CN112864402B - Preparation and application of oxygen reduction catalyst of Fe-N co-doped mesoporous carbon - Google Patents
Preparation and application of oxygen reduction catalyst of Fe-N co-doped mesoporous carbon Download PDFInfo
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 42
- 239000001301 oxygen Substances 0.000 title claims abstract description 42
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 230000009467 reduction Effects 0.000 title claims abstract description 34
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims description 6
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims abstract description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 34
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 29
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000009210 therapy by ultrasound Methods 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 12
- 239000013522 chelant Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 150000002506 iron compounds Chemical class 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- 239000012990 dithiocarbamate Substances 0.000 claims description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 36
- 239000000446 fuel Substances 0.000 abstract description 9
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- 238000000034 method Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000003763 carbonization Methods 0.000 abstract description 4
- 229910002804 graphite Inorganic materials 0.000 abstract description 4
- 239000010439 graphite Substances 0.000 abstract description 4
- 125000004434 sulfur atom Chemical group 0.000 abstract description 4
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical group [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract description 2
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- 239000012153 distilled water Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 230000009920 chelation Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
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- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KJAMZCVTJDTESW-UHFFFAOYSA-N tiracizine Chemical compound C1CC2=CC=CC=C2N(C(=O)CN(C)C)C2=CC(NC(=O)OCC)=CC=C21 KJAMZCVTJDTESW-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8652—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites as mixture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to the technical field of fuel cells and discloses an oxygen reduction catalyst of Fe-N co-doped mesoporous carbon, namely mesoporous carbonThe mesoporous carbon has the advantages of uniform and rich hierarchical mesoporous structure, higher specific surface area and contribution to the transmission of substances in the process of oxygen reduction reaction, N is doped in mesoporous carbon and mainly exists in an active structure of pyridine nitrogen and graphite nitrogen, the graphite nitrogen structure can improve the charge arrangement and the conductivity of a mesoporous carbon matrix, and the pyridine nitrogen structure and Fe nanoparticles form FeN 4 The sulfur atom in the dithiocarbamic acid is doped around FeN4 catalytic neutrality in the high-temperature carbonization process, so that the band gap of mesoporous carbon can be reduced, the conductivity of the mesoporous carbon can be improved, the electron transfer is promoted, the electronegativity of the sulfur atom is low, and the FeN can be adjusted 4 The charge distribution and the electronic structure of the active sites show excellent oxygen reduction catalytic activity.
Description
Technical Field
The invention relates to the technical field of fuel cells, in particular to preparation and application of an oxygen reduction catalyst of Fe-N codoped mesoporous carbon.
Background
The fuel cell is a novel and efficient energy conversion and storage technology, such as a hydrogen fuel cell, a methanol fuel cell, and the like, and has the advantages of high energy density, environmental protection, and the like, and the electrode reaction of the fuel cell mainly comprises anode oxygen evolution and cathode oxygen reduction reactions, but the kinetic reaction of the cathode oxygen reduction reaction is slow, so that the overpotential is very high, and the technical development and the practical application of the fuel cell are severely limited.
The porous carbon material has rich pore channel structures, large specific surface area and excellent electrochemical property, can be used as a catalyst carrier and has wide application in the field of electrocatalysis of lithium ion batteries, super capacitors and the like, wherein the metal-nitrogen-carbon catalyst, such as Fe-N-C catalyst, has unique electronic structure and property and rich site activity FeN 4 And the oxygen reduction catalytic active site of C-N are the most promising oxygen reduction catalyst, so the research and the synthesis of novel Fe-N-C oxygen reduction catalyst with high efficiency, low price and easy obtaining become research hotspots and difficulties.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the preparation and the application of the Fe-N co-doped mesoporous carbon oxygen reduction catalyst, and the Fe-N co-doped mesoporous carbon oxygen reduction catalyst has excellent oxygen reduction catalytic activity.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the Fe-N co-doped mesoporous carbon oxygen reduction catalyst comprises the following steps:
(1) Adding deionized water and beta-cyclodextrin into a beaker, adding potassium hydroxide until the beta-cyclodextrin is dissolved, placing the beaker in a constant-temperature water bath kettle, heating the beaker to 40-70 ℃, adding ethylenediamine, dropwise adding epichlorohydrin, stirring and reacting for 2-4h, cooling, adding dilute hydrochloric acid to adjust the pH value of the solution to be neutral, carrying out reduced pressure distillation, and washing with distilled water and diethyl ether to obtain the aminated beta-cyclodextrin.
(2) Adding an ethylene glycol solvent and aminated beta-cyclodextrin into a beaker, carrying out ultrasonic treatment until the mixture is uniformly dispersed, placing the beaker in a constant-temperature water bath kettle, heating the beaker to 40-60 ℃, adding carbon disulfide, carrying out reflux reaction for 12-24h, cooling, adding deionized water to precipitate, washing with distilled water and ethanol to obtain the dithiocarbamated cyclodextrin.
(3) Adding deionized water, an iron compound and dithiocarbamated cyclodextrin into a beaker, performing ultrasonic treatment until the mixture is uniformly dispersed, stirring for 2 to 4 hours, then standing and adsorbing for 24 to 48 hours, filtering a solvent, and washing with distilled water to obtain Fe 3+ Dithiocarbamated cyclodextrin chelates.
(4) Mixing Fe 3+ Uniformly mixing the dithiocarbamated cyclodextrin chelate and potassium hydroxide, calcining in an atmosphere tube furnace, washing a calcined product to be neutral by deionized water to obtain the Fe-N codoped mesoporous carbon oxygen reduction catalyst, and applying the Fe-N codoped mesoporous carbon oxygen reduction catalyst to the cathode oxygen reduction reaction of a fuel cell.
Preferably, the mass ratio of the beta-cyclodextrin, the ethylenediamine and the epichlorohydrin in the step (1) is 10-150.
Preferably, the mass ratio of the aminated beta-cyclodextrin to the carbon disulfide in the step (2) is 10-100.
Preferably, the iron compound in the step (3) is FeCl 3 、Fe 2 (SO 4 ) 3 、Fe(NO 3 ) 3 In a mass ratio to the dithiocarbamated cyclodextrin of 60 to 120.
Preferably, fe in said step (4) 3+ Mass ratio of dithiocarbamate Cyclodextrin chelate to Potassium hydroxide15-30 parts of a material with the weight ratio of 10.
Preferably, the calcining condition in the step (4) is nitrogen atmosphere, and the calcining time is 2-3h at 700-800 ℃.
(III) advantageous technical effects
Compared with the prior art, the invention has the following chemical mechanism and beneficial technical effects:
according to the Fe-N codoped mesoporous carbon oxygen reduction catalyst, in a potassium hydroxide alkali system, through the crosslinking effect of epoxy chloropropane, ethylenediamine is grafted to beta-cyclodextrin to obtain aminated beta-cyclodextrin, so that a large amount of amino is introduced into a beta-cyclodextrin molecular chain, the amino and carbon disulfide are subjected to xanthation reaction to obtain a large amount of dithiocarbamate groups, and the dithiocarbamate groups are used for Fe 3+ Has strong chelation and coordination, and simultaneously, the unique cavity structure of the beta-cyclodextrin leads a great amount of Fe under the synergistic action 3+ Uniformly adsorbing into a matrix of beta-cyclodextrin to form Fe 3+ Beta-cyclodextrin is easy to dehydrate and carbonize at high temperature and has high carbon forming rate, so that beta-cyclodextrin molecular chains are used as a carbon source, a carbamic acid matrix is used as a nitrogen source, and adsorbed Fe is adsorbed by high-temperature calcination carbonization and potassium hydroxide etching activation 3+ And (3) carrying out thermal reduction to generate Fe nano particles, thereby obtaining the Fe-N co-doped mesoporous carbon oxygen reduction catalyst.
According to the Fe-N codoped mesoporous carbon oxygen reduction catalyst, mesoporous carbon is uniform and rich in hierarchical mesoporous structure, the specific surface area is higher, the transmission of substances in the oxygen reduction reaction process is facilitated, N is doped in the mesoporous carbon and mainly exists in an active structure of pyridine nitrogen and graphite nitrogen, the graphite nitrogen structure can improve the charge arrangement and conductivity of a mesoporous carbon matrix, and the pyridine nitrogen structure and Fe nanoparticles form FeN 4 Since Fe is reduced by chelation and coordination 3+ The Fe nanoparticles are uniformly absorbed into a matrix of beta-cyclodextrin, so that the generated Fe nanoparticles can be highly dispersed in the mesoporous carbon matrix in the carbonization process, the agglomeration of the Fe nanoparticles is avoided, and the Fe nanoparticles can better form rich and uniformly dispersed FeN with pyridine nitrogen 4 The catalytic sites and sulfur atoms in dithiocarbamic acid are doped around FeN4 catalytic neutrality in the high-temperature carbonization process, so that the band gap of mesoporous carbon can be reduced, the conductivity of mesoporous carbon can be improved, the transfer of electrons can be promoted, the electrocatalytic oxygen reduction reaction can be facilitated, the electronegativity of the sulfur atoms is low, and the FeN can be adjusted 4 The charge distribution and the electronic structure of the active sites enable the Fe-N codoped mesoporous carbon oxygen reduction catalyst to have higher initial potential and half-wave potential, reduce the overpotential of oxygen reduction reaction, and show excellent oxygen reduction catalytic activity.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: an oxygen reduction catalyst of Fe-N codoped mesoporous carbon is prepared by the following steps:
(1) Adding deionized water and beta-cyclodextrin into a beaker, adding potassium hydroxide until the beta-cyclodextrin is dissolved, placing the beaker in a constant-temperature water bath kettle, heating the beaker to 40-70 ℃, adding ethylenediamine, dropwise adding epichlorohydrin, controlling the mass ratio of the beta-cyclodextrin to the ethylenediamine to the epichlorohydrin to be within 50-150.
(2) Adding an ethylene glycol solvent and amination beta-cyclodextrin into a beaker, performing ultrasonic treatment until the mixture is uniformly dispersed, placing the beaker in a constant-temperature water bath kettle, heating the beaker to 40-60 ℃, adding carbon disulfide, wherein the mass ratio of the amination beta-cyclodextrin to the carbon disulfide is 10-100, performing reflux reaction for 12-24h, cooling, adding deionized water to precipitate, and washing the precipitate with distilled water and ethanol to obtain dithiocarbamated cyclodextrin.
(3) Adding deionized water, an iron compound and dithiocarbamated cyclodextrin in a mass ratio of 60-120, wherein the iron compound is FeCl 3 、Fe 2 (SO 4 ) 3 、Fe(NO 3 ) 3 Ultrasonic treating any one of the above components until the dispersion is uniform, stirring for 2-4h, standing for adsorption for 24-48h, filtering the solvent, and washing with distilled water to obtain Fe 3+ Dithiocarbamated cyclodextrin chelates.
(4) Mixing Fe with the mass ratio of 10 3+ Uniformly mixing the dithiocarbamated cyclodextrin chelate and potassium hydroxide, placing the mixture in an atmosphere tube furnace, calcining the mixture for 2 to 3 hours at 700 to 800 ℃ in nitrogen atmosphere, washing the calcined product with deionized water to be neutral, and obtaining the Fe-N codoped mesoporous carbon oxygen reduction catalyst which is applied to the cathode oxygen reduction reaction of a fuel cell.
Example 1
(1) Adding deionized water and beta-cyclodextrin into a beaker, adding potassium hydroxide until the beta-cyclodextrin is dissolved, placing the beaker in a constant-temperature water bath kettle, heating the beaker to 40 ℃, adding ethylenediamine, dropwise adding epichlorohydrin, controlling the mass ratio of the beta-cyclodextrin to the ethylenediamine to the epichlorohydrin to be 10.
(2) Adding an ethylene glycol solvent and aminated beta-cyclodextrin into a beaker, carrying out ultrasonic treatment until the mixture is uniformly dispersed, placing the beaker in a constant-temperature water bath, heating to 40 ℃, adding carbon disulfide, wherein the mass ratio of the aminated beta-cyclodextrin to the carbon disulfide is 10, carrying out reflux reaction for 12h, cooling, adding deionized water to precipitate, and washing with distilled water and ethanol to obtain the dithiocarbamated cyclodextrin.
(3) Adding deionized water and FeCl with the mass ratio of 60 3 And dithiocarbamic acid cyclodextrin, performing ultrasonic treatment to disperse uniformly, stirring for 2h, then standing for adsorption for 24h, filtering the solvent, and washing with distilled water to obtain Fe 3+ Dithiocarbamated cyclodextrin chelates.
(4) Mixing Fe with the mass ratio of 10 3+ Uniformly mixing the dithiocarbamated cyclodextrin chelate and potassium hydroxide, placing the mixture in an atmosphere tube furnace, calcining the mixture for 2h of deionized water at 700 ℃ in a nitrogen atmosphere, and washing the calcined product to be neutral to obtain the Fe-N codoped mesoporous carbon oxygen reduction catalyst.
Example 2
(1) Adding deionized water and beta-cyclodextrin into a beaker, adding potassium hydroxide until the beta-cyclodextrin is dissolved, placing the beaker in a constant-temperature water bath kettle, heating the beaker to 70 ℃, adding ethylenediamine, dropwise adding epichlorohydrin, controlling the mass ratio of the beta-cyclodextrin to the ethylenediamine to the epichlorohydrin to be 10.
(2) Adding an ethylene glycol solvent and amination beta-cyclodextrin into a beaker, performing ultrasonic treatment until the mixture is uniformly dispersed, placing the beaker in a constant-temperature water bath kettle, heating the beaker to 50 ℃, adding carbon disulfide, wherein the mass ratio of the amination beta-cyclodextrin to the carbon disulfide is 10.
(3) Adding deionized water and Fe with the mass ratio of 80 2 (SO 4 ) 3 And dithiocarbamated cyclodextrin, performing ultrasonic treatment until the mixture is uniformly dispersed, stirring for 2 hours, standing for adsorption for 48 hours, filtering the solvent, and washing with distilled water to obtain Fe 3+ Dithiocarbamated cyclodextrin chelates.
(4) Mixing Fe with the mass ratio of 10 3+ Uniformly mixing the dithiocarbamated cyclodextrin chelate and potassium hydroxide, placing the mixture in an atmosphere tube furnace, calcining the mixture for 3h at 750 ℃ in a nitrogen atmosphere, washing the calcined product with deionized water to be neutral, and obtaining the Fe-N codoped mesoporous carbon oxygen reduction catalyst.
Example 3
(1) Adding deionized water and beta-cyclodextrin into a beaker, adding potassium hydroxide until the beta-cyclodextrin is dissolved, placing the beaker in a constant-temperature water bath kettle, heating the beaker to 60 ℃, adding ethylenediamine, dropwise adding epichlorohydrin, controlling the mass ratio of the beta-cyclodextrin to the ethylenediamine to the epichlorohydrin to be 10.
(2) Adding an ethylene glycol solvent and amination beta-cyclodextrin into a beaker, performing ultrasonic treatment until the mixture is uniformly dispersed, placing the beaker in a constant-temperature water bath kettle, heating the beaker to 50 ℃, adding carbon disulfide, wherein the mass ratio of the amination beta-cyclodextrin to the carbon disulfide is 10, performing reflux reaction for 18 hours, cooling, adding deionized water to separate out a precipitate, and washing the precipitate with distilled water and ethanol to obtain dithiocarbamated cyclodextrin.
(3) Deionized water, fe (NO 3 ) 3 And dithiocarbamated cyclodextrin, performing ultrasonic treatment until the mixture is uniformly dispersed, stirring for 3 hours, standing for adsorption for 36 hours, filtering the solvent, and washing with distilled water to obtain Fe 3+ Dithiocarbamated cyclodextrin chelates.
(4) Mixing Fe with the mass ratio of 10 3+ Uniformly mixing the dithiocarbamated cyclodextrin chelate and potassium hydroxide, placing the mixture in an atmosphere tube furnace, calcining the mixture for 2.5h at 750 ℃ in a nitrogen atmosphere, washing the calcined product with deionized water to be neutral, and obtaining the Fe-N codoped mesoporous carbon oxygen reduction catalyst.
Example 4
(1) Adding deionized water and beta-cyclodextrin into a beaker, adding potassium hydroxide until the beta-cyclodextrin is dissolved, placing the beaker in a constant-temperature water bath kettle, heating the beaker to 70 ℃, adding ethylenediamine, dropwise adding epichlorohydrin, controlling the mass ratio of the beta-cyclodextrin to the ethylenediamine to the epichlorohydrin to be 10.
(2) Adding an ethylene glycol solvent and aminated beta-cyclodextrin into a beaker, carrying out ultrasonic treatment until the mixture is uniformly dispersed, placing the beaker in a constant-temperature water bath, heating the beaker to 60 ℃, adding carbon disulfide, wherein the mass ratio of the aminated beta-cyclodextrin to the carbon disulfide is 10.
(3) Adding deionized water and FeCl with the mass ratio of 120 3 And dithiocarbamated cyclodextrin, performing ultrasonic treatment until the mixture is uniformly dispersed, stirring for 4 hours, standing for adsorption for 48 hours, filtering the solvent, and washing with distilled water to obtain Fe 3+ Dithiocarbamated cyclodextrin chelates.
(4) Mixing Fe with the mass ratio of 10 3+ Uniformly mixing the dithiocarbamated cyclodextrin chelate and potassium hydroxide, placing the mixture in an atmosphere tube furnace, calcining the mixture for 3h at 800 ℃ in nitrogen atmosphere, washing the calcined product with deionized water to be neutral, and obtaining the Fe-N codoped mesoporous carbon oxygen reduction catalyst.
Comparative example 1
(1) Adding deionized water and beta-cyclodextrin into a beaker, adding potassium hydroxide until the beta-cyclodextrin is dissolved, placing the beaker in a constant-temperature water bath kettle, heating the beaker to 70 ℃, adding ethylenediamine, dropwise adding epichlorohydrin, controlling the mass ratio of the beta-cyclodextrin to the ethylenediamine to the epichlorohydrin to be 10.
(2) Adding an ethylene glycol solvent and amination beta-cyclodextrin into a beaker, performing ultrasonic treatment until the mixture is uniformly dispersed, placing the beaker in a constant-temperature water bath kettle, heating the beaker to 50 ℃, adding carbon disulfide, wherein the mass ratio of the amination beta-cyclodextrin to the carbon disulfide is 10.
(3) Deionized water, fe (NO 3 ) 3 And dithiocarbamated cyclodextrin, performing ultrasonic treatment until the mixture is uniformly dispersed, stirring for 3 hours, standing for adsorption for 36 hours, filtering the solvent, and washing with distilled water to obtain Fe 3+ Dithiocarbamated cyclodextrin chelates.
(4) Mixing Fe with the mass ratio of 10 3+ Uniformly mixing the dithiocarbamated cyclodextrin chelate and potassium hydroxide, placing the mixture in an atmosphere tube furnace, calcining the mixture for 2h at 800 ℃ in a nitrogen atmosphere, washing the calcined product with deionized water to be neutral, and obtaining the Fe-N codoped mesoporous carbon oxygen reduction catalyst.
Mixing an oxygen reduction catalyst of Fe-N codoped mesoporous carbon, nafion solution and isopropanol solvent to form slurry, coating the slurry on the surface of a disc electrode, drying to obtain a working electrode, and testing the catalytic activity of the oxygen reduction catalyst in an Autolab PGSTAT302N electrochemical workstation by using a scanning voltammetry method and a chronoamperometry method by using a Pt electrode as a counter electrode and Ag/AgCl as a reference electrode.
Claims (3)
1. An oxygen reduction catalyst of Fe-N codoped mesoporous carbon is characterized in that: the preparation method of the Fe-N co-doped mesoporous carbon oxygen reduction catalyst comprises the following steps: (1) Adding deionized water and beta-cyclodextrin into a beaker, adding potassium hydroxide until the beta-cyclodextrin is dissolved, placing the beaker in a constant-temperature water bath kettle, heating the beaker to 40-70 ℃, adding ethylenediamine, dropwise adding epoxy chloropropane, and stirring the mixture for reaction for 2-4 hours to obtain aminated beta-cyclodextrin; (2) Adding an ethylene glycol solvent and aminated beta-cyclodextrin into a beaker, carrying out ultrasonic treatment until the mixture is uniformly dispersed, placing the mixture in a constant-temperature water bath, heating the mixture to 40-60 ℃, adding carbon disulfide, and carrying out reflux reaction for 12-24 hours to obtain dithiocarbamated cyclodextrin; (3) Adding deionized water, an iron compound and dithiocarbamated cyclodextrin into a beaker, performing ultrasonic treatment until the mixture is uniformly dispersed, stirring for 2-4h, and then standing and adsorbing for 24-48h to obtain Fe 3+ -a dithiocarbamate cyclodextrin chelate; (4) Mixing Fe 3+ Uniformly mixing the dithiocarbamated cyclodextrin chelate and potassium hydroxide, and calcining in an atmosphere tubular furnace to obtain an oxygen reduction catalyst of Fe-N co-doped mesoporous carbon;
wherein the mass ratio of the beta-cyclodextrin, the ethylenediamine and the epichlorohydrin in the step (1) is 10-150;
wherein the mass ratio of the aminated beta-cyclodextrin to the carbon disulfide in the step (2) is 10-100;
wherein the iron compound in the step (3) is FeCl 3 、Fe 2 (SO 4 ) 3 、Fe(NO 3 ) 3 Is 60 to 120 mass ratio to the dithiocarbamate cyclodextrin.
2. According to the rightThe Fe-N co-doped mesoporous carbon oxygen reduction catalyst of claim 1, which is characterized in that: fe in the step (4) 3+ The mass ratio of the dithiocarbamate cyclodextrin chelate to potassium hydroxide is 10-30.
3. The Fe-N co-doped mesoporous carbon oxygen reduction catalyst according to claim 1, characterized in that: the calcining condition in the step (4) is nitrogen atmosphere, and calcining is carried out for 2-3h at 700-800 ℃.
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