activity of the porous carbon material is improved, N doping can enhance C atoms in the carbon material to oxygen reduction products O2And reaction intermediate H2O2Thereby promoting the progress of the oxygen reduction reaction.
According to the Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst and the preparation method thereof, a Co-based MOFs material is used as a precursor, a core-shell nano structure which forms a porous carbon material coated cobalt compound through calcination has a richer morphology structure, so that the catalyst has better mass transfer performance, and the cobalt compound formed after the Co-based MOFs with the nano structure is calcined is uniformly loaded into a pore channel of the porous carbon material, so that the graphitization degree of the carbon material is improved by the cobalt compound, the conductivity of the carbon material is greatly increased, the diffusion and migration rates of electrons between an electrode material and electrolyte in the oxygen reduction reaction are increased, the forward progress of the oxygen reduction reaction is promoted, meanwhile, the electron cloud density of the catalyst is improved by the cobalt compound, the electrochemical stability of the catalyst is enhanced, and the activity of the oxygen reduction reaction is improved.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst and a preparation method thereof comprise the following formula raw materials in parts by weight: 6-21 parts of Fe-based MOFs, 20-22 parts of hydroxyethylidene diphosphonic acid, 22-25 parts of chitosan, 14-16 parts of glycine, 1-3 parts of esterification catalyst, 12-15 parts of composite alkali catalyst and 10-13 parts of condensing agent.
The esterification catalyst is p-toluenesulfonic acid, the composite base catalyst is 4-dimethylaminopyridine and potassium carbonate, the molar ratio of the two substances is 1:1.2-1.8, and the condensing agent is 1-hydroxy-7-azobenzotriazole.
Preferably, the preparation method of the Fe-based MOFs comprises the following steps:
(1) adding Co (NO) into a mixed solvent of distilled water and absolute ethyl alcohol with the volume ratio of 1:2-43)2·6H2O and an organic ligand 2,4, 6-tris [ (p-carboxyphenyl) amino group]1,3, 5-triazine, the molar ratio of the two substances is 1:1.5-2.5, placing the solution in an ultrasonic treatment instrument for ultrasonic dispersion treatment for 1-2h, transferring the solution into a reaction kettle, heating to 240 ℃, reacting for 4-6h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with a proper amount of absolute ethyl alcohol and distilled water in sequence, and fully drying to prepare the Fe-based MOFs.
The preparation method of the Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst comprises the following steps:
(1) adding a sulfuric acid solution into an ethylene glycol solvent to adjust the pH value of the solution to 3-4, sequentially adding 22-25 parts of chitosan, 14-16 parts of glycine and 1-3 parts of esterification catalyst p-toluenesulfonic acid, transferring the solution into a reaction kettle, heating to 140-.
(2) Adding 6-21 parts of Fe-based MOFs and the phosphate-amidated chitosan prepared in the step (1) into absolute ethyl alcohol, placing the solution into an ultrasonic treatment instrument, heating to 40-50 ℃, wherein the ultrasonic frequency is 20-28KHz, performing ultrasonic dispersion treatment for 2-3h, filtering the solution to remove the solvent, and fully drying to obtain the phosphate-amidated chitosan-coated Fe-based MOFs.
(3) Putting the phosphate-amidated chitosan coated Fe-based MOFs prepared in the step (2) into a crucible, adding a proper amount of ammonia water, putting the crucible into an atmosphere resistance furnace, and introducing high-purity N2The temperature rise rate is 5-10 ℃, the calcination is carried out for 6-8h at 950-980 ℃, and the annealing is carried out for 2-3h at 950-980 ℃ to prepare the Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst.
Example 1:
(1) preparing Fe-based MOFs component 1: preparation of Co (NO) added to a mixed solvent of distilled water and anhydrous ethanol at a volume ratio of 1:23)2·6H2O and an organic ligand 2,4, 6-tris [ (p-carboxyphenyl) amino group]The method comprises the following steps of (1) -1,3, 5-triazine, placing the solution into an ultrasonic treatment instrument for ultrasonic dispersion treatment for 1h, transferring the solution into a reaction kettle, heating to 220 ℃, reacting for 4h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with appropriate amount of absolute ethyl alcohol and distilled water in sequence, and fully drying to obtain the Fe-based MOFs component 1.
(2) Preparation of phosphate-amidated chitosan component 1: adding a sulfuric acid solution into an ethylene glycol solvent to adjust the pH value of the solution to 3, sequentially adding 22 parts of chitosan, 14 parts of glycine and 1 part of esterification catalyst p-toluenesulfonic acid, transferring the solution into a reaction kettle, heating to 140 ℃, reacting for 10 hours, cooling the reaction kettle to room temperature, adding a proper amount of sodium hydroxide, adjusting the pH value of the solution to 7, sequentially adding 20 parts of hydroxy ethylidene diphosphonic acid, 12 parts of composite alkali catalyst and 10 parts of condensing agent, heating the reaction kettle to 120 ℃, reacting for 25 hours, cooling the reaction kettle to room temperature, removing the solvent from the solution through a high-speed centrifuge, sequentially washing a solid product with a proper amount of anhydrous ethanol and distilled water, and fully drying to obtain the phosphate ester-amidated chitosan component 1.
(3) Preparing a phosphate-amidated chitosan-coated Fe-based MOFs component 1: adding 21 parts of Fe-based MOFs component 1 and the phosphate-amidated chitosan component 1 prepared in the step (2) into absolute ethyl alcohol, placing the solution into an ultrasonic treatment instrument, heating to 40 ℃, wherein the ultrasonic frequency is 20KHz, performing ultrasonic dispersion treatment for 3 hours, filtering the solution to remove the solvent, and fully drying to obtain the phosphate-amidated chitosan coated Fe-based MOFs component 1.
(4) Preparing an oxygen reduction catalyst 1 of Co-based MOFs-heteroatom doped porous carbon: putting the phosphate-amidated chitosan coated Fe-based MOFs component 1 prepared in the step (3) into a crucible, adding a proper amount of ammonia water, placing the crucible into an atmosphere resistance furnace, and introducing high-purity N2And the temperature rise rate is 5 ℃, the calcination is carried out for 6h at 950 ℃, and the annealing is carried out for 2h at 950 ℃, so as to prepare the Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst 1.
Example 2:
(1) preparation of Fe-based MOFs component 2: preparation of Co (NO) added to a mixed solvent of distilled water and anhydrous ethanol at a volume ratio of 1:43)2·6H2O and an organic ligand 2,4, 6-tris [ (p-carboxyphenyl) amino group]Putting the solution into an ultrasonic treatment instrument for ultrasonic dispersion treatment for 2 hours, transferring the solution into a reaction kettle, heating to 220 ℃, reacting for 6 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with appropriate amount of absolute ethyl alcohol and distilled water in sequence, and fully drying to prepare the Fe-basedMOFs component 2.
(2) Preparation of phosphate-amidated chitosan component 2: adding a sulfuric acid solution into an ethylene glycol solvent to adjust the pH value of the solution to 4, sequentially adding 23 parts of chitosan, 14.5 parts of glycine and 1.5 parts of esterification catalyst p-toluenesulfonic acid, transferring the solution into a reaction kettle, heating to 150 ℃, reacting for 10 hours, cooling the reaction kettle to room temperature, adding a proper amount of sodium hydroxide to adjust the pH value of the solution to 7, sequentially adding 20.5 parts of hydroxy ethylidene diphosphonic acid, 12.5 parts of a composite alkali catalyst and 11 parts of a condensing agent, heating the reaction kettle to 140 ℃, reacting for 30 hours, cooling the reaction kettle to room temperature, removing the solvent from the solution through a high-speed centrifuge, sequentially washing a solid product with a proper amount of anhydrous ethanol and distilled water, and fully drying to obtain the phosphate amidated chitosan component 2.
(3) Preparing a phosphate-amidated chitosan-coated Fe-based MOFs component 2: adding 17 parts of Fe-based MOFs component 2 and the phosphate-amidated chitosan component 2 prepared in the step (2) into absolute ethyl alcohol, placing the solution into an ultrasonic treatment instrument, heating to 50 ℃, wherein the ultrasonic frequency is 28KHz, performing ultrasonic dispersion treatment for 2 hours, filtering the solution to remove the solvent, and fully drying to obtain the phosphate-amidated chitosan coated Fe-based MOFs component 2.
(4) Preparing an oxygen reduction catalyst 2 of Co-based MOFs-heteroatom doped porous carbon: putting the phosphate-amidated chitosan coated Fe-based MOFs component 2 prepared in the step (3) into a crucible, adding a proper amount of ammonia water, placing the crucible into an atmosphere resistance furnace, and introducing high-purity N2And the temperature rise rate is 10 ℃, the calcination is carried out for 8h at 950 ℃, and the annealing is carried out for 2h at 950 ℃, so as to prepare the Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst 2.
Example 3:
(1) preparing Fe-based MOFs component 3: preparation of Co (NO) added to a mixed solvent of distilled water and anhydrous ethanol at a volume ratio of 1:23)2·6H2O and an organic ligand 2,4, 6-tris [ (p-carboxyphenyl) amino group]Putting the solution into an ultrasonic treatment instrument for ultrasonic dispersion treatment for 2 hours, transferring the solution into a reaction kettle, heating to 230 ℃, reacting for 5 hours, cooling the solution to room temperature, filteringAnd removing the solvent, washing the solid product by using a proper amount of absolute ethyl alcohol and distilled water in sequence, and fully drying to prepare the Fe-based MOFs component 3.
(2) Preparation of phosphate-amidated chitosan component 3: adding a sulfuric acid solution into an ethylene glycol solvent to adjust the pH value of the solution to 4, sequentially adding 23.5 parts of chitosan, 15 parts of glycine and 2 parts of esterification catalyst p-toluenesulfonic acid, transferring the solution into a reaction kettle, heating to 145 ℃, reacting for 13h, cooling the reaction kettle to room temperature, adding a proper amount of sodium hydroxide to adjust the pH value of the solution to 7, sequentially adding 21 parts of hydroxyethylidene diphosphonic acid, 13.5 parts of a composite alkali catalyst and 11 parts of a condensing agent, heating the reaction kettle to 130 ℃, reacting for 28h, cooling the reaction kettle to room temperature, removing the solvent from the solution through a high-speed centrifuge, sequentially washing a solid product with a proper amount of absolute ethyl alcohol and distilled water, and fully drying to obtain the phosphate ester-amidated chitosan component 3.
(3) Preparing a phosphate-amidated chitosan-coated Fe-based MOFs component 3: adding 14 parts of Fe-based MOFs component 3 and the phosphate-amidated chitosan component 3 prepared in the step (2) into absolute ethyl alcohol, placing the solution into an ultrasonic treatment instrument, heating to 45 ℃, wherein the ultrasonic frequency is 25KHz, performing ultrasonic dispersion treatment for 3 hours, filtering the solution to remove the solvent, and fully drying to obtain the phosphate-amidated chitosan coated Fe-based MOFs component 3.
(4) Preparing a Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst 3: putting the phosphate-amidated chitosan coated Fe-based MOFs component 3 prepared in the step (3) into a crucible, adding a proper amount of ammonia water, placing the crucible into an atmosphere resistance furnace, and introducing high-purity N2And the temperature rise rate is 10 ℃, the calcination is carried out for 8h at 980 ℃, and the annealing is carried out for 3h at 970 ℃, so as to prepare the Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst 3.
Example 4:
(1) preparing Fe-based MOFs component 4: preparation of Co (NO) added to a mixed solvent of distilled water and anhydrous ethanol at a volume ratio of 1:43)2·6H2O and an organic ligand 2,4, 6-tris [ (p-carboxyphenyl) amino group]1,3, 5-triazine with the molar ratio of the two substances being 1:1.5, placing the solution in an ultrasonic processor for ultrasonic treatmentAnd (3) performing sound dispersion treatment for 2h, transferring the solution into a reaction kettle, heating to 220 ℃, reacting for 6h, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with a proper amount of absolute ethyl alcohol and distilled water in sequence, and fully drying to obtain the Fe-based MOFs component 4.
(2) Preparation of phosphate-amidated chitosan component 4: adding a sulfuric acid solution into an ethylene glycol solvent to adjust the pH value of the solution to 3, sequentially adding 24 parts of chitosan, 15.5 parts of glycine and 2.5 parts of esterification catalyst p-toluenesulfonic acid, transferring the solution into a reaction kettle, heating to 150 ℃, reacting for 15h, cooling the reaction kettle to room temperature, adding a proper amount of sodium hydroxide to adjust the pH value of the solution to 7, sequentially adding 21.5 parts of hydroxy ethylidene diphosphonic acid, 14 parts of a composite base catalyst and 12.5 parts of a condensing agent, heating the reaction kettle to 120 ℃, reacting for 30h, cooling the reaction kettle to room temperature, removing the solvent from the solution through a high-speed centrifuge, sequentially washing a solid product with a proper amount of anhydrous ethanol and distilled water, and fully drying to obtain the phosphate amidated chitosan component 4.
(3) Preparing a phosphate-amidated chitosan-coated Fe-based MOFs component 4: and (3) adding 10 parts of Fe-based MOFs component 4 and the phosphate-amidated chitosan component 4 prepared in the step (2) into absolute ethyl alcohol, placing the solution into an ultrasonic treatment instrument, heating to 50 ℃, wherein the ultrasonic frequency is 28KHz, performing ultrasonic dispersion treatment for 2 hours, filtering the solution to remove the solvent, and fully drying to obtain the phosphate-amidated chitosan coated Fe-based MOFs component 4.
(4) Preparing a Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst 4: putting the phosphate-amidated chitosan coated Fe-based MOFs component 4 prepared in the step (3) into a crucible, adding a proper amount of ammonia water, placing the crucible into an atmosphere resistance furnace, and introducing high-purity N2And the temperature rise rate is 10 ℃, the calcination is carried out for 7h at the temperature of 980 ℃, the annealing is carried out for 3h at the temperature of 980 ℃, and the Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst 4 is prepared.
Example 5:
(1) preparing Fe-based MOFs component 5: preparation of Co (NO) added to a mixed solvent of distilled water and anhydrous ethanol at a volume ratio of 1:43)2·6H2O and an organic ligand 2, wherein the organic ligand is a ligand,4, 6-tris [ (p-carboxyphenyl) amino group]The preparation method comprises the following steps of (1) -1,3, 5-triazine, placing the solution into an ultrasonic treatment instrument for ultrasonic dispersion treatment for 2 hours with the mass molar ratio of the two substances being 1:2.5, transferring the solution into a reaction kettle, heating to 240 ℃, reacting for 6 hours, cooling the solution to room temperature, filtering to remove the solvent, washing the solid product with appropriate amount of absolute ethyl alcohol and distilled water in sequence, and fully drying to prepare the Fe-based MOFs component 5.
(2) Preparation of phosphate-amidated chitosan component 5: adding a sulfuric acid solution into an ethylene glycol solvent to adjust the pH value of the solution to 3, sequentially adding 25 parts of chitosan, 16 parts of glycine and 3 parts of esterification catalyst p-toluenesulfonic acid, transferring the solution into a reaction kettle, heating to 150 ℃, reacting for 15 hours, cooling the reaction kettle to room temperature, adding a proper amount of sodium hydroxide, adjusting the pH value of the solution to 7, sequentially adding 22 parts of hydroxy ethylidene diphosphonic acid, 15 parts of composite alkali catalyst and 13 parts of condensing agent, heating the reaction kettle to 140 ℃, reacting for 30 hours, cooling the reaction kettle to room temperature, removing the solvent from the solution through a high-speed centrifuge, sequentially washing a solid product with a proper amount of anhydrous ethanol and distilled water, and fully drying to obtain the phosphate ester-amidated chitosan component 5.
(3) Preparing a phosphate-amidated chitosan-coated Fe-based MOFs component 5: adding 6 parts of Fe-based MOFs component 5 and the phosphate-amidated chitosan component 5 prepared in the step (2) into absolute ethyl alcohol, placing the solution into an ultrasonic treatment instrument, heating to 50 ℃, wherein the ultrasonic frequency is 28KHz, performing ultrasonic dispersion treatment for 3 hours, filtering the solution to remove the solvent, and fully drying to obtain the phosphate-amidated chitosan coated Fe-based MOFs component 5.
(4) Preparing a Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst 5: putting the phosphate-amidated chitosan coated Fe-based MOFs component 5 prepared in the step (3) into a crucible, adding a proper amount of ammonia water, placing the crucible into an atmosphere resistance furnace, and introducing high-purity N2And the temperature rise rate is 10 ℃, the calcination is carried out for 8h at the temperature of 980 ℃, and the annealing is carried out for 3h at the temperature of 980 ℃ to prepare the Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst 5.
In summary, the Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst and the preparation method thereof are prepared by calciningThe porous carbon material is prepared from the phosphate-amidated chitosan, rich pore channels are formed in the carbon material by N/P co-doping, and a large number of mesoporous structures are formed on the surface of the carbon material, so that the carbon material forms a large specific surface area, rich active sites are provided, the formation of the active sites and the medium transmission of an oxygen reduction reaction are facilitated by the rich pore channels and the large number of mesoporous structures, the forward proceeding of the oxygen reduction reaction is promoted, the P doping enhances the electron supply capability of the carbon material, the electrocatalytic activity of the porous carbon material is improved, and the N doping can enhance the C atoms in the carbon material to the oxygen reduction product O2And reaction intermediate H2O2Thereby promoting the progress of the oxygen reduction reaction.
By using the Co-based MOFs material as a precursor, the core-shell nano structure which is calcined to form the porous carbon material coated with the cobaltite has a richer morphology structure, so that the catalyst has better mass transfer performance, and the cobaltite formed after the Co-based MOFs with the nano structure is calcined is uniformly loaded into a pore channel of the porous carbon material, so that the graphitization degree of the carbon material is improved by the cobaltite, the conductivity of the carbon material is greatly increased, the diffusion and migration rates of electrons between an electrode material and electrolyte in an oxygen reduction reaction are increased, the forward progress of the oxygen reduction reaction is promoted, meanwhile, the electron cloud density of the catalyst is improved by the cobaltite, the electrochemical stability of the catalyst is enhanced, and the activity of the oxygen reduction reaction is improved.
Claims (7)
1. The Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst comprises the following formula raw materials in parts by weight, and is characterized in that: 6-21 parts of Fe-based MOFs, 20-22 parts of hydroxyethylidene diphosphonic acid, 22-25 parts of chitosan, 14-16 parts of glycine, 1-3 parts of esterification catalyst, 12-15 parts of composite alkali catalyst and 10-13 parts of condensing agent.
2. The Co-based MOFs-heteroatom-doped porous carbon oxygen reduction catalyst and the preparation method thereof according to claim 1, wherein: the esterification catalyst is p-toluenesulfonic acid.
3. The Co-based MOFs-heteroatom-doped porous carbon oxygen reduction catalyst and the preparation method thereof according to claim 1, wherein: the composite base catalyst is 4-dimethylamino pyridine and potassium carbonate, and the weight molar ratio of the two substances is 1: 1.2-1.8.
4. The Co-based MOFs-heteroatom-doped porous carbon oxygen reduction catalyst and the preparation method thereof according to claim 1, wherein: the condensing agent is 1-hydroxy-7-azobenzotriazole.
5. The Co-based MOFs-heteroatom-doped porous carbon oxygen reduction catalyst and the preparation method thereof according to claim 1, wherein: the preparation method of the Fe-based MOFs comprises the following steps:
(1) adding Co (NO) into a mixed solvent of distilled water and absolute ethyl alcohol with the volume ratio of 1:2-43)2·6H2O and an organic ligand 2,4, 6-tris [ (p-carboxyphenyl) amino group]1,3, 5-triazine, and placing the solution in an ultrasonic processor for ultrasonic dispersion treatment for 1-2 h.
(2) Transferring the solution into a reaction kettle, heating to 240 ℃ for reaction for 4-6h, cooling, filtering, washing and drying the solution to prepare the Fe-based MOFs.
6. The Co-based MOFs-heteroatom-doped porous carbon oxygen reduction catalyst and the preparation method thereof according to claim 5, wherein: the Co (NO)3)2·6H2O and an organic ligand 2,4, 6-tris [ (p-carboxyphenyl) amino group]The molar ratio of the substances of-1, 3, 5-triazine is 1: 1.5-2.5.
7. The Co-based MOFs-heteroatom-doped porous carbon oxygen reduction catalyst and the preparation method thereof according to claim 1, wherein: the preparation method of the Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst comprises the following steps:
(1) adding a sulfuric acid solution into an ethylene glycol solvent to adjust the pH value of the solution to 3-4, sequentially adding 22-25 parts of chitosan, 14-16 parts of glycine and 1-3 parts of esterification catalyst p-toluenesulfonic acid, transferring the solution into a reaction kettle, heating to 140 ℃ and 150 ℃, and reacting for 10-15 h.
(2) Cooling the reaction kettle to room temperature, adding a proper amount of sodium hydroxide, adjusting the pH value of the solution to 7, sequentially adding 20-22 parts of hydroxyethylidene diphosphonic acid, 12-15 parts of composite base catalyst and 10-13 parts of condensing agent, heating the reaction kettle to 140 ℃, and reacting for 25-30 h.
(3) And cooling the reaction kettle to room temperature, removing the solvent from the solution through a high-speed centrifuge, and washing and drying the solid product to obtain the phosphate-amidated chitosan.
(4) Adding 6-21 parts of Fe-based MOFs and the phosphate-amidated chitosan prepared in the step (1) into absolute ethyl alcohol, placing the solution into an ultrasonic treatment instrument, heating to 40-50 ℃, wherein the ultrasonic frequency is 20-28KHz, performing ultrasonic dispersion treatment for 2-3h, filtering, washing and drying the solution to obtain the phosphate-amidated chitosan-coated Fe-based MOFs.
(5) Putting the phosphate-amidated chitosan coated Fe-based MOFs prepared in the step (4) into a crucible, adding a proper amount of ammonia water, placing the crucible into an atmosphere resistance furnace, and introducing high-purity N2The temperature rise rate is 5-10 ℃, the calcination is carried out for 6-8h at 950-980 ℃, and the annealing is carried out for 2-3h at 950-980 ℃ to prepare the Co-based MOFs-heteroatom doped porous carbon oxygen reduction catalyst.
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| CN114054089A (en) * | 2020-08-05 | 2022-02-18 | 苏州倍友环保科技有限公司 | Hydrogenation and dehydrogenation catalyst, and preparation method and application thereof |
| CN114335566A (en) * | 2021-12-15 | 2022-04-12 | 河南工业大学 | Ni/Co-N doped porous carbon-oxygen reduction catalyst and preparation method thereof |
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| CN114054089A (en) * | 2020-08-05 | 2022-02-18 | 苏州倍友环保科技有限公司 | Hydrogenation and dehydrogenation catalyst, and preparation method and application thereof |
| CN114054089B (en) * | 2020-08-05 | 2023-12-19 | 苏州倍友环保科技有限公司 | Hydrogenation and dehydrogenation catalyst and preparation method and application thereof |
| CN114335566A (en) * | 2021-12-15 | 2022-04-12 | 河南工业大学 | Ni/Co-N doped porous carbon-oxygen reduction catalyst and preparation method thereof |
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