CN114059085A - Nitrogen-sulfur-containing ordered mesoporous carbon-coated nano Co3O4In the presence of a catalyst for oxygen evolution - Google Patents
Nitrogen-sulfur-containing ordered mesoporous carbon-coated nano Co3O4In the presence of a catalyst for oxygen evolution Download PDFInfo
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- CN114059085A CN114059085A CN202111561342.7A CN202111561342A CN114059085A CN 114059085 A CN114059085 A CN 114059085A CN 202111561342 A CN202111561342 A CN 202111561342A CN 114059085 A CN114059085 A CN 114059085A
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- nitrogen
- thiophene
- mesoporous carbon
- oxygen evolution
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 39
- 239000001301 oxygen Substances 0.000 title claims abstract description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 31
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 title claims description 17
- 229910021281 Co3O4In Inorganic materials 0.000 title description 2
- 239000013315 hypercross-linked polymer Substances 0.000 claims abstract description 28
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 24
- RABBMOYULJIAFU-UHFFFAOYSA-N 1h-pyrrole;thiophene Chemical compound C=1C=CNC=1.C=1C=CSC=1 RABBMOYULJIAFU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 53
- 238000010438 heat treatment Methods 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 36
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 28
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 24
- 239000012298 atmosphere Substances 0.000 claims description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- -1 carboxyl thiophene pyrrole Chemical compound 0.000 claims description 20
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- WFAUTYMJPKHYQF-UHFFFAOYSA-N 2-(4-thiophen-2-ylphenyl)thiophene Chemical compound C1=CSC(C=2C=CC(=CC=2)C=2SC=CC=2)=C1 WFAUTYMJPKHYQF-UHFFFAOYSA-N 0.000 claims description 12
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 12
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001994 activation Methods 0.000 claims description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 11
- 238000003763 carbonization Methods 0.000 claims description 11
- 238000001308 synthesis method Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 8
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 239000011159 matrix material Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- ZQRGREQWCRSUCI-UHFFFAOYSA-N [S].C=1C=CSC=1 Chemical group [S].C=1C=CSC=1 ZQRGREQWCRSUCI-UHFFFAOYSA-N 0.000 abstract 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical group N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 abstract 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical group N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 abstract 1
- 125000000524 functional group Chemical group 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000004440 column chromatography Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000003480 eluent Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000000446 fuel Substances 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- GDSOQCSYONDNAJ-UHFFFAOYSA-N 2-thiophen-2-ylbenzoic acid Chemical class OC(=O)C1=CC=CC=C1C1=CC=CS1 GDSOQCSYONDNAJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005863 Friedel-Crafts acylation reaction Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
- C25B11/093—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to the technical field of electrochemical energy, and discloses nitrogen and sulfur containing ordered mesoporous carbon coated nano Co3O4The oxygen evolution catalyst has large specific surface area of carboxyl-containing thiophene pyrrole hypercrosslinked polymer, and has a certain micropore structure, and the main chain contains rich aromatic carboxyl which can be reacted with Co2+Strong metal coordination occurs, thereby enabling Co2+Uniformly loaded into the matrix of the hypercrosslinked polymer to generate nano Co3O4Uniformly growing in the matrix of the ordered mesoporous carbon, wherein functional groups such as pyridine nitrogen, pyrrole nitrogen, thiophene sulfur and the like contained in the ordered mesoporous carbon enable the mesoporous carbon to have higher electrochemical performance, excellent conductivity, more active catalytic sites, large specific surface area and excellent wettability with electrolyte, so that the ordered mesoporous carbon containing nitrogen and sulfur coats the nano Co3O4The oxygen evolution catalyst shows in catalyzing the oxygen evolution reactionBetter overpotential.
Description
Technical Field
The invention relates to the technical field of electrochemical energy, in particular to nitrogen and sulfur containing ordered mesoporous carbon coated nano Co3O4The oxygen evolution catalyst of (1).
Background
In the electrochemical reaction process of the fuel cell, the anodic Oxygen Evolution Reaction (OER) is slow in reaction kinetics due to high overpotential, so that the electrochemical energy storage and conversion process of the fuel cell is limited, a novel high-efficiency non-noble metal oxygen evolution reaction catalyst is developed, the progress of the fuel cell oxygen evolution reaction is promoted to have important significance, wherein transition metal oxides such as cobalt oxide, iron oxide and the like are cheap and easy to obtain, the catalytic activity is high, and the transition metal oxides have wide application prospects in the oxygen evolution reaction catalyst, for example, patent CN108855181B discloses that BCNO nanosheet loaded Co is disclosed3O4The composite catalyst can be used as an oxygen evolution reaction electrocatalyst in the fields of zinc-air batteries, clean energy and the like, and is nano Co3O4Has a large specific surface area and excellent catalytic activity, but Co3O4The nano Co catalyst has low electronic conductivity, is easy to agglomerate in electrolyte, reduces the catalytic efficiency of oxygen evolution reaction, and blocks the nano Co3O4The invention aims to apply the nano Co in oxygen evolution reaction3O4Loaded into the nitrogen-sulfur-containing ordered mesoporous carbon to obtain the oxygen evolution reaction catalyst with high catalytic performance and high efficiency.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a nitrogen-sulfur-containing ordered mesoporous carbon-coated nano Co3O4The oxygen evolution catalyst of (1) is applied to an oxygen evolution reaction of a fuel cell.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: nitrogen-sulfur-containing ordered mesoporous carbon-coated nano Co3O4The synthesis method of the oxygen evolution catalyst comprises the following steps:
(1) adding carboxyl thiophene pyrrole containing hypercrosslinked polymer into N, N-dimethylformamide, adding aqueous solution of cobalt salt, and performing ultrasonic treatment at 30-50 deg.CDispersing for 30-60min, heating to 50-75 ℃, stirring for 12-36h, then vacuum drying to remove the solvent, placing the mixed product in an atmosphere furnace, heating for pre-oxidation, then heating for carbonization, uniformly mixing the carbonized product with potassium hydroxide, placing in the atmosphere furnace for heating and activation, washing the product to be neutral by deionized water, and obtaining the nitrogen-sulfur-containing ordered mesoporous carbon-coated nano Co3O4The oxygen evolution catalyst of (1).
Preferably, the dosage of the cobalt salt is 15-40% of the carboxyl-containing thiophene pyrrole hypercrosslinked polymer.
Preferably, the pre-oxidation process is carried out in an air atmosphere, and the temperature is increased to 300-350 ℃ for treatment for 1-2 h; in the carbonization process, the temperature is raised to 700-850 ℃ for treatment for 2-3h in the nitrogen atmosphere; the activation process is carried out for 1-2h at the temperature of 700-800 ℃.
Preferably, the synthesis method of the carboxyl-containing thiophene pyrrole hypercrosslinked polymer comprises the following steps:
(1) dissolving phthalic anhydride and 2- (4- (thiophene-2-yl) phenyl) thiophene in dichloromethane, adding a catalyst of aluminum trichloride in a nitrogen atmosphere, heating and refluxing for reaction, concentrating under reduced pressure after the reaction, and performing column chromatography separation by using an eluant of petroleum ether and ethyl acetate which are 3-10:1 to obtain the p-phenylene bis (carboxyl benzene) thiophene compound.
(2) Dissolving a p-phenylene bis (carboxyl benzene) thiophene compound and pyrrole into 1, 2-dichloromethane, adding dimethoxymethane and ferric trichloride in nitrogen atmosphere, uniformly stirring, heating to 70-85 ℃, reacting for 15-30h, cooling after reaction, distilling under reduced pressure, and extracting by sequentially using methanol, tetrahydrofuran and dichloromethane to obtain the carboxyl-containing thiophene pyrrole hypercrosslinked polymer.
Preferably, the molar ratio of the phthalic anhydride, the 2- (4- (thiophene-2-yl) phenyl) thiophene and the aluminum trichloride in the step (1) is 2-2.8:1: 2.2-3.6.
Preferably, the reflux reaction in the step (1) is carried out at 25-50 ℃ for 12-24 h.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the sulfur containing nitrogen hasMesoporous carbon coated nano Co3O4The oxygen evolution catalyst is characterized in that phthalic anhydride and 2- (4- (thiophene-2-yl) phenyl) thiophene are subjected to Friedel-crafts acylation reaction to obtain a p-phenylene bis (carboxyl benzene) thiophene compound, then the p-phenylene bis (carboxyl benzene) thiophene compound and pyrrole monomers are subjected to hypercrosslinking to obtain a carboxyl-containing thiophene pyrrole hypercrosslinked polymer, the obtained hypercrosslinked polymer has a large specific surface area and a certain microporous structure, and a main chain of the polymer contains rich aromatic carboxyl which can be mixed with Co2+Strong metal coordination occurs, thereby enabling Co2+Uniformly loaded into the matrix of the hypercrosslinked polymer and then, in a pre-oxidation process, Co2+Oxidized to generate nano Co3O4Carbonizing the hypercrosslinked polymer to form nitrogen-sulfur-containing ordered mesoporous carbon in the carbonization and activation processes to generate nano Co3O4Uniformly grows in the matrix of the ordered mesoporous carbon, overcomes the defect of nano Co3O4The mesoporous carbon has higher electrochemical performance, excellent conductivity, more active catalytic sites, large specific surface area and excellent wettability with electrolyte, provides a diffusion path for electrons and reactants, and enables the nitrogen and sulfur containing ordered mesoporous carbon to coat the nano Co3O4The oxygen evolution catalyst has excellent catalytic activity of oxygen evolution reaction in the catalytic oxygen evolution reaction.
Drawings
FIG. 1 is a reaction scheme for the synthesis of terephthal (carboxyphenyl) thiophene compounds;
FIG. 2 is an infrared spectrum of a hypercrosslinked polymer of thiophene pyrrole containing carboxyl group of example 2;
FIG. 3 is the LSV profile of the example and comparative oxygen evolution catalysts in a 0.1mol/L KOH solution.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: nitrogen-sulfur-containing ordered mesoporous carbon-coated nano Co3O4The synthesis method of the oxygen evolution catalyst comprises the following steps:
(1) dissolving phthalic anhydride and 2- (4- (thiophene-2-yl) phenyl) thiophene in dichloromethane, adding a catalyst of aluminum trichloride in a nitrogen atmosphere, heating to 25-50 ℃ for reaction for 12-24h, concentrating under reduced pressure after the reaction, and performing column chromatography separation by using an eluent of petroleum ether and ethyl acetate which are 3-10:1 to obtain the p-phenylene bis (carboxyl benzene) thiophene compound, wherein the molar ratio of the phthalic anhydride to the 2- (4- (thiophene-2-yl) phenyl) thiophene to the aluminum trichloride is 2-2.8:1: 2.2-3.6.
(2) Dissolving a p-phenylene bis (carboxyl benzene) thiophene compound and pyrrole into 1, 2-dichloromethane, adding dimethoxymethane and ferric trichloride in nitrogen atmosphere, uniformly stirring, heating to 70-85 ℃, reacting for 15-30h, cooling after reaction, distilling under reduced pressure, and extracting by sequentially using methanol, tetrahydrofuran and dichloromethane to obtain the carboxyl-containing thiophene pyrrole hypercrosslinked polymer.
(3) Adding the carboxyl-containing thiophene pyrrole hypercrosslinked polymer into N, N-dimethylformamide, adding an aqueous solution of cobalt salt, wherein the dosage of the cobalt salt is 15-40% of that of the carboxyl-containing thiophene pyrrole hypercrosslinked polymer, carrying out ultrasonic dispersion treatment at 30-50 ℃ for 30-60min, then heating to 50-75 ℃, stirring for 12-36h, and then carrying out vacuum drying to remove the solvent.
(4) Placing the mixed product in an atmosphere furnace, heating to 300-350 ℃ in air atmosphere for pre-oxidation treatment for 1-2h, then heating to 700-850 ℃ in nitrogen atmosphere for carbonization treatment for 2-3h, uniformly mixing the carbonized product with potassium hydroxide, placing in the atmosphere furnace, heating to 700-800 ℃ for activation treatment for 1-2h, washing the product to neutrality with deionized water, and obtaining the nitrogen-sulfur-containing ordered mesoporous carbon-coated nano Co with nano carbon3O4The oxygen evolution catalyst of (1).
Oxygen evolution reaction catalytic activity test: coating nitrogen-sulfur-containing ordered mesoporous carbon with nano Co3O4The oxygen evolution catalyst and the Nafion solution are dispersed into the isopropanol solvent by ultrasonic, then the solution is transferred and dropped on the surface of the glassy carbon electrode, and the loading capacity of the catalyst is controlled to be 0.8mg/cm2An LSV scanning test was performed in an electrochemical workstation with a scanning rate of 10mV/s using 0.1mol/L potassium hydroxide solution as the electrolyte, a Pt electrode and Ag/AgCl as the counter and reference electrodes.
Example 1
(1) 0.6g of phthalic anhydride and 0.5g of 2- (4- (thiophen-2-yl) phenyl) thiophene are dissolved in 20mL of dichloromethane, 0.62g of catalyst aluminum trichloride is added in a nitrogen atmosphere, the mixture is heated to 25 ℃ and refluxed for reaction for 12 hours, after the reaction, the mixture is decompressed and concentrated, and column chromatography separation is carried out by using an eluent of petroleum ether and ethyl acetate which are 3:1, so as to prepare the p-phenylene bis (carboxyl benzene) thiophene compound.
(2) Dissolving 1g of p-phenylene bis (carboxyl benzene) thiophene compound and 0.3g of pyrrole into 80mL of 1, 2-dichloromethane, adding 1.2g of dimethoxymethane and 1.1g of ferric trichloride into nitrogen atmosphere, uniformly stirring, heating to 70 ℃, reacting for 15h, cooling after reaction, distilling under reduced pressure, and extracting by sequentially using methanol, tetrahydrofuran and dichloromethane to obtain the carboxyl-containing thiophene pyrrole hypercrosslinked polymer.
(3) Adding 2g of carboxyl-containing thiophene pyrrole hypercrosslinked polymer into 50mL of N, N-dimethylformamide, adding an aqueous solution containing 0.3g of cobalt nitrate, carrying out ultrasonic dispersion treatment at 30 ℃ for 30min, then heating to 50 ℃, stirring for 12h, and then carrying out vacuum drying to remove the solvent.
(4) Placing 2g of the mixed product in an atmosphere furnace, heating to 300 ℃ in the air atmosphere for preoxidation treatment for 1h, then heating to 700 ℃ in the nitrogen atmosphere for carbonization treatment for 2h, uniformly mixing 1g of the carbonized product with 2g of potassium hydroxide, placing in the atmosphere furnace, heating to 700 ℃ for activation treatment for 1h, washing the product with deionized water to be neutral, and obtaining the nitrogen-sulfur-containing ordered mesoporous carbon-coated nano Co3O4The overpotential of the oxygen evolution catalyst of (1) was 420.1mV with a current density of 10 mV/s.
Example 2
(1) 0.65g of phthalic anhydride and 0.5g of 2- (4- (thiophen-2-yl) phenyl) thiophene are dissolved in 20mL of dichloromethane, 0.7g of catalyst aluminum trichloride is added in nitrogen atmosphere, the mixture is heated to 40 ℃ and refluxed for reaction for 18h, after the reaction, the mixture is decompressed and concentrated, and column chromatography separation is carried out by using an eluent of petroleum ether and ethyl acetate which are 5:1, so as to prepare the p-phenylene bis (carboxyl benzene) thiophene compound.
(2) Dissolving 1g of p-phenylene bis (carboxyl benzene) thiophene compound and 0.4g of pyrrole into 100mL of 1, 2-dichloromethane, adding 1.4g of dimethoxymethane and 1.25g of ferric trichloride in nitrogen atmosphere, stirring uniformly, heating to 70 ℃, reacting for 30h, cooling after reaction, distilling under reduced pressure, and extracting by sequentially using methanol, tetrahydrofuran and dichloromethane to obtain the carboxyl-containing thiophene pyrrole hypercrosslinked polymer.
(3) Adding 2g of carboxyl-containing thiophene pyrrole hypercrosslinked polymer into 100mL of N, N-dimethylformamide, adding an aqueous solution containing 0.35g of cobalt nitrate, carrying out ultrasonic dispersion treatment at 40 ℃ for 60min, then heating to 65 ℃, stirring for 36h, and then carrying out vacuum drying to remove the solvent.
(4) Placing 2g of the mixed product in an atmosphere furnace, heating to 350 ℃ in the air atmosphere for preoxidation treatment for 2h, then heating to 750 ℃ in the nitrogen atmosphere for carbonization treatment for 2h, uniformly mixing 1g of the carbonized product with 2.5g of potassium hydroxide, placing in the atmosphere furnace, heating to 800 ℃ for activation treatment for 1h, washing the product to be neutral by deionized water, and obtaining the nitrogen-sulfur-containing ordered mesoporous carbon-coated nano Co3O4The overpotential of the oxygen evolution catalyst of (1) was 384.7mV with a current density of 10 mV/s.
Example 3
(1) 0.72g of phthalic anhydride and 0.5g of 2- (4- (thiophen-2-yl) phenyl) thiophene are dissolved in 30mL of dichloromethane, 0.75g of catalyst aluminum trichloride is added in a nitrogen atmosphere, the mixture is heated to 40 ℃ and refluxed for reaction for 18h, after the reaction, the reaction is decompressed and concentrated, and column chromatography separation is carried out by using an eluent of petroleum ether and ethyl acetate which are 15:1, so as to prepare the p-phenylene bis (carboxyl benzene) thiophene compound.
(2) Dissolving 1g of p-phenylene bis (carboxyl benzene) thiophene compound and 0.48g of pyrrole into 120mL of 1, 2-dichloromethane, adding 1.6g of dimethoxymethane and 1.5g of ferric trichloride into nitrogen atmosphere, uniformly stirring, heating to 75 ℃, reacting for 24h, cooling after the reaction, distilling under reduced pressure, and extracting by sequentially using methanol, tetrahydrofuran and dichloromethane to obtain the carboxyl-containing thiophene pyrrole hypercrosslinked polymer.
(3) Adding 2g of carboxyl-containing thiophene pyrrole hypercrosslinked polymer into 120mL of N, N-dimethylformamide, adding an aqueous solution containing 0.45g of cobalt chloride, carrying out ultrasonic dispersion treatment at 40 ℃ for 40min, then heating to 70 ℃, stirring for 20h, and then carrying out vacuum drying to remove the solvent.
(4) Placing 2g of the mixed product in an atmosphere furnace, heating to 320 ℃ in the air atmosphere for preoxidation treatment for 1h, then heating to 800 ℃ in the nitrogen atmosphere for carbonization treatment for 3h, uniformly mixing 1g of the carbonized product with 2.5g of potassium hydroxide, placing in the atmosphere furnace, heating to 750 ℃ for activation treatment for 2h, washing the product to be neutral by deionized water, and obtaining the nitrogen-sulfur-containing ordered mesoporous carbon-coated nano Co3O4The overpotential of the oxygen evolution catalyst was 351.2mV with a current density of 10 mV/s.
Example 4
(1) 0.85g of phthalic anhydride and 0.5g of 2- (4- (thiophene-2-yl) phenyl) thiophene are dissolved in 40mL of dichloromethane, 1g of catalyst aluminum trichloride is added in nitrogen atmosphere, the mixture is heated to 60 ℃ for reflux reaction for 24 hours, after the reaction, the mixture is decompressed and concentrated, and column chromatography separation is carried out by using an eluent of petroleum ether and ethyl acetate which are 10:1, so as to prepare the p-phenylene bis (carboxyl benzene) thiophene compound.
(2) Dissolving 1g of p-phenylene bis (carboxyl benzene) thiophene compound and 0.6g of pyrrole into 150mL of 1, 2-dichloromethane, adding 2g of dimethoxymethane and 1.8g of ferric trichloride in nitrogen atmosphere, uniformly stirring, heating to 85 ℃, reacting for 30h, cooling after reacting, distilling under reduced pressure, and extracting by sequentially using methanol, tetrahydrofuran and dichloromethane to obtain the carboxyl-containing thiophene pyrrole hypercrosslinked polymer.
(3) Adding 2g of carboxyl-containing thiophene pyrrole hypercrosslinked polymer into 200mL of N, N-dimethylformamide, adding an aqueous solution containing 0.6g of cobalt sulfate, carrying out ultrasonic dispersion treatment at 50 ℃ for 60min, then heating to 75 ℃, stirring for 36h, and then carrying out vacuum drying to remove the solvent.
(4) Placing 2g of the mixed product in an atmosphere furnace, heating to 350 ℃ in the air atmosphere for preoxidation treatment for 2h, then heating to 850 ℃ in the nitrogen atmosphere for carbonization treatment for 3h, uniformly mixing 1g of the carbonized product with 3g of potassium hydroxide, placing in the atmosphere furnace, heating to 800 ℃ for activation treatment for 2h, washing the product with deionized water to be neutral, and obtaining the nitrogen-sulfur-containing ordered mesoporous carbon-coated nano Co3O4The overpotential of the oxygen evolution catalyst of (1) was 464 at a current density of 10 mV/s.0mV。
Comparative example 1
(1) 0.6g of phthalic anhydride and 0.5g of 2- (4- (thiophen-2-yl) phenyl) thiophene are dissolved in 20mL of dichloromethane, 0.8g of catalyst aluminum trichloride is added in nitrogen atmosphere, the mixture is heated to 25 ℃ and refluxed for reaction for 24 hours, after the reaction, the mixture is decompressed and concentrated, and column chromatography separation is carried out by using an eluent of petroleum ether and ethyl acetate which are 5:1, thus obtaining the p-phenylene bis (carboxyl benzene) thiophene compound.
(2) Dissolving 1g of p-phenylene bis (carboxyl benzene) thiophene compound and 0.4g of pyrrole into 120mL of 1, 2-dichloromethane, adding 1.3g of dimethoxymethane and 1.1g of ferric trichloride into nitrogen atmosphere, uniformly stirring, heating to 85 ℃, reacting for 15h, cooling after reaction, distilling under reduced pressure, and extracting by sequentially using methanol, tetrahydrofuran and dichloromethane to obtain the carboxyl-containing thiophene pyrrole hypercrosslinked polymer.
(3) Placing 2g of carboxyl-containing thiophene pyrrole hypercrosslinked polymer in an atmosphere furnace, heating to 700 ℃ in nitrogen atmosphere for carbonization treatment for 3h, taking 1g of carbonized product to be uniformly mixed with 3g of potassium hydroxide, placing in the atmosphere furnace, heating to 750 ℃ for activation treatment for 2h, and washing the product with deionized water to be neutral to prepare the nitrogen-sulfur-containing ordered mesoporous carbon oxygen evolution catalyst, wherein the current density is 10mV/s, and the overpotential is 562.0 mV.
Claims (6)
1. Nitrogen-sulfur-containing ordered mesoporous carbon-coated nano Co3O4The synthesis method of the oxygen evolution catalyst is characterized in that: the synthesis method comprises the following steps:
(1) adding carboxyl thiophene pyrrole hypercrosslinked polymer into N, N-dimethylformamide, adding aqueous solution of cobalt salt, carrying out ultrasonic dispersion treatment for 30-60min at 30-50 ℃, then heating to 50-75 ℃, stirring for 12-36h, placing the mixed product into an atmosphere furnace, heating for pre-oxidation, then heating for carbonization, uniformly mixing the carbonized product with potassium hydroxide, placing the mixture into the atmosphere furnace, heating for activation, and obtaining the nitrogen-sulfur-containing ordered mesoporous carbon-coated nano Co3O4The oxygen evolution catalyst of (1).
2. The method of claim 1Nitrogen-sulfur-containing ordered mesoporous carbon-coated nano Co3O4The synthesis method of the oxygen evolution catalyst is characterized in that: the dosage of the cobalt salt is 15-40% of the carboxyl-containing thiophene pyrrole hypercrosslinked polymer.
3. The nitrogen and sulfur containing ordered mesoporous carbon coated nano Co as claimed in claim 13O4The synthesis method of the oxygen evolution catalyst is characterized in that: the pre-oxidation process is carried out in an air atmosphere, and the temperature is raised to 300-350 ℃ for treatment for 1-2 h; in the carbonization process, the temperature is raised to 700-850 ℃ for treatment for 2-3h in the nitrogen atmosphere; the activation process is carried out for 1-2h at the temperature of 700-800 ℃.
4. The nitrogen and sulfur containing ordered mesoporous carbon coated nano Co as claimed in claim 13O4The synthesis method of the oxygen evolution catalyst is characterized in that: the synthesis method of the carboxyl-containing thiophene pyrrole hypercrosslinked polymer comprises the following steps:
(1) dissolving phthalic anhydride and 2- (4- (thiophene-2-yl) phenyl) thiophene into dichloromethane, adding a catalyst of aluminum trichloride into a nitrogen atmosphere, and carrying out heating reflux reaction to obtain a p-phenylene bis (carboxyl benzene) thiophene compound;
(2) dissolving a p-phenylene bis (carboxyl benzene) thiophene compound and pyrrole into 1, 2-dichloromethane, adding dimethoxymethane and ferric trichloride in a nitrogen atmosphere, uniformly stirring, heating to 70-85 ℃, and reacting for 15-30h to obtain the carboxyl-containing thiophene pyrrole hypercrosslinked polymer.
5. The nitrogen and sulfur containing ordered mesoporous carbon coated nano Co as claimed in claim 43O4The synthesis method of the oxygen evolution catalyst is characterized in that: in the step (1), the molar ratio of phthalic anhydride, 2- (4- (thiophene-2-yl) phenyl) thiophene to aluminum trichloride is 2-2.8:1: 2.2-3.6.
6. The nitrogen and sulfur containing ordered mesoporous carbon coated nano Co as claimed in claim 43O4The synthesis method of the oxygen evolution catalyst is characterized in that: the steps areIn the step (1), the reflux reaction is carried out for 12-24h at 25-50 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107199044A (en) * | 2017-06-13 | 2017-09-26 | 兰州理工大学 | A kind of preparation method of nitrogen-doped carbon supported cobaltosic oxide catalyst |
| CN110010878A (en) * | 2019-04-17 | 2019-07-12 | 安徽大学 | The porous carbon coating Co of N doping3O4Composite nano materials, preparation method and applications |
| CN111525117A (en) * | 2020-05-11 | 2020-08-11 | 喻明兵 | Three-dimensional porous carbon coated Co3O4The negative electrode material of the sodium ion battery and the preparation method thereof |
| CN111697244A (en) * | 2020-06-29 | 2020-09-22 | 周华模 | Nitrogen-rich porous carbon coated nano Co3O4Oxygen reduction catalyst and process for producing the same |
| CN112599744A (en) * | 2020-12-15 | 2021-04-02 | 桐乡市鸿信科技合伙企业(有限合伙) | Nitrogen-sulfur Co-doped porous carbon modified Co3O4Lithium ion battery cathode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107199044A (en) * | 2017-06-13 | 2017-09-26 | 兰州理工大学 | A kind of preparation method of nitrogen-doped carbon supported cobaltosic oxide catalyst |
| CN110010878A (en) * | 2019-04-17 | 2019-07-12 | 安徽大学 | The porous carbon coating Co of N doping3O4Composite nano materials, preparation method and applications |
| CN111525117A (en) * | 2020-05-11 | 2020-08-11 | 喻明兵 | Three-dimensional porous carbon coated Co3O4The negative electrode material of the sodium ion battery and the preparation method thereof |
| CN111697244A (en) * | 2020-06-29 | 2020-09-22 | 周华模 | Nitrogen-rich porous carbon coated nano Co3O4Oxygen reduction catalyst and process for producing the same |
| CN112599744A (en) * | 2020-12-15 | 2021-04-02 | 桐乡市鸿信科技合伙企业(有限合伙) | Nitrogen-sulfur Co-doped porous carbon modified Co3O4Lithium ion battery cathode material and preparation method thereof |
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