CN106744848A - The preparation of the iron cobalt of multistage pore canal and the three-dimensional grapheme of nitrogen ternary codope - Google Patents
The preparation of the iron cobalt of multistage pore canal and the three-dimensional grapheme of nitrogen ternary codope Download PDFInfo
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- CN106744848A CN106744848A CN201611235510.2A CN201611235510A CN106744848A CN 106744848 A CN106744848 A CN 106744848A CN 201611235510 A CN201611235510 A CN 201611235510A CN 106744848 A CN106744848 A CN 106744848A
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- cobalt
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- nitrogen
- molysite
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 53
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000011148 porous material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 54
- 239000001301 oxygen Substances 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- 229920002480 polybenzimidazole Polymers 0.000 claims abstract description 31
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000000197 pyrolysis Methods 0.000 claims abstract description 23
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 21
- 150000001868 cobalt Chemical class 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 230000000694 effects Effects 0.000 claims abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000446 fuel Substances 0.000 claims abstract description 14
- 238000003780 insertion Methods 0.000 claims abstract description 14
- 230000037431 insertion Effects 0.000 claims abstract description 14
- 230000009467 reduction Effects 0.000 claims abstract description 13
- -1 iron ion Chemical class 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 7
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 7
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 6
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006479 redox reaction Methods 0.000 claims abstract description 6
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 5
- 239000011833 salt mixture Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims 2
- 229910002651 NO3 Inorganic materials 0.000 claims 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 2
- 239000002105 nanoparticle Substances 0.000 claims 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000013339 cereals Nutrition 0.000 claims 1
- 230000005611 electricity Effects 0.000 claims 1
- 229940050410 gluconate Drugs 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims 1
- 239000002798 polar solvent Substances 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 15
- 238000005868 electrolysis reaction Methods 0.000 abstract description 6
- 229920002521 macromolecule Polymers 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 41
- 229910021389 graphene Inorganic materials 0.000 description 30
- 230000003197 catalytic effect Effects 0.000 description 25
- 239000000463 material Substances 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- 230000033116 oxidation-reduction process Effects 0.000 description 12
- 238000006722 reduction reaction Methods 0.000 description 11
- 239000003990 capacitor Substances 0.000 description 9
- 239000003575 carbonaceous material Substances 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052723 transition metal Inorganic materials 0.000 description 8
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 230000027756 respiratory electron transport chain Effects 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 150000003624 transition metals Chemical class 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000001237 Raman spectrum Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920000767 polyaniline Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 150000003233 pyrroles Chemical class 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000003411 electrode reaction Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229920000128 polypyrrole Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 206010011224 Cough Diseases 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- MCONQMQZJCTYCP-UHFFFAOYSA-N [N].[Fe].[Co] Chemical compound [N].[Fe].[Co] MCONQMQZJCTYCP-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000004664 delocalization energy Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- SXGMVGOVILIERA-UHFFFAOYSA-N (2R,3S)-2,3-diaminobutanoic acid Natural products CC(N)C(N)C(O)=O SXGMVGOVILIERA-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- SCNCIXKLOBXDQB-UHFFFAOYSA-K cobalt(3+);2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Co+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O SCNCIXKLOBXDQB-UHFFFAOYSA-K 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical class [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- 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
- Y02E60/13—Energy storage using capacitors
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Abstract
The preparation method of the three-dimensional grapheme of iron cobalt and nitrogen ternary codope multistage pore canal with catalyzing cooperation effect is invented.With the polybenzimidazoles of soluble full armaticity(PBI)PBI is prepared with iron ion and the complex of cobalt ions with molysite and cobalt salt, addition nano-calcium carbonate is template, pyrolysis, the carbon dioxide of Decomposition of Calcium Carbonate generation is discharged and to form aperture and be mutually communicated with the macropore for going to generate after removing template, prepares the three-dimensional grapheme of the multistage pore canal insertion of iron cobalt and nitrogen ternary codope.PBI preferably uses the macromolecule of the full armaticity such as ABPBI, mPBI, and viscosity average molecular weigh is 2 ~ 40,000;Molysite is 1 with the mol ratio of cobalt salt:2~2:1;PBI is 1 with the mass ratio of molysite cobalt salt mixture:2~2:1;The nm of particle diameter 30 ~ 100 of template calcium carbonate;PBI is 2 with template mass ratio:1~1:4;Pyrolysis temperature is 800 DEG C ~ 1100 DEG C.Product can be used for redox reaction catalyst, fuel cell, metal-air battery oxygen reduction catalyst, electrolysis water oxygen and separate out the fields such as catalyst, ultracapacitor.
Description
Technical field
Belong to field of nano material preparation, for the redox reaction catalyst in Chemical Manufacture, clean energy resource field
Fuel cell, the cathod catalyst of metal-air battery, electrolysis water catalyst, lithium ion battery material, super capacitor electrode
The field such as pole material and electrochemical sensor.
Background technology
Graphene is the nano material of the lattice structure of the regular hexagon extension being made up of carbon atom, due to its performance
It is excellent and with various potential applications, however, easily layer-layer is overlapped mutually shape again between macrocosm, two-dimensional graphene
Into graphite-structure, so that its excellent performance is lost.Therefore, the preparation of three-dimensional grapheme and performance study turn into current nanometer
Study hotspot (Biener J, et al. Adv Mater (advanced material), 2012,24 of Material Field: 5083).Research
It was found that, the Graphene of N doping sends out the cloud density in graphene molecules due to the polarity between C-N keys in graphene molecules
Changing, therefore the performance such as nitrogen-doped graphene catalytic oxidation-reduction is better than Graphene.
Contribute to the generation of active sites by doping metals, if during nitrogen-containing group is active with metal-complexing formation M-N-C
The heart, metal further increases its catalytic performance, enhancing catalysis activity and raising stability (Peng H with the synergy of nitrogen
L, et al. Science (science), 2013,3:2045).Research shows that adulterate nitrogen and transition metal in Graphene(Such as iron,
Cobalt etc.)Afterwards, more avtive spots can be formed, so as to product catalytic oxidation-reduction catalysis activity can be improved further.Particularly shape
Into the transition metal and nitrogen co-doped catalyst of three-dimensional structure, its two-dimentional lamellar structure can be preferably kept without being superimposed
And aggregation, its catalytic active site is more, and loose structure is conducive to the transmission of fortification substance.Due to its unique advantage, should
Class material is considered as most one of development potentiality oxygen reduction catalyst, attracts widespread attention (Zitolo A, et
Al. Nature materials (nature material), 2015,14 (9): 937).Transition metal and nitrogen co-doped Graphene tool
There is extensive use, can be used as oxygen reduction catalyst(Jiang H L, et al. ACS Appl. Mater. Interfaces
(American Chemical Society-application material and interface), 2015, 7 (38): 21511)Or hydrogen separates out catalyst(Morozan A, et
Al. J. Electrochem. Soc. (U.S.'s electrochemistry can will), 2015,162: H719);In sensor, ultracapacitor
With the field such as lithium ion battery(Salavagione H J, et al. J. Mater. Chem. A (materials chemistry magazine A),
2014, 2: 14289)Application have document report.Metal, the graphene preparation method of N doping have a lot:Such as, warm high
Solution transition macrocyclic complex (Beck F J, et al. Appl. Electrochem. (Applied Electrochemistry magazine), 1977,
7: 239);Heat treatment organic compounds containing nitrogen(Such as ethylenediamine, pyridine)M-N-C clusters are obtained with transition metal salt(Lefè
Vre M, et al. Science (science) 2009,324:71);Pass through high temperature pyrolysis system with melamine and etal molysite
Standby Fe-N-C cluster catalysts(Jiang W J, et al. J. Am. Chem. Soc (JACS) 2016,
138: 3570), also useful polypyrrole and etal molysite prepare Fe-N-C cluster catalysts by high temperature pyrolysis(Zheng Y
P, et al. Nano Energy (the nanometer energy), 2016,30: 433);With polyaniline combination iron and the heat treatment system of cobalt
Standby class M/N/C catalyst (Wu G, et al. Science (science), 2011,332:443) etc..
The present invention is that a kind of preparation has the iron cobalt and nitrogen ternary codope of reinforcing mass transfer effect and synergic catalytic effect many
The method of level duct three-dimensional grapheme.With the polybenzimidazoles of soluble full armaticity(PBI)Macromolecule and molysite and cobalt salt
Mixed liquor reaction, the complex of generation, complex reaction mixture is well mixed in nano-calcium carbonate template, and complex exists
Template rule of surface is arranged, and under inert gas shielding, pyrolysis, complex forms iron cobalt and nitrogen three by dehydrogenation-cyclisation-carbonization
The Graphene of first codope, the carbon dioxide of Decomposition of Calcium Carbonate generation discharges the macropore phase to form aperture and go to be generated after removing template
Mutual insertion, prepares the three-dimensional grapheme of the multistage pore canal insertion of iron cobalt and nitrogen ternary codope;Product is used for redox reaction
Catalyst, fuel cell, metal-air battery oxygen reduction catalyst, electrolysis water oxygen separate out the fields such as catalyst, ultracapacitor.
The iron cobalt and nitrogen ternary codope multistage pore canal three-dimensional grapheme for obtaining, due to iron cobalt and the co-doped and three of nitrogen
Dimension loose structure so that the increase of its specific surface area, catalytic active site increase.Due to Graphene big π bond structures in itself, iron or cobalt
Inside graphene molecules, whole molecule forms big π bond structures to the polar bond formed with nitrogen, and the delocalization energy of its molecular orbit increases
Greatly, the energy level between HUMO tracks and LOMO tracks diminishes so that the environment of its catalytic active center is especially as porphyrin, phthalocyanine are matched somebody with somebody
The environment of compound, can so substantially reduce the overpotential of catalytic oxidation-reduction, and the catalysis thermodynamic property of catalyst gets a promotion;
In addition, the iron in product is different from the extranuclear strucure of cobalt, its electron outside nucleus cloud can influence each other, so as to produce catalyzing cooperation
Effect, can increase the catalysis activity of catalyst and stability;Furthermore, the three-dimensional porous structure of multistage pore canal insertion is conducive to
Reinforcing mass transfer so that electrode reaction dynamic performance is improved.
It is of the invention with simple itrogenous organic substance and transient metal complex or nitrogen containing polymer, such as pollopas, melamine
Metal-nitrogen-Spectra of Carbon Clusters difference that polyimide resin etc. is prepared with transition metal mixture pyrolysis is that metal-nitrogen-Spectra of Carbon Clusters is not
It is graphene-structured, the effect without big π, so catalytic performance is not high, its metal is easily removed by acid, so durability is inadequate
It is good, especially because metal-nitrogen-Spectra of Carbon Clusters is not bad loose structure its mass transfer effect, so, its catalysis activity and durable
Property is not good enough.Difference with the catalyst that polyaniline, polypyrrole are pyrolyzed formation together with transition metal is, polyaniline and poly- pyrrole
Cough up because it can not be dissolved, so, it cannot be covered with paint, lacquer, colour wash, etc. on template surface, so its operating characteristics is deteriorated, and PBI is solvable
Property, its very easy covering with paint is on template surface, and its operating performance is good.
The content of the invention
The present invention is that a kind of preparation has the iron cobalt and nitrogen ternary codope of reinforcing mass transfer effect and synergic catalytic effect many
The method of level duct three-dimensional grapheme.With the polybenzimidazoles of soluble full armaticity(PBI)Macromolecule and molysite and cobalt salt
Mixed liquor reaction, the complex of generation, complex reaction mixture is well mixed in nano-calcium carbonate template, and complex exists
Template rule of surface is arranged, and under inert gas shielding, pyrolysis, complex forms iron cobalt and nitrogen three by dehydrogenation-cyclisation-carbonization
The Graphene of first codope, the carbon dioxide of Decomposition of Calcium Carbonate generation discharges the macropore phase to form aperture and go to be generated after removing template
Mutual insertion, prepares the three-dimensional grapheme of the multistage pore canal insertion of iron cobalt and nitrogen ternary codope;Product is used for redox reaction
Catalyst, fuel cell, metal-air battery oxygen reduction catalyst, electrolysis water oxygen separate out the fields such as catalyst, ultracapacitor.
The iron cobalt and nitrogen ternary codope multistage pore canal three-dimensional grapheme for obtaining, due to iron cobalt and the co-doped and three of nitrogen
Dimension loose structure so that the increase of its specific surface area, catalytic active site increase.Due to Graphene big π bond structures in itself, iron or cobalt
Inside graphene molecules, whole molecule forms big π bond structures to the polar bond formed with nitrogen, and the delocalization energy of its molecular orbit increases
Greatly, the energy level between HUMO tracks and LOMO tracks diminishes so that the environment of its catalytic active center is especially as porphyrin, phthalocyanine are matched somebody with somebody
The environment of compound, can so substantially reduce the overpotential of catalytic oxidation-reduction, and the catalysis thermodynamic property of catalyst gets a promotion;
In addition, the iron in product is different from the extranuclear strucure of cobalt, its electron outside nucleus cloud can influence each other, so as to produce catalyzing cooperation
Effect, can increase the catalysis activity of catalyst and stability;Furthermore, the three-dimensional porous structure of multistage pore canal insertion is conducive to
Reinforcing mass transfer so that electrode reaction dynamic performance is improved.
It is of the invention with simple itrogenous organic substance and transient metal complex or nitrogen containing polymer, such as pollopas, melamine
Metal-nitrogen-Spectra of Carbon Clusters difference that polyimide resin etc. is prepared with transition metal mixture pyrolysis is that metal-nitrogen-Spectra of Carbon Clusters is not
It is graphene-structured, the effect without big π, so catalytic performance is not high, its metal is easily removed by acid, so durability is inadequate
It is good, especially because metal-nitrogen-Spectra of Carbon Clusters is not bad loose structure its mass transfer effect, so, its catalysis activity and durable
Property is not good enough.Difference with the catalyst that polyaniline, polypyrrole are pyrolyzed formation together with transition metal is, polyaniline and poly- pyrrole
Cough up because it can not be dissolved, so, it cannot be covered with paint, lacquer, colour wash, etc. on template surface, so its operating characteristics is deteriorated, and PBI is solvable
Property, its very easy covering with paint is on template surface, and its operating performance is good.
Viscosity average molecular weigh being soluble between 20,000~40,000 prepared by full armaticity PBI solid phase methods or liquid phase method
DMAc, DMF, DMSO, in 1-METHYLPYRROLIDONE equal solvent.Molecular weight is too big, and the solubility property of PBI is deteriorated;Molecular weight is too small
Its viscosity is too small, it is impossible to coated die plate agent well.
The method of preparation of the duct three-dimensional grapheme of iron cobalt and nitrogen ternary multistage codope is:The degree of polymerization is prepared first to fit
When PBI, PBI dissolving form solution in a solvent, to the mixed liquor that a certain amount of molysite and cobalt salt are added in solution, plus
Heat, stirring reaction 5 ~ 8 hours, obtain the complex reaction solution that PBI is formed with iron ion and cobalt ions, are added in the reaction solution
Appropriate particle diameter is the template calcium carbonate of 30 ~ 100 nm, and stirring makes it be sufficiently mixed uniformly.Under agitation, heat, at leisure
Solvent is steamed near dry, is transferred in vacuum drying chamber and is dried at 60 ~ 120 DEG C.It is finely ground in mortar, porcelain boat bottom is laid in, put
Enter in electric tube furnace, under argon gas protection, at 800~1100 DEG C, be pyrolyzed 2 ~ 3h.Treat that furnace temperature is cooled to room temperature, take out, with dilute
Sour repeatedly washing dries to obtain product to go template agent removing, suction filtration to be washed with deionized water only.
In the reaction of PBI and molysite and cobalt salt, molysite is 1 with the mol ratio of cobalt salt to the present invention:2~2:1;Salt-mixture
Addition is critically important, and it determines the doping of iron and cobalt in the product of preparation, also determines catalysis of the product as catalyst
How much is active sites.Because iron ion and cobalt ions are coordinated with the imidazoles nitrogen in PBI macromolecules, it is ensured that four imidazole ring correspondences one
Individual iron ion or a cobalt ions are advisable, and experiment finds that PBI is 1 with the mass ratio of molysite and cobalt salt mixture:2~2:Between 1,
The change of its proportioning is determined by different types of molysite and cobalt salt.
In the present invention, template is nano-calcium carbonate particles.The nitrogen co-doped multistage pore canal of-cobalt-that taps a blast furnace can be prepared
Three-dimensional grapheme, the particle diameter and addition of template are crucial:The particle diameter of template determines the aperture of the material of preparation;Template
The addition of agent determines the number of plies of the Graphene of preparation, the formation of aperture and performance.Addition very little, can only obtain iron cobalt and
Nitrogen co-doped porous carbon materials, it is impossible to obtain the material of multi-layer graphene structure;Add excessively, the iron cobalt and nitrogen for obtaining are co-doped with
The miscellaneous three-dimensional grapheme number of plies very little, after removing template agent removing, is easily collapsed, and can only obtain broken fragment.The particle of template
Spend and the amount for adding template had a certain impact, granularity is small, its specific surface area it is big, it is necessary to template amount it is just few;Instead
It, if granularity it is big, it is necessary to template amount if it is many;Consider that Decomposition of Calcium Carbonate can produce aperture, the aperture of aperture 2 ~
5nm, so, the particle diameter of calcium carbonate selects 30 ~ 100nm;The consumption of template is:PBI is 2 with the mass ratio of template:1~1:
4;Ratio change is relevant with the granularity of template.It is pyrolyzed under inert gas shielding, the regularly arranged cooperation on template surface
Thing can occur a series of heat chemistry change such as dehydrogenation-cyclisation-carbonization, finally give product.The formation of the pore channels of insertion
Decomposition during with the amount of nano-calcium carbonate and pyrolysis is relevant, and below 800 DEG C, calcium carbonate is not decomposed pyrolysis temperature, it is impossible to formed
The passage of aperture insertion.The aperture of aperture is relevant with the amount of calcium carbonate, and the amount of the carbon dioxide that calcium carbonate is produced is big, then can be with shape
Into aperture aperture it is just big, if the amount of the carbon dioxide for producing is small, the aperture for being formed is just small.In inert gas shielding
Lower pyrolysis, pyrolysis temperature is:800~1100 DEG C;The formation of aperture and pore size are the carbon dioxide of Decomposition of Calcium Carbonate generation
Produce, the factor such as amount and pyrolysis temperature of calcium carbonate determines aperture and the insertion performance of aperture.Such multistage insertion it is porous
Material has invigoration effect to the mass transfer of electrode reaction.
Washing diluted acid, after repeatedly template agent removing is removed in washing, is washed with deionized to neutrality and dries.
Pyrolysis temperature is critically important, and pyrolysis temperature range is 800~1100 DEG C.The too low PBI pyrolysis of temperature is incomplete, is produced
The electric conductivity of product is poor;Below 800 DEG C, calcium carbonate is not decomposed, it is impossible to form the passage of aperture insertion.Pyrolysis temperature is reached most
After good temperature, then to raise pyrolysis temperature its performance constant, but, oxidation reaction, institute can occur when inert gas shielding is insufficient
It is unsuitable too high with pyrolysis temperature.
The Graphene characterizing method of the multistage pore canal of three-dimensional iron cobalt nitrogen ternary codope is:Aperture, porosity, pore volume and ratio
Surface area nitrogen adsorption instrument(BET), the Morphology analysis SEM of product(SEM)It is micro- with projection electron
Mirror(TEM), the Graphene number of plies can be by high power transmission electron microscope(HRTEM)Characterized with Raman spectrum.The stone of product
Blackization degree, graphene-structured and the number of plies can use X-ray powder diffraction(XRD), Raman spectrum characterizes.The element of product
Composition, valence state can use x-ray photoelectron spectroscopy(XPS)Characterized, used rotating disk electrode (r.d.e)(RDE)Carry out test product
Catalytic oxidation-reduction reaction(ORR)Performance, water electrolysis oxygen evolution reaction(EOR), evolving hydrogen reaction(EHR)With the capacitive property of product
Test can use cyclic voltammetric(CV), linear volt-ampere(LSV), Tafel curve and charge-discharge performance test.Product is used as urging
The durability test of agent can use CV, LSV and chronoa mperometric plot(i-t).The catalytic performance of product finally needs assembling
Metal-air battery, hydrogen-oxygen fuel cell, the electrolytic cell of electrolysis water, ultracapacitor and sensor test its performance.
Specific embodiment
The preparation of [embodiment 1] mPBI:Polyphosphoric acids is added in the there-necked flask protected equipped with electric stirring and nitrogen
(PPA) (100g), lower 160 DEG C of nitrogen protection stirs 1h to remove unnecessary moisture and air.By DABz (4g, 18.7
Mmol) and M-phthalic acid (3.1g, 18.7 mmol) is well mixed, it is slowly added in there-necked flask.Control nitrogen
Flow velocity, prevents DABz to be oxidized, while reaction temperature being lifted to 200 DEG C and continuing insulation, stirring reaction 5-8h.With reaction
The increase of time, polymerization system gradually becomes sticky.Stop reaction when viscosity is suitable, reaction mixture is slowly transferred to largely
Reeled off raw silk from cocoons in deionized water, clean, dry, crushed, deionized water is repeatedly washed to remove polyphosphoric acids and unreacted reactant, i.e.,
MPBI is obtained, with the molecular weight of determination of ubbelohde viscometer mPBI.
[embodiment 2] Solid phase synthesis mPBI:By DABz (4g, 18.7 mmol) and M-phthalic acid
(3.1g, 18.7 mmol) are well mixed in mortar, being fully ground, and are transferred to three mouthfuls of burnings with nitrogen protection, agitator
In bottle.Lead to nitrogen 15min to drain the air in flask.N2Protection, under stirring, 225 DEG C of heating of oil bath keep 3h.After cooling
Take out, finely ground, N2Under protection, heating in electric furnace is warmed up to 270-275 DEG C, keeps 3h.Room temperature is cooled to, product is taken out, is ground
Carefully, that is, mPBI is obtained, with the molecular weight of determination of ubbelohde viscometer mPBI.
The preparation method of ABPBI is similar with mPBI, simply with 3,4- diaminobenzoic acids(DABA)Substitute DABz and
Phthalic acid.Only it is that can obtain ABPBI with a kind of raw material.Other reaction conditions and operating procedure are with embodiment 1 and implementation
Example 2.
[embodiment 3] is template with the calcium carbonate of particle diameter 30nm, and molysite and cobalt salt use acetate, mol ratio 1:1;Two
With the mass ratio of mPBI it is 1 after the mixing of kind of salt:2, it is 1 with mPBI and calcium carbonate template mass ratio:As a example by 1:In the burning of 250mL
In cup, the mPBI of 1g is added(Viscosity average molecular weigh 2 ~ 30,000)With 20mL DMAc, heating, stirring are dissolved it, are added under agitation
The mixture of 0.5 g cobalt acetates and ferric acetate(Two kinds of salt are according to mol ratio 1:1 mixing)20mL DMAc solution, insulation 80 DEG C ~
At 100 DEG C, stirring reaction 5 ~ 8 hours is slowly added into the calcium carbonate granule of the nanometer that 1g particle diameters are 30nm, stirs 4 ~ 6 hours, makes
It is uniformly dispersed.The viscous liquid for obtaining heats and is concentrated near dry under agitation, is done at 60 ~ 120 DEG C in the vacuum drying chamber
Dry, solid is finely ground in mortar, is transferred in porcelain boat, under argon gas protection, is pyrolyzed 2-3h at 900 DEG C in the electric furnace, treats furnace temperature
Room temperature is down to, is taken out, it is finely ground, black powder solid is obtained, it is transferred in 250 mL conical flasks, the watery hydrochloric acid of 70 mL is added,
Heating, stirring 24h, suction filtration are so washed three times with watery hydrochloric acid, are washed to neutrality, are dried to obtain black powder solid product
0.75g.BET tests show that its pore-size distribution is 30 nm, and the nm specific surface areas of aperture 2 ~ 4 are 1331 m2 g-1, SEM test tables
Bright, the product for obtaining is porous foam shape carbon material, TEM and HRTEM analysis shows, product is three-dimensional grapheme structure carbon materials
Material, aperture is 30 nm, and the nm Graphenes of aperture 2 ~ 4 are drawn a bow to the full back and are shown to be 2 ~ 4 layer graphenes.XRD and Raman spectrum test show, produce
Product are 2 ~ 4 layers of graphene-structured;XPS analysis show that product iron content 0.7%, cobalt content is 0.8%, and nitrogen content is 6.8%, and
Nitrogen is pyridine type nitrogen and pyrroles's type nitrogen.Illustrate, product is the material of the multistage pore canal three-dimensional grapheme structure of iron-cobalt-nitrogen co-doped
Material.Catalytic oxidation-reduction performance under its 0.1 mol/L KOH, oxygen initial reduction current potential is 1.01 V vs RHE, electron transfer number
It is 3.99, durability is good;Magnesium air cell performance is up to 127 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 674
mW/cm2, it is 1.46 V vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L, and limiting current density reaches
140 mA/cm2.Ultracapacitor specific capacitance is 523 F g-1, be recycled 10000 times still holding capacitor value 98%.
[embodiment 4] as described in Example 3, other conditions are identical, and simply mPBI is changed into 2 with the quality of calcium carbonate:1,
It is similarly obtained the solid powder of black.BET tests show that its pore-size distribution is still 30 nm, the nm of aperture 2 ~ 4, but it compares table
Area is then reduced to 747 m2 g-1, its SEM and TEM tests show, are the carbon material of loose structure inside it, and surface is multilayer stone
Black alkene structure, XRD and Raman data show, 7 ~ 8 layers of the number of plies of its Graphene.XPS data are similar with the product of embodiment 3.Its
Catalytic oxidation-reduction performance under 0.1 mol/L KOH, oxygen initial reduction current potential is 0.86 V vs RHE, and electron transfer number is
3.69, durability is good;Magnesium air cell performance is up to 78 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 376 mW/
cm2, it is 1.57 V vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L, and limiting current density reaches 60
mA/cm2.Ultracapacitor specific capacitance is 238 F g-1, be recycled 10000 times still holding capacitor value 95%.
[embodiment 5] as described in Example 3, other conditions are identical, and simply mPBI is changed into 1 with the quality of calcium carbonate:2,
It is similarly obtained the solid powder of black.BET is tested and shown, its pore size distribution range 10 ~ 30 nm, the nm of aperture 3 ~ 5, but it compares
Surface area is then reduced to 868 m2 g-1, its SEM and TEM tests show, are the carbon material of loose structure inside it, and surface is multilayer
Graphene-structured, XRD and Raman data show, 7 ~ 8 layers of the number of plies of its Graphene.XPS data are similar with the product of embodiment 3.
Catalytic oxidation-reduction performance under its 0.1 mol/L KOH, oxygen initial reduction current potential is 0.88 V vs RHE, and electron transfer number is
3.76, durability is good;Magnesium air cell performance is up to 84 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 368 mW/
cm2, it is 1.56 V vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L, and limiting current density reaches 70
mA/cm2.Ultracapacitor specific capacitance is 364 F g-1, be recycled 10000 times still holding capacitor value 95%.
[embodiment 6] as described in Example 3, other conditions are identical, and simply pyrolysis temperature is respectively 700 DEG C.Obtain black
The powdered g of solid product 0.79 of color.BET tests show that its pore-size distribution is 30 nm, the nm of aperture 2 ~ 4, and specific surface area is
1098 m2 g-1, SEM tests show, the product for obtaining is porous foam shape carbon material, TEM and HRTEM analysis shows, and product is
Three-dimensional grapheme structure carbon material, aperture is 30 nm, and the nm of aperture 2 ~ 4, Graphene is drawn a bow to the full back and is shown to be 2 ~ 4 layer graphenes.XRD and
Raman spectrum test shows that product is 2 ~ 4 layers of graphene-structured;XPS analysis show, product iron content 0.7%, and cobalt content is
0.7%, nitrogen content is 6.8%, and nitrogen is pyridine type nitrogen and pyrroles's type nitrogen.Illustrate, product is the three-dimensional grapheme structure of N doping
Material.Catalytic oxidation-reduction performance under its 0.1mol/L KOH, oxygen initial reduction current potential is 0.87 V vs RHE, and electronics turns
It is 3.74 to move number, and durability is slightly worse good;Magnesium air cell performance reaches 69mW/cm2.For hydrogen-oxygen fuel cell, its peak power is
281 mW/cm2, it is 1.66 V vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L, and limiting current density reaches
To 50 mA/cm2.Ultracapacitor specific capacitance is 274 F g-1, be recycled 10000 times still holding capacitor value 94%.
[embodiment 7] the other the same as in Example 3, simply pyrolysis temperature is 1100 DEG C.Obtain black powder solid product
0.59 g.BET tests show that its pore-size distribution is 30 nm, and the nm of aperture 3 ~ 4, specific surface area is 865 m2 g-1, SEM test tables
Bright, the product for obtaining is porous foam shape carbon material, TEM and HRTEM analysis shows, product is three-dimensional grapheme structure carbon materials
Material, aperture is 30 nm, and the nm of aperture 3 ~ 4, Graphene is drawn a bow to the full back and is shown to be 2 ~ 4 layer graphenes.XRD and Raman spectrum are tested and shown,
Product is 2 ~ 4 layers of graphene-structured;XPS analysis show that product iron content 0.6%, cobalt content is 0.5%, and nitrogen content is 6.2%,
And nitrogen is pyridine type nitrogen and pyrroles's type nitrogen.Illustrate, product is the material of the three-dimensional grapheme structure of N doping.Its 0.1 mol/L
Catalytic oxidation-reduction performance under KOH, oxygen initial reduction current potential is 0.96 V vs RHE, and electron transfer number is 3.95, and durability is good
It is good;Magnesium air cell performance is up to 88 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 454 mW/cm2, 0.5 mol/L's
It is 1.59 V vs RHE that oxygen separates out take-off potential in sulfuric acid solution, and limiting current density reaches 80 mA/cm2.Ultracapacitor
Specific capacitance is 357 F g-1, be recycled 10000 times still holding capacitor value 96%.
[embodiment 8] as described in Example 3, other conditions are identical, simply with particle diameter for 50 nm calcium carbonate granules do
Template, at this moment, because the particle diameter of template becomes big, its surface area increases small, the consumption reduction of mPBI, then mPBI and template
Mass ratio is changed to be 1:2, the product for obtaining is similar to Example 3, and simply its pore-size distribution compares table in 50 nm, the nm of aperture 4 ~ 5
Area is 1181 m2 g-1, it is 3 ~ 5 layers of three-dimensional nitrogen-doped graphene material, catalytic oxidation-reduction starting under 0.1 mol/L KOH
Current potential is 0.96V vs RHE, and electron transfer number is 3.96, and durability is good;Magnesium air cell performance is up to 106 mW/cm2.With
In hydrogen-oxygen fuel cell, its peak power is 452 mW/cm2, it is 1.55 that oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L
V vs RHE, limiting current density reaches 110 mA/cm2.Ultracapacitor specific capacitance is 321F g-1, it is recycled 10000
The 97% of secondary still holding capacitor value.
[embodiment 9] as described in Example 3, other conditions are identical, simply with particle diameter for 100 nm calcium carbonate granules do
Template, at this moment because the particle diameter of template increases, its surface area reduces, and the consumption of mPBI is reduced, then mPBI and template
Mass ratio is changed to be 1:4, the product for obtaining is similar to Example 3, and simply its pore-size distribution is in 100 nm, the nm specific surfaces of aperture 5
Product is 867 m2 g-1, it is 3 ~ 5 layers of three-dimensional nitrogen-doped graphene material, catalytic oxidation-reduction take-off potential is 0.94V vs RHE,
Electron transfer number is 3.90, and durability is good;Magnesium air cell performance is up to 81 mW/cm2.For its peak work(of hydrogen-oxygen fuel cell
Rate is 338 mW/cm2, it is 1.58 V vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5mol/L, and carrying current is close
Degree reaches 70 mA/cm2.Ultracapacitor specific capacitance is 221 F g-1, be recycled 10000 times still holding capacitor value 95%.
[embodiment 10] uses calcium carbonate template, and particle diameter is 30 nanometers, molysite and cobalt salt citrate, itself and ABPBI
Mass ratio be 2:1.Other experiment conditions are with embodiment 3.ABPBI is 1 with the mass ratio of template:1.Its result and embodiment
3 are similar to.Aperture is 30 nm, aperture 2 ~ 4 nm, 1315 m2 g-1, it is 2 ~ 4 layer graphenes.Iron content 0.8%, cobalt content 0.8%,
Nitrogen content is 6.7%, and nitrogen is pyridine type nitrogen and pyrroles's type nitrogen.Catalytic oxidation-reduction performance under its 0.1 mol/L KOH, oxygen rises
Beginning reduction potential is 1.02 V vs RHE, and electron transfer number is 3.99, and durability is good;Magnesium air cell performance is up to 118 mW/
cm2.For hydrogen-oxygen fuel cell, its peak power is 618 mW/cm2, oxygen precipitation take-off potential is in the sulfuric acid solution of 0.5 mol/L
1.54 V vs RHE, limiting current density reaches 110 mA/cm2.Ultracapacitor specific capacitance is 549 F g-1, it is recycled
10000 times still holding capacitor value 97%.
[embodiment 11] other molysite, cobalt salt situation are similar to the above embodiments, simply change PBI mixed with molysite and cobalt salt
The ratio of compound.
The situation of the product that [embodiment 12] ABPBI is mixed with the calcium carbonate of other particle diameters, same to above-described embodiment, its
Performance is better than the product under similarity condition with mPBI.
Mole such as the 1 of [embodiment 13] other molysite, cobalt salt:2 or 2:1, other operating procedures are obtained with embodiment 3
Product catalytic performance be not so good as 1:1 it is good.
Claims (6)
1. the preparation side of the three-dimensional grapheme of iron cobalt and nitrogen ternary codope multistage pore canal with catalyzing cooperation effect has been invented
Method, it is characterised in that:With the polybenzimidazoles of soluble full armaticity(PBI)PBI and iron ion are prepared with molysite and cobalt salt
With the complex of cobalt ions, addition nano-calcium carbonate is template, is well mixed, and is evaporated, and complex is in template rule of surface
Arrangement, under inert gas shielding, pyrolysis, complex forms the graphite of iron cobalt and nitrogen ternary codope by dehydrogenation-cyclisation-carbonization
Alkene, the carbon dioxide of Decomposition of Calcium Carbonate generation is discharged and to form aperture and be mutually communicated with the macropore for going to generate after removing template, prepares iron
The three-dimensional grapheme of the multistage pore canal insertion of cobalt and nitrogen ternary codope;The above-mentioned multi-stage porous for preparing iron cobalt and nitrogen ternary codope
The three-dimensional grapheme of road insertion is used for redox reaction catalyst, fuel cell, metal-air battery oxygen reduction catalyst, electricity
Solution water oxygen separates out the fields such as catalyst, ultracapacitor.
2. the PBI of full armaticity according to claim 1, it is characterised in that:Whole polymer molecule forms a big π
Key, molecule belongs to rigidity, aroma type compound, such as poly-(2,5- benzimidazoles)(ABPBI), it is poly- [2,2 '-(phenyl) -5,
5 '-bibenzimidaz sigmale] (mPBI) etc.;Its structural formula is as follows:
The structural formula of the structural formula mPBI of ABPBI
Polymer viscosity average molecular weigh is between 2~40,000;It is soluble in dimethylacetylamide(DMAc), dimethylformamide
(DMF), dimethyl sulfoxide (DMSO)(DMSO), 1-METHYLPYRROLIDONE, in the organic solvent such as dimethylbenzene.
3. molysite according to claim 1 and cobalt salt, it is characterised in that can be dispersed or dissolved in intensive polar solvent
Salt;Can select, acetate, citrate, nitrate, hydrochloride, perchlorate, gluconate etc., preferably acetate,
Citrate, nitrate, hydrochloride;Molysite is 1 with the mol ratio of cobalt salt:2~2:1.
4. nano template according to claim 1 is nano level calcium carbonate, it is characterised in that:Nano-particle diameter exists
30~100 nm;800 DEG C of the nano particle starts to decompose;Can be receiving for the shapes such as spherical, cube, cylinder or polygon prism
Rice grain.
5. PBI according to claim 1 is with the mass ratio of molysite and cobalt salt mixture: 2:1~1:2;PBI and nanometer mould
The mass ratio of plate agent is 2:1~1:4;Hybrid mode is:PBI solution mixes with the mixed liquor of molysite and cobalt salt, heating, stirring
Reaction 5 ~ 8 hours, PBI forms complex solution with iron ion and cobalt ions;Template, stirring is added to be well mixed for 4 ~ 6 hours,
The lower heating of stirring steams solvent near dry, 60 ~ 120 DEG C of vacuum drying, finely ground, is pyrolyzed under inert gas shielding, with Diluted Acid Washing with
Remove template agent removing.
6. inert gas according to claim 1 is argon gas or high pure nitrogen, and pyrolysis temperature is 800~1100 DEG C.
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Cited By (4)
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CN108059145A (en) * | 2017-12-14 | 2018-05-22 | 同济大学 | A kind of preparation method of multi-stage porous N doping porous carbon |
CN108878909A (en) * | 2018-07-13 | 2018-11-23 | 中南大学 | A kind of three-dimensional porous composite material and preparation method and application based on biomass |
CN113060719A (en) * | 2021-03-17 | 2021-07-02 | 山东省科学院新材料研究所 | Wood-based carbon foam and preparation method thereof, cathode electrocatalyst, cathode and metal-air battery |
CN113531539A (en) * | 2021-07-20 | 2021-10-22 | 浙江红狮环保股份有限公司 | Method for resource utilization of sodium chloride waste salt |
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CN104108708A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Nitrogen-doped graphene and preparation method thereof |
CN104475172A (en) * | 2014-11-21 | 2015-04-01 | 东华大学 | Preparation method and application of three-dimensional porous heteroatom-doped graphene |
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US5618615A (en) * | 1994-07-06 | 1997-04-08 | Matsushita Electric Industrial Co., Ltd. | Graphite layer material |
CN104108708A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Nitrogen-doped graphene and preparation method thereof |
CN104475172A (en) * | 2014-11-21 | 2015-04-01 | 东华大学 | Preparation method and application of three-dimensional porous heteroatom-doped graphene |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108059145A (en) * | 2017-12-14 | 2018-05-22 | 同济大学 | A kind of preparation method of multi-stage porous N doping porous carbon |
CN108878909A (en) * | 2018-07-13 | 2018-11-23 | 中南大学 | A kind of three-dimensional porous composite material and preparation method and application based on biomass |
CN113060719A (en) * | 2021-03-17 | 2021-07-02 | 山东省科学院新材料研究所 | Wood-based carbon foam and preparation method thereof, cathode electrocatalyst, cathode and metal-air battery |
CN113531539A (en) * | 2021-07-20 | 2021-10-22 | 浙江红狮环保股份有限公司 | Method for resource utilization of sodium chloride waste salt |
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