CN106622329A - Method for preparing two-dimensional nitrogen-doped graphene in microreactor confined in vertical direction - Google Patents
Method for preparing two-dimensional nitrogen-doped graphene in microreactor confined in vertical direction Download PDFInfo
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- CN106622329A CN106622329A CN201611234516.8A CN201611234516A CN106622329A CN 106622329 A CN106622329 A CN 106622329A CN 201611234516 A CN201611234516 A CN 201611234516A CN 106622329 A CN106622329 A CN 106622329A
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- abpbi
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- doped graphene
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000011229 interlayer Substances 0.000 claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000001301 oxygen Substances 0.000 claims abstract description 42
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 42
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000197 pyrolysis Methods 0.000 claims abstract description 25
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 20
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000446 fuel Substances 0.000 claims abstract description 16
- -1 alkyl dimethyl benzyl ammonium bromide Chemical compound 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 5
- 239000007772 electrode material Substances 0.000 claims abstract description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 230000003197 catalytic effect Effects 0.000 claims description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000003780 insertion Methods 0.000 claims description 9
- 230000037431 insertion Effects 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 125000002883 imidazolyl group Chemical group 0.000 claims description 5
- 229910052573 porcelain Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229920001600 hydrophobic polymer Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000006479 redox reaction Methods 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 2
- UERFYFDULXZCSY-UHFFFAOYSA-N [NH4+].[Br-].C(C1=CC=CC=C1)[PH3+].[Br-] Chemical compound [NH4+].[Br-].C(C1=CC=CC=C1)[PH3+].[Br-] UERFYFDULXZCSY-UHFFFAOYSA-N 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 229940113088 dimethylacetamide Drugs 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 230000009467 reduction Effects 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 39
- 239000000243 solution Substances 0.000 description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 239000010410 layer Substances 0.000 description 18
- 229910052901 montmorillonite Inorganic materials 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 11
- 239000003990 capacitor Substances 0.000 description 11
- 229910052749 magnesium Inorganic materials 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- 230000033116 oxidation-reduction process Effects 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 229920000767 polyaniline Polymers 0.000 description 10
- 230000027756 respiratory electron transport chain Effects 0.000 description 9
- 229920002521 macromolecule Polymers 0.000 description 7
- 229920002480 polybenzimidazole Polymers 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 150000003384 small molecules Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000002861 polymer material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920000128 polypyrrole Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- DPZVOQSREQBFML-UHFFFAOYSA-N 3h-pyrrolo[3,4-c]pyridine Chemical class C1=NC=C2CN=CC2=C1 DPZVOQSREQBFML-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- NULGSOGHGHDGBH-UHFFFAOYSA-N n,n-dimethyl-1-phenylmethanamine;hydrobromide Chemical compound [Br-].C[NH+](C)CC1=CC=CC=C1 NULGSOGHGHDGBH-UHFFFAOYSA-N 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- 150000003233 pyrroles Chemical class 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003483 aging Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 2
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000005087 graphitization Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- YECIFGHRMFEPJK-UHFFFAOYSA-N lidocaine hydrochloride monohydrate Chemical class O.[Cl-].CC[NH+](CC)CC(=O)NC1=C(C)C=CC=C1C YECIFGHRMFEPJK-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 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
- HEMGYNNCNNODNX-UHFFFAOYSA-N 3,4-diaminobenzoic acid Chemical class NC1=CC=C(C(O)=O)C=C1N HEMGYNNCNNODNX-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 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
- 241000446313 Lamella Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000006182 dimethyl benzyl group Chemical group 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/50—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a method for preparing two-dimensional nitrogen-doped graphene in a microreactor confined in a vertical direction. The microreactor confined in the vertical direction takes C4-C16 alkyl dimethyl benzyl ammonium bromide modified montmorillonoid hydrophobic layered materials as templates, and poly(2,5-benzimidazole) (ABPBI) is injected into the hydrophobic interlayers by a vacuum assisted method to serve as a carbon source and a nitrogen source. Benzimidazole rings in the ABPBI molecules are regularly in the template agent interlayers, and nitrogen-doped graphene with high nitrogen content is obtained after pyrolyzing and template agent removing. The ABPBI selects and uses a dissoluble oligomer; the distances between the layered template agent interlayers are adjusted by the sizes of cationic surfactant alkyl chains adsorbed by the interlayers, and the interlayer spacings are between 0.2 and 0.6 nm; the mass ratio of the ABPBI to the layered template agent is (2:1) to (1:3); and the pyrolysis temperature is 700 to 1100 DEG C. The prepared two-dimensional nitrogen-doped graphene with high nitrogen content is applied in the fields of an oxygen reduction catalyst of a fuel battery or metal air battery cathode, an oxygen evolution catalyst of an electrolysis water anode, an electrode material of a supercapacitor and the like.
Description
Technical field
Belong to field of nano material preparation, the negative electrode for the fuel cell in clean energy resource field, metal-air battery is urged
Agent, electrolysis water catalyst, the field such as electrode material for super capacitor and electrochemical sensor.
Background technology
Graphene is the individual layer two dimension carbonaceous material being made up of carbon atom, due to fabulous electricity, optics, machinery etc.
Performance and the attention of people (Bacsa R R, et al. Carbon (carbon), 2015,89: 350).Hetero atom（Such as, N, P,
B and S etc.）Graphene performance after doping is more projected, it is also possible to codope or three doping etc..In all kinds of Heteroatom doping graphite
In alkene, nitrogen-doped graphene（NG）Most study, wherein, only pyridine nitrogen and pyrroles's nitrogen are planar structures, and verified tool
There is oxygen reduction activity（Nie Yao etc., Journal of Chemical Industry and Engineering）, 2015, 66: 3305）, conversely, the nitrogen-atoms of three-dimensional structure is not lived
Property.Preparing the method for nitrogen-doped graphene has：Graphite oxide reducing process, the heat-treatment oxidation Graphene (Li under ammonia atmosphere
X, et al. J Am Chem Soc（JACS）2009, 131: 15939)；Micromechanics stripping method (Zhao W F,
Et al. J. Mater. Chem. (materials chemistry magazine), 2010; 20, 5817)；Chemical vapour deposition technique（CVD）
(Jin Z, et al. ACS Nano (American Chemical Society-nanometer), 2011,5 (5): 4112)；Directly it is pyrolyzed nitrogen atom
2,6- diamino-pyridines (Zhao Y, the et al. J Am Chem Soc (American Chemical Societies of abundant Fe, Co coordination polymerization
Will), 2012,134 (48): 19528)；Prepared for the reduction of template ethylenediamine in silica etc. with graphene oxide three-dimensional
The nitrogen-doped graphene of structure has been reported（Yang S B, et al. Angew Chem Int Ed (German applied chemistry),
2011, 123: 5451）Etc..
Template is done with stratified material, aniline prepares polyaniline in stratiform template internal-response, and pyrolysis prepares two-dimentional nitrogen and mixes
Miscellaneous Graphene had been reported that (Ding W, et al. Angew Chem Int Ed (German applied chemistry-world version),
2013, 52: 1175）, the polyaniline planar alignment of its synthesis, being pyrolyzed the two-dimentional nitrogen-doped graphene for preparing can be containing more
Pyridine nitrogen and pyrroles's nitrogen, it shows excellent catalytic oxidation-reduction performance.The method of document is that template montmorillonite is changed using acid
Property prepare H+The montmorillonite of type, obtains the interlayer of hydrophilic；It is aniline that small molecule aniline generates in acid condition hydrophilic
Hydrochloride, in being conducive to the interlayer for insert hydrophilic, small molecule is also easy to enter in interlayer, it is not necessary to carry out the operation of complexity；
There is polymerisation in aniline, obtain polyaniline in interlayer, and the process of its polymerization is just controlled by vertical direction area size.
The molecule of the polyaniline plane for arriving, is pyrolyzed under inert gas shielding, obtains the Graphene of two-dimentional N doping.
The present invention is the macromolecular material using the benzimidazole unit of armaticity, is gathered（2,5- benzimidazoles）（ABPBI）
For carbon source and nitrogen source, the pyrolysis under inert gas shielding prepares the material with carbon element of N doping.Covered with cationic surfactant is modified
De- soil stratified material, obtains hydrophobic interlayer and does template, makes rigid ABPBI molecules regularly arranged in interlayer, occurs without a large amount of
Stacking, curling etc. are unfavorable for generating the situation of Graphene to prepare the material of multilayer two-dimension nitrogen-doped graphene structure.The present invention
It is with document difference：First, be to stratiform mould material acid modification, to increase interlamellar spacing and cation easily in positive
Ionic surface active agent replaces.It is modified process with cationic surfactant again so as to which interlayer becomes hydrophobic, and layer
Spacing becomes big so as to be conducive to hydrophobic macromolecular material to be inserted in interlayer；Secondly, high score is made using the method for vacuum aided
Sub- ABPBI molecules can be entered in interlayer；Third, the drying in interlayer of rigid ABPBI molecules can reach the rule of molecule
Arrangement, desirably prevents a large amount of stackings, curling etc. to be unfavorable for generating the situation of Graphene.Protect in inert gas after insertion ABPBI
The lower pyrolysis of shield, obtains the Graphene of two-dimentional N doping by removing template agent removing.
And the method for document is the modified preparation H of template montmorillonite employing acid+The montmorillonite of type, obtains the folder of hydrophilic
Layer；Small molecule aniline generates in acid condition water-soluble anilinechloride, in being conducive to the interlayer for insert hydrophilic；Again
Person, small molecule is also easy to enter in interlayer, it is not necessary to carry out the operation of complexity；There is polymerisation in aniline, obtain in interlayer
Polyaniline, the process of its polymerization is just controlled by area size.The molecule of the polyaniline plane for obtaining, in inert gas shielding
Lower pyrolysis, obtains the Graphene of two-dimentional N doping.
The key technology of the present invention is the silicic acid anhydride of interlayer, the control of interlamellar spacing, the insertion of ABPBI molecules and rule
The factors such as the proportioning of arrangement and ABPBI and template.Hydrophobic treatment is the basis of macromolecule insertion, interlamellar spacing control and template
Agent decides the macromolecule regular degree for arranging and the number of plies for obtaining Graphene with ABPBI proportionings.
Poly- 2,5- benzimidazoles (ABPBI）It is simplest one kind in PBI families, adopts 3, the 4- diaminobenzoic acids to be
Raw material, under nitrogen protection, 200 DEG C in polyphosphoric acids (PPA) under the conditions of condensation polymerization be obtained.It prepares reaction equation such as
Under：
Polybenzimidazoles（PBI）It is high molecular polymer that a class contains benzimidazole group, benzimidazole ring belongs in molecule
The stiffening ring of armaticity, easily piles up aggregation in PBI molecules.
The invention is by the use of the benzimidazole of armaticity as offer carbon and the raw material of nitrogen, under inert gas argon gas shielded
Pyrolysis prepares nitrogenous material with carbon element.PBI solution is pressed between the interlayer of hydrophobic stratified material by the method for vacuum aided,
Vacuum removes solvent, makes the benzimidazole ring in interlayer in PBI regularly arranged, plane flush system structure is formed, in indifferent gas
The lower pyrolysis of body protection, PBI vertical direction in interlayer limits its reaction, the plane N doping of two dimension can be formed in the horizontal direction
Graphene-structured, goes template agent removing to obtain two-dimentional nitrogen-doped graphene.Change ratio, the Control architecture interlamellar spacing of ABPBI and template
To control the number of plies and performance of the nitrogen-doped graphene of preparation, preferable multilayer two-dimension nitrogen-doped graphene is finally given.
It is conventional method that macromolecular material method for pyrolysis prepares material with carbon element, such as uses phenolic resin, pollopas and trimerization
The pyrolysis such as melamine resin prepare material with carbon element.Compare with melmac Polymer material with phenolic resin, pollopas,
The difference of ABPBI is the stiffening ring benzimidazole ring that it contains armaticity, and the imidazoles nitrogen on imidazole ring contains it
Nitrogen quantity is more enriched.It is therefore high temperature pyrolysis ABPBI can obtain the material with carbon element of the N doping of high-load and suitable by introducing
The orientation and the restriction of vertical direction of the fragrant plane of a loop of template or control molecule, can obtain after pyrolysis multilayer nitrogen and mix
Miscellaneous grapheme material.Compare with polyaniline with polypyrrole Polymer material, ABPBI can dissolve, it is easy to be inserted into template
In interlayer, and polyaniline, polypyrrole etc. are insoluble, it is impossible to mix with template.
The content of the invention
The present invention, has invented a kind of preparation method of the two-dimentional nitrogen-doped graphene of high nitrogen-containing.With the benzo of armaticity
The macromolecular material of imidazole unit, gathers（2,5- benzimidazoles）（ABPBI）For carbon source and nitrogen source, changed with cationic surfactant
Property montmorillonite layered material, obtain hydrophobic interlayer and do template, make rigid hydrophobic ABPBI molecules insert hydrophobic interlayer, and
And it is regularly arranged in interlayer, prevent a large amount of stackings, curling etc. and be unfavorable for generating the situation of Graphene to prepare multilayer two
The material of dimension nitrogen-doped graphene structure.By the molecular structure for selecting cationic surfactant, regulate and control hydrophobic interlayer interlayer
Away from the number of plies of nitrogen-doped graphene prepared by further regulation and control.Control raw material inserts interlayer with the mass ratio and raw material of template
Method controlling arrangement mode of the ABPBI molecules in interlayer, and then control to generate the quality and performance of nitrogen-doped graphene.
The present invention is with document difference：First, be to stratiform mould material acid modification, to increase interlamellar spacing.
It is modified process with cationic surfactant again so as to which interlayer becomes hydrophobic, and interlamellar spacing becomes big, by adjusting
The alkyl chain of cationic surfactant is adjusting the interlamellar spacing of interlayer so as to be conducive to hydrophobic macromolecular material to be inserted into folder
It is in layer and regularly arranged.Cationic surfactant selects C4~C16Alkyl dimethyl benzyl ammonium bromide etc.；Secondly, using vacuum
The method of auxiliary allows macromolecule ABPBI molecules to enter in interlayer；Third, the hydrophobicity of the method for vacuum aided and interlayer can
So that rigid ABPBI molecules reach the regularly arranged of molecule when being dried in interlayer, a large amount of stackings, curling etc. are desirably prevented
It is unfavorable for that the situation for generating Graphene occurs.It is pyrolyzed under inert gas shielding after insertion ABPBI, obtains by removing template agent removing
The Graphene of two-dimentional N doping.
And the method for document is the modified preparation H of template montmorillonite employing acid+The montmorillonite of type, obtains the folder of hydrophilic
Layer；Small molecule aniline generates in acid condition water-soluble anilinechloride, in being conducive to the interlayer for insert hydrophilic；Again
Person, small molecule is also easy to enter in interlayer, it is not necessary to carry out the operation of complexity；There is polymerisation in aniline, obtain in interlayer
Polyaniline；And this method can not be used as hydrophobic high-molecular material A BPBI, because, first, acid type montmorillonite is hydrophilic
Property；Second, the interlamellar spacing of acid type montmorillonite is too little, macromolecule cannot be introduced into；ABPBI regular can not be arranged under 3rd free state
Row, under the conditions of vacuum aided and hydrophobic environment is conducive to that ABPBI's is regularly arranged.Only regularly arranged ABPBI is in argon gas
A series of thermal chemical reactions such as dehydrogenation-cyclisation-carbonization occur under protection during pyrolysis could form nitrogen-doped graphene structure.
The key technology of the present invention is the silicic acid anhydride of interlayer, the control of interlamellar spacing, the insertion of ABPBI molecules and regularly arranged
And the factor such as the proportioning of ABPBI and template.Hydrophobic treatment be hydrophobic polymer insertion basis, cation surface activating
The structure of agent can regulate and control the interlamellar spacing of interlayer.Template and ABPBI proportionings and the side of auxiliary ABPBI rigid macromolecule insertions
Formula, the regular degree that decide arrangement of the macromolecule in interlayer and the number of plies and performance that obtain Graphene.
By the interlamellar spacing for adjusting the alkyl chain of cationic surfactant to adjust interlayer, ABPBI is controlled with template
The methods such as mass percent, the injection mode of ABPBI solution and pyrolytic process are regulating and controlling the number of plies of the nitrogen-doped graphene of preparation.
The materials application in fuel cell, the Cathodic oxygen reduction catalyst of metal-air battery, electrolysis water oxygen separate out catalyst and
The fields such as carrier, ultracapacitor, sensor material.
ABPBI is with above phenolic resin, pollopas and melmac Polymer material difference：ABPBI
Benzimidazole ring belongs to the stiffening ring of armaticity in molecule, contains imidazoles nitrogen in molecule on imidazole ring, belongs to the aroma type of rich nitrogen
High molecular polymer.Therefore, if under suitable template action, the grapheme material of multilayer N doping can be obtained.If
The plane of the aromatic rings of control molecule is arranged according to a direction, and pyrolysis can obtain the graphene-structured of N doping.With polyphenyl
It is amine, poly-（O-phenylenediamine）, unlike polypyrrole Polymer material：ABPBI family macromolecules are soluble in DMAc, DMSO etc.
In organic solvent, easily it is inserted in hydrophobic interlayer, because it is soluble, it has when nitrogen-doped graphene nano material is prepared
There is good operability.However, polyaniline compound, polypyrrole Polymer material are insoluble, it is impossible to insert in the interlayer of template.
ABPBI macromolecular chains are made up of the rigid benzimidazole of armaticity, and containing the imidazole ring rich in nitrogen and end in molecule
Amino.ABPBI is that viscosity average molecular weigh prepared by solid phase method or liquid phase method is soluble in DMAc, DMF between 10,000～30,000,
DMSO, in 1-METHYLPYRROLIDONE equal solvent.Molecular weight is too big, and the solubility property of ABPBI is deteriorated；Too little its pyrolysis system of molecular weight
Standby Graphene performance is not good enough.
The method of the preparation of the Graphene of two-dimentional N doping is：Montmorillonite first carries out acidification, cleans drying, respectively
The cationic surfactant for adding different alkyl chains is modified, and prepares the montmorillonite of hydrophobic interlayer as template.One
Quantitative template is put in the container that can be vacuumized, and a certain amount of ABPBI dissolvings are formed in a solvent solution, waits to fill
After the min of container vacuum-pumping 30 of template, valve is closed, the solution of appropriate ABPBI is injected in container with syringe, treat molten
Immersion there is not after template, begins to warm up, vacuumizes, and solvent is steamed at leisure near dry, so repeated multiple times until ABPBI's is molten
Liquid is finished.Take out, dry at 60 ~ 120 DEG C in drying box.It is finely ground in mortar, porcelain boat bottom is laid in, it is put into electric tube furnace
It is interior, under argon gas protection, at 700～1100 DEG C, it is pyrolyzed 2 ~ 3h.Treat that furnace temperature is cooled to room temperature, take out, repeatedly washed with hydrofluoric acid
Wash to go removing template montmorillonite, suction filtration, deionized water to clean, drying obtains two-dimentional nitrogen-doped graphene.
In the present invention：The optional quaternary ammonium surfactants of cationic surfactant：Such as use C4~C16Alkyl dimethyl benzyl
Base ammonium bromide etc..The hydrophobicity that the length of its alkyl can not only control interlayer is strong and weak, and can adjust the interlamellar spacing of interlayer.
Alkyl carbon chain is longer, and the hydrophobicity of interlayer is stronger, interlamellar spacing is bigger, and vice versa.The interbedded distance of template is determined
The amount of ABPBI can be injected, and then determines the number of plies of prepared Graphene.In the case of ABPBI insertions sufficiently, interlamellar spacing
Wider, it is more that ABPBI is inserted, and the number of plies of the Graphene for obtaining is also more.Therefore, the modification of cationic surfactant is very
It is important.Another key technology of the present invention is fillings and arranging situation of the ABPBI in interlayer：Require that ABPBI is filled first
Full interlayer；Secondly, it is desirable to which ABPBI is regularly arranged in interlayer.Only in this way can just obtain complete two-dimentional nitrogen-doped graphene.
This requires that ABPBI solution is repeatedly sucked, and waits a moment and repeat after draining slowly repeatedly.
ABPBI is 2 with the mass ratio of template modified montmorillonoid:1～1:3；Hybrid mode is：Weigh a certain amount of template
Agent modified montmorillonoid 160～220 DEG C of heating 2h in high temperature furnace, to remove multilayer material interlayer in adsorb water, gas or impurity.
Room temperature to be cooled to, is transferred in the pressure vessel for being connected with vavuum pump, vacuumizes 30～40 min, with syringe into pressure vessel
A certain amount of ABPBI solution is injected, makes ABPBI solution soak template, continue to vacuumize, after no liquid in container, continued
Aforesaid operations run out up to ABPBI solution, drain.The template of suction ABPBI solution, take out in vacuum drying chamber
Interior 60～120 DEG C of ageings, drying is cooled to room temperature, finely ground, is put into porcelain boat, 700 ~ 1100 under argon gas protection in high temperature furnace
2～3h is pyrolyzed at DEG C, after furnace temperature cooling, sample is taken out, with hydrofluoric acid template is washed away, deionized water washes away acid, is dried,
Obtain the two-dimentional nitrogen-doped graphene product of black.
Pyrolysis temperature is critically important, and pyrolysis temperature range is 700～1100 DEG C.The too low ABPBI of temperature can not be pyrolyzed, and be produced
The electric conductivity of product is poor；Pyrolysis temperature is reached after optimum temperature, then to raise pyrolysis temperature its performance constant, so pyrolysis temperature is not
It is preferably too high.
The Graphene characterizing method of two-dimentional N doping is：Aperture, porosity, pore volume and specific surface area nitrogen adsorption instrument
（BET）, the Morphology analysis SEM of product（SEM）And projection electron microscope（TEM）, the Graphene number of plies
High power transmission electron microscope can be passed through（HRTEM）To characterize.The degree of graphitization of product, graphene-structured and the number of plies can be with
Use X-ray powder diffraction（XRD）, Raman spectrum to be characterizing.The element composition of product, valence state can use X-ray photoelectron energy
Spectrum（XPS）Characterized, used rotating disk electrode (r.d.e)（RDE）Carry out the catalytic oxidation-reduction reaction of test product（ORR）Performance, water power
Solution oxygen evolution reaction（EOR）, evolving hydrogen reaction（EHR）Cyclic voltammetric can be used with the capacitive property test of product（CV）, linear volt
Peace（LSV）, Tafel curve and charge-discharge performance to be testing.Product can use CV, LSV as the durability test of catalyst
And chronoa mperometric plot（i-t）.The catalytic performance of product finally needs to assemble metal-air battery, hydrogen-oxygen fuel cell, electrolysis
The electrolytic cell of water, ultracapacitor and sensor are testing its performance.
Specific embodiment
The preparation of [embodiment 1] ABPBI（Method one, solid phase method）：Take appropriate 3,4- diaminobenzoic acids（DABA）In
In mortar, it is transferred to after being fully ground equipped with electric stirring, inert gas shielding there-necked flask, leads to nitrogen 15min to arrange
Air to the greatest extent in flask.Nitrogen is protected, and under stirring, 225 DEG C of heating of oil bath keep 3h.Take out after cooling, finely ground, nitrogen protection
Under, heating in electric furnace is warmed up to 270-275 DEG C, keeps 3h.Be cooled to room temperature, by product take out, it is finely ground, that is, obtain ABPBI,
With the molecular weight of determination of ubbelohde viscometer ABPBI.
The preparation of [embodiment 2] ABPBI（Method two, liquid phase method）：Polyphosphoric acids (PPA) (50 g) is added to three
In mouth flask, under nitrogen protection, 160 DEG C are stirred 1 h to remove moisture and air.Addition 3,4- diaminobenzoic acids (6 g,
39.5 mmol) and the h of stirring reaction 5 ~ 8 at temperature is increased to into 200 DEG C, about 5 g P are dividedly in some parts in course of reaction2O5With
The water generated during absorbing reaction.With the increase in reaction time, polymerization system gradually becomes sticky.Reaction mixture is slowly
In being transferred to deionized water, reel off raw silk from cocoons, form fibrous black solid, take out drying, crush, in washing to remove reactant mixture
Polyphosphoric acids and unreacted raw material.Obtain ABPBI products.With the molecular weight of determination of ubbelohde viscometer ABPBI.
The sour modification of [embodiment 3] montmorillonite and cationic surfactant are modified.
The acid of montmorillonite is modified：Take 10 g montmorillonites（Na-MMT）In being put into 1000mL beakers, 600 mL 0.1 are added
The HCl of mol/L, under stirring, immersion 2 days, suction filtration is repeatedly washed with substantial amounts of deionized water, suction filtration, and 60 DEG C sour modifiedly dry
Montmorillonite（H-MMT）.Its ion exchange capacity is determined for 0.25 meq/g.
Cationic surfactant C16The modified montmorillonite of Alkyl dimethyl benzyl ammonium bromide（MMTC16B）, weigh 5 g H-
MMT（0.25 meq/g）, 2 h are dried at 120 ~ 220 DEG C, to remove the impurity such as its water for adsorbing, it is slowly added under agitation
0.5 g's uses C16Alkyl dimethyl benzyl ammonium bromide cationic surfactant is dissolved in 300 mL deionized water solutions,
4h is sufficiently stirred in 60 DEG C of water-baths so as to be uniformly dispersed, stand overnight, suction filtration, deionized water is cleaned to without bromide ion, 120
Dry at DEG C, grinding obtains using C16Alkyl dimethyl benzyl ammonium bromide surfactant（It is abbreviated as C16B）Modified MMT brief notes
For MMTC16B。
C can be carried out in aforementioned manners4~C15The modified illiteracy of Alkyl dimethyl benzyl ammonium bromide cationic surfactant
De- soil, is abbreviated as MMTCXB, wherein X is the carbon number of alkyl.
[embodiment 4] uses MMTC16BAs template, with ABPBI and template mass ratio as 1:As a example by 1：In 250 mL
Beaker in, add 1 g ABPBI（Viscosity average molecular weigh 1 ~ 30,000）With 20 mL DMAc, heating, stirring dissolve it, solution is taken out
Filter, it is standby to remove insoluble matter.In the bottle,suction of 250 mL of vavuum pump is connected with, 1 g MMT are addedC16BIt is laid in it
Bottom of bottle, after vacuumizing 30 min, closes valve, stops vacuumizing, and adds the DMAc solution of ABPBI with syringe so as to fully
Wetting template, heating continues to vacuumize to remove solvent, it is to be dried after, repeat more than operate, it is repeated multiple times until handle
The DMAc solution of ABPBI is all added, and after draining, is taken out, and in 60～120 DEG C of ageings, drying, treats cold taking-up, finely ground, is put into porcelain
Boat, in the high temperature furnace 800 DEG C under argon gas protection at be pyrolyzed 2～3h, cooling is taken out, is repeatedly washed with hydrofluoric acid, to remove removing template
Agent, deionized water is washed till neutrality, and in vacuum drying the g of black powder solid 0.66 is obtained.BET is tested and shown, its surface
Product is 542 m2 g-1, aperture is 15 ~ 20 nm, and SEM tests show that the product for obtaining is porous material, and TEM and HRTEM is analyzed
Show, product is multi-layer graphene structural material, Graphene is drawn a bow to the full back as 3 ~ 4 layer graphenes.XRD and Raman spectrum are tested and shown,
Product is 3 ~ 4 layers of graphene-structured；XPS analysis show that product nitrogen content is 6.7%, and nitrogen is pyridine type nitrogen and pyrroles's type
Nitrogen.Illustrate, product is the two-dimensional graphene of N doping.In its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, initial oxygen
Reduction potential is 0.98 V vs RHE, and electron transfer number is 3.98, and durability is good；Magnesium air cell performance is up to 112 mW/
cm2.For hydrogen-oxygen fuel cell, its peak power is 547 mW/cm2, oxygen precipitation take-off potential is in the sulfuric acid solution of 0.5 mol/L
1.54 Vvs RHE, limiting current density reaches 80 mA/cm2.Ultracapacitor specific capacitance is 451 F/g, capable of circulation
10000 times still holding capacitor value 97%.
[embodiment 5] as described in Example 4, other conditions are identical, and simply pyrolysis temperature is changed to 700 DEG C.The product for obtaining
Product are 0.70 g black powders, and test result shows that its product remains as the material of 3 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Material, only because its degree of graphitization is relatively low, its electronic conductivity is slightly worse, so its chemical property is slightly worse：It 0.1
In mol/L KOH solutions, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.81 V vs RHE, and electron transfer number is
3.55, durability is good；Magnesium air cell performance is up to 64 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 219 mW/
cm2, it is 1.64 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 40
mA/cm2.Ultracapacitor specific capacitance be 252 F/g, 10000 times capable of circulation still holding capacitor value 94%.
[embodiment 6] as described in Example 4, other conditions are identical, simply change pyrolysis temperature and are changed to 900 DEG C.Obtain
Product be 0.65 g black powders, test result shows that its product remains as 3 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Material, in its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.99 V vs RHE, electric
Son transfer number is 3.98, and durability is good；Magnesium air cell performance is up to 116 mW/cm2.For its peak power of hydrogen-oxygen fuel cell
For 549 mW/cm2, oxygen separates out take-off potential for 1.53 V vs RHE in the sulfuric acid solution of 0.5 mol/L, limiting current density
Reach 90 mA/cm2.Ultracapacitor specific capacitance be 428 F/g, 10000 times capable of circulation still holding capacitor value 97%.
[embodiment 7] as described in Example 4, other conditions are identical, and simply pyrolysis temperature is changed to 1100 DEG C.Obtain
Product is 0.60 g black powders, and test result shows that its product remains as the material of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Material, in its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential be 0.93 V vs RHE, electronics
Transfer number is 3.87, and durability is good；Magnesium air cell performance is up to 87 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is
327 mW/cm2, it is 1.59 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 be 189 F/g, 10000 times capable of circulation still holding capacitor value 97%.
[embodiment 8] as described in Example 4, other conditions are identical, simply change ABPBI and MMTC16BTemplate
Ratio is 1：2.The product for obtaining is 0.70 g black powders, and test result shows that its product remains as 2 ~ 4 layers of two-dimentional nitrogen and mixes
The material of miscellaneous graphene-structured, due to MMTC16BThe increase of amount so that ABPBI fillings are not abundant enough, the two-dimentional N doping for obtaining
Graphene sheet layer diminishes, and its electric conductivity is deteriorated, in its 0.1 mol/LKOH solution, catalytic oxidation-reduction performance, and oxygen starting is also
Former current potential is 0.90 V vs RHE, and electron transfer number is 3.64, and durability is good；Magnesium air cell performance is up to 81 mW/cm2。
For hydrogen-oxygen fuel cell, its peak power is 278 mW/cm2.Oxygen precipitation take-off potential is in the sulfuric acid solution of 0.5 mol/L
1.59 V vs RHE, limiting current density reaches 60 mA/cm2.Ultracapacitor specific capacitance is 346 F/g, capable of circulation
10000 times still holding capacitor value 94%.
[embodiment 9] as described in Example 4, other conditions are identical, simply change ABPBI and MMTC16BTemplate
Ratio is 1：3.The product for obtaining is 0.71 g black powders, and test result shows that its product remains as 2 ~ 4 layers of two-dimentional nitrogen and mixes
The material of miscellaneous graphene-structured, only because MMTC16BThe increase of amount so that ABPBI fillings are not abundant enough, the two-dimentional nitrogen for obtaining
Doped graphene lamella diminishes, and its electric conductivity is deteriorated.In its 0.1 mol/LKOH solution, catalytic oxidation-reduction performance, oxygen rises
Beginning reduction potential is 0.76 V vs RHE, and electron transfer number is 3.57, and durability is good；Magnesium air cell performance is up to 57 mW/
cm2.For hydrogen-oxygen fuel cell, its peak power is 187 mW/cm2, oxygen precipitation take-off potential is in the sulfuric acid solution of 0.5 mol/L
1.66 vs RHE, limiting current density reaches 40 mA/cm2.Ultracapacitor specific capacitance be 236 F/g, capable of circulation 10000
The 93% of secondary still holding capacitor value.
[embodiment 10] as described in Example 4, other conditions are identical, simply change ABPBI and MMTC16BTemplate
Ratio is 2：1.The product for obtaining is 0.67 g black powders, and test result shows, its product is except 2 ~ 4 layers of two-dimentional N doping
Outside the material of graphene-structured, the also material with carbon element of part N doping.This is due to the increase of ABPBI amounts so that ABPBI is removed
Outside filling interlayer space, also some residual, remaining ABPBI forms the porous carbon of N doping in template Surface coating
Material, its catalytic performance is deteriorated.In its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is
0.73 V vs RHE, electron transfer number is 3.55, and durability is good；Magnesium air cell performance is up to 64 mW/cm2.For hydrogen-oxygen
Its peak power of fuel cell is 179 mW/cm2, it is 1.67 vs that oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L
RHE, limiting current density reaches 40 mA/cm2.Ultracapacitor specific capacitance is 194 F/g, is still kept for 10000 times capable of circulation
The 90% of capacitance.
[embodiment 11] as described in Example 4, other conditions are identical, and simply template uses MMT insteadC6B.The product for obtaining
Product are 0.64 g black powders, and test result shows that its product remains as the material of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
With nitrogen-doped carbon material, only because the alkyl carbon chain of cationic surfactant is shorter so that MMTC6 BInterlamellar spacing reduces, and makes
The amount of the ABPBI that must be added is on the high side, there is part nitrogen-doped carbon material in product.In its 0.1 mol/LKOH solution, catalysis oxygen is also
Originality energy, oxygen initial reduction current potential is 0.79 V vs RHE, and electron transfer number is 3.86, and durability is good；Magnesium air cell
Performance is up to 56 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 148 mW/cm2, oxygen analysis in the sulfuric acid solution of 0.5 mol/L
It is 1.59 V vs RHE to go out take-off potential, and limiting current density reaches 40 mA/cm2.Ultracapacitor specific capacitance is 236 F/
G, 10000 times capable of circulation still holding capacitor value 95%.
[embodiment 12] as described in Example 4, other conditions are identical, simply MMTC8B.The product for obtaining is 0.66 g
Black powder, test result shows that its product is the material and part nitrogen-doped carbon of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure
Material, only because the alkyl carbon chain of cationic surfactant is shorter so that MMTC8BInterlamellar spacing reduces so that add ABPBI
Amount it is on the high side.In its 0.1 mol/LKOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.87 V vs RHE,
Electron transfer number is 3.86, and durability is good；Magnesium air cell performance is up to 75 mW/cm2.For its peak work(of hydrogen-oxygen fuel cell
Rate is 206 mW/cm2.It is 1.57 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 50 mA/cm2.Ultracapacitor specific capacitance be 243 F/g, 10000 times capable of circulation still holding capacitor value 95%.
[embodiment 13] as described in Example 4, other conditions are identical, simply MMTC14B.The product for obtaining is 0.70 g
Black powder, test result shows that its product remains as the material of 2 ~ 4 layers of two-dimentional nitrogen-doped graphene structure, its 0.1mol/
In L KOH solutions, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.96 V vs RHE, and electron transfer number is 3.96,
Durability is good；Magnesium air cell performance is up to 95 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 365 mW/cm2, 0.5
It is 1.54 V vs RHE that the sulfuric acid solution oxygen of mol/L separates out take-off potential, and limiting current density reaches 80 mA/cm2.Super electricity
Container specific capacitance be 341 F/g, 10000 times capable of circulation still holding capacitor value 97%.
[embodiment 14] as described in Example 4, other conditions are identical, simply without the method for vacuum aided, direct handle
MMTC16BIn being added to the solution of ABPBI, be uniformly dispersed under stirring, steam near dry, 60 ~ 120 DEG C in the vacuum drying chamber at do
It is dry, it is finely ground, be laid in porcelain boat bottom, under argon gas protection 900 DEG C in high temperature furnace, be pyrolyzed 2 ~ 3h, cooling, it is finely ground, use hydrofluoric acid
Repeatedly washing, removes template agent removing, and it is 0.70 g black powders to obtain product, and test result shows that its product remains as porous nitrogen
The material with carbon element of doping, in its 0.1 mol/L KOH solution, catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.79 V vs
RHE, electron transfer number is 3.54, and durability is good；Magnesium air cell performance is up to 45 mW/cm2.For hydrogen-oxygen fuel cell its
Peak power is 126 mW/cm2, it is 1.67 V vs RHE that the sulfuric acid solution oxygen of 0.5 mol/L separates out take-off potential, carrying current
Density reaches 20 mA/cm2.Ultracapacitor specific capacitance be 127 F/g, 10000 times capable of circulation still holding capacitor value 90%.
Claims (5)
1. a kind of method that two-dimentional nitrogen-doped graphene is prepared in the microreactor of vertical direction confinement, it is characterised in that：Hang down
Microreactor C of the Nogata to confinement4~C16In the interlayer of Alkyl dimethyl benzyl ammonium bromide modified montmorillonoid, its interlamellar spacing can
To be adjusted by the alkyl chain length of cationic surfactant, its interlamellar spacing determine to be filled as carbon source and nitrogen source
It is poly-（2,5- benzimidazoles）（ABPBI）How much, and then determine to obtain the number of plies of nitrogen-doped graphene after pyrolysis；Soluble
The method of the solution vacuum aided of ABPBI is filled in the interlayer of template, and the aromatic rings in ABPBI molecules is advised in interlayer
Then arrange, under inert gas shielding, be pyrolyzed, remove template with hydrofluoric acid wash, prepare the two-dimentional N doping of high nitrogen-containing
Graphene；ABPBI solution and the stratiform template of different interlamellar spacings, lower high temperature furnace is protected according to different quality than mixing, argon gas
2 ~ 3h of interior pyrolysis, the two-dimentional nitrogen-doped graphene obtained by going template with hydrofluoric acid；Described two-dimentional nitrogen-doped graphene, should
For the catalyst of catalytic oxidation-reduction reaction, used in metal-air battery, fuel cell；Can also be used for the precipitation of catalytic electrolysis water oxygen
The catalyst of reaction；Can be additionally used in the electrode material of ultracapacitor.
2. the microreactor of vertical direction confinement according to claim 1, it is characterised in that：Use C4~C16Alkyl dimethyl
The modified montmorillonite of Benzylphosphonium Bromide ammonium, its interlamellar spacing can be adjusted by the alkyl chain length of cationic surfactant, its
The interlamellar spacing of interlayer is changed into hydrophobic between 0.2～0.6nm, interlayer, it is easy to the insertion of hydrophobic polymer ABPBI molecules.
3. ABPBI according to claim 1, it is characterised in that：Macromolecular chain is by the rigid benzimidazole group of armaticity
Into, and containing the imidazole ring rich in nitrogen and Amino End Group in molecule；Polymer viscosity average molecular weigh, can be with molten between 1～30,000
Solution is in dimethyl acetamide（DMAc）, dimethylformamide（DMF）, dimethyl sulfoxide (DMSO)（DMSO）Have with 1-METHYLPYRROLIDONE etc.
Machine solvent.
4. ABPBI according to claim 1 and the mass ratio of template modified montmorillonoid are 2:1～1:3；Concrete operations side
Formula is：A certain amount of microreactor modified montmorillonoid 160～220 DEG C of heating 2h in high temperature furnace are weighed, to remove multilayer material
Adsorb water, gas or impurity, room temperature to be cooled in interlayer, be transferred in the pressure vessel for being connected with vavuum pump, vacuumize 30～40
Min, with syringe a certain amount of ABPBI solution is injected into pressure vessel, makes ABPBI solution soak modified montmorillonoid, is continued
Vacuumize, force ABPBI molecules to add in reactor interlayer, after no liquid in container, continue aforesaid operations until ABPBI is molten
Liquid runs out, and drains；Suction ABPBI solution modified montmorillonoid, take out in vacuum drying chamber 60～120 DEG C it is old
Change, drying, the sample for being cooled to room temperature takes out, finely ground, is put into porcelain boat, under argon gas protection in high temperature furnace 2～3h is pyrolyzed, treat
After furnace temperature cooling, sample is taken out, with hydrofluoric acid modified montmorillonoid is washed away, deionized water washes away acid, be dried, that is, obtain black
Two-dimentional nitrogen-doped graphene product.
5. pyrolysis temperature according to claim 1 is 700 ~ 1100 DEG C.
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